research papers on zeolite

A Review on Zeolite: Application, Synthesis and Effect of Synthesis Parameters on Product Properties

• Published: 10 September 2022
• Volume 5 , pages 1889–1906, ( 2022 )

Cite this article

• Nurudeen Salahudeen   ORCID: orcid.org/0000-0002-7537-8011 1  

1904 Accesses

10 Citations

Explore all metrics

Zeolite synthesis involves artificial formation of crystals under reaction conditions similar to that of formation of natural zeolites. Synthesis methods are categorized as either hydrothermal, solvothermal or ionothermal. Irrespective of the method employed, zeolite can be synthesized via either of the three synthesis mechanisms, which are: liquid phase transformation mechanism; two-phase transformation mechanism and solid phase transformation mechanism. Synthesis parameters such as temperature, time, precursor pH and presence or absence of template and ultrasonic treatment are key in determining success of synthesis and quality of product. Most zeolite frameworks are favourably synthesizable at certain alkaline pH range. The presence of template and ultrasonic treatment enhance progress of zeolite synthesis in a particular framework and morphological direction resulting into a particular stable phase with minimum or no competing impurity phases. Ultrasonic treatment improves product crystallinity, BET surface area and reduces both crystal size and crystallization time in zeolite synthesis.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save.

• Get 10 units per month
• Download Article/Chapter or eBook
• 1 Unit = 1 Article or 1 Chapter
• Cancel anytime

Price includes VAT (Russian Federation)

Instant access to the full article PDF.

Rent this article via DeepDyve

Institutional subscriptions

Similar content being viewed by others

Mel zeolites: synthesis, properties, and catalytic applications.

Theoretical design for zeolite synthesis

Synthesis methods and recent advances in hierarchical zeolites: a brief review

Davis ME (2002) Ordered porous materials for emerging applications. Nature 417:813–821

Article   CAS   Google Scholar  

Xu R, Pang W, Yu J, Huo Q, Chen J (2007) Chemistry of zeolites and related porous materials: synthesis and structure. Wiley, Singapore

Book   Google Scholar  

Kianfar E (2018) Synthesis and characterization of AlPO 4 /ZSM-5 catalyst for methanol conversion to dimethylether. Russ J Appl Chem 91:1710–1720

Article   Google Scholar  

Baerlocher C, Meier WH, Olson DH (2007) Atlas of zeolite framework types, 6th edn. Elsevier, Amsterdam

Google Scholar  

Iyoki K, Itabashi K, Okubo T (2014) Progress in seed-assisted synthesis of zeolites without using organic structure-directing agents. Microporous Mesoporous Mater 189:22–30

Vermeiren W, Gilson JP (2009) Impact of zeolites on the petroleum and petrochemical industry. Top Catal 52:1131–1161

Treacy MM J, Higgins JB (2001) Collection of simulated XRD powders for zeolites. Published on behalf of the Synthesis Commission of the International Zeolite Association. Elsevier, Amsterdam

Hayakawa E, Himeno S (2021) Preparation of Al-containing ZSM-58 zeolite membranes using rapid thermal processing for CO 2 /CH 4 mixture separation. Membranes 11:623

Pires J, de Carvalho MB, Ribeiro FR, Derouane EG (1993) Carbon dioxide in Y and ZSM-20 zeolites: adsorption and infrared studies. J Mol Catal 85(3):295–303

Warrender SJ, Wright PA, Zhou W, Lightfoot P, Camblor MA, Shin CH, Kim DJ, Hong SB (2005) Structure of the novel large pore gallosilicate TNU-7. Stud Surf Sci Catal 158(A):89–96

Zhong S, Song S, Wang B, Bu N, Ding X, Zhou R, Jin W (2018) Fast preparation of ERI-structure AlPO-17 and SAPO-17 in the presences of isomorphous and heterogeneous seeds. Microporous Mesoporous Mater 263:11–20

Kubu M, Millini R, Žilková N (2018) 10-ring zeolites: synthesis, characterization and catalytic applications. Catal Today. https://doi.org/10.1016/j.cattod.2018.06.011 ( In Press )

Suharbiansah RSR, Pyra K, Liebau M, Poppitz D, Gora-Marek K, Glaser R, Jabłonska M (2021) Micro-/mesoporous copper-containing zeolite Y applied in NH3-SCR DeNOx. Microporous Mesoporous Mater 334:111793

Li Q, Cong W, Li K, Xu C, Bing L, Han FWD, Wang G (2021) Transformation synthesis of SSZ-13 zeolite from ZSM-35 zeolite. J Solid State Chem 304:122635

Akolekar DB, Kaliaguine S (1994) MAPO-43 molecular sieve: synthesis, characterization and thermal stability. Microporous Mater 2(2):137–144

Güngor D, Ozen S (2021) Development and characterization of clinoptilolite-, mordenite-, and analcime-based geopolymers: a comparative study. Case Stud Constr Mater 15:e00576

Umamaheswari V, Böhlmann W, Pöppl A, Vinu A, Hartmann M (2006) Spectroscopic characterization of iron-containing MCM-58. Microporous Mesoporous Mater 89(1):47–57

Novembre D, Gimeno D, Vecchio AD (2021) Synthesis and characterization of Na-P1 (GIS) zeolite using a kaolinitic rock. Sci Rep 11:4872

Rhodes CJ (2010) Properties and applications of zeolites. Sci Prog 93(3):223–284

Hussain T, Hussain AI, Chatha SAS, Ali A, Rizwan M, Ali S, Ahamd P, Wijaya L, Alyemeni MN (2021) Synthesis and characterization of Na-Zeolites from textile waste ash and its application for removal of lead (Pb) from wastewater. Int J Environ Res Public Health 18:3373

Bouchiba N, Toumi N, Bengueddach A (2021) Preparation of a new micro-mesoporous omega zeolite by hydrothermal route: effect of crystallization time. Silicon First Online. https://doi.org/10.1007/s12633-021-01254-6

Thoma SG, Nenoff TM (2000) A novel synthesis of zeolite W using organometallic precursors. Microporous Mesoporous Mater 34:301–306

Kim HS, Kang SK, Zhang H, Tikue ET, Lee JH, Lee PS (2021) Al-ZSM-5 nanocrystal catalysts grown from silicalite-1 seeds for methane conversion. Energies 14:485

Thangaraj A, Kumar R, Ratnasamy P (1991) NMR study of the location and configuration of pyrrolidine in ZSM-5, -23, -48, and -51 zeolites. Zeolites 11(6):573–576

Zones SI, Hwang SJ, Davis ME (2001) Studies of the synthesis of SSZ-25 zeolite in a mixed-template system. Chem A Eur J 7(9):1990–2001

Kim YM, Lee SJ, Kim IJ (2007) Synthesis and characterization of TMA-A zeolite nanocrystals. Solid State Phenom 124–126:563–566

Bu X, Feng P, Gier TE, Stucky GD (1998) Two ethylenediamine-templated-type structures in zinc arsenate and cobalt phosphate systems. J Solid State Chem 136:210–215

Cheung O, Bacsik Z, Fil N, Krokidas P, Wardecki D, Hedin N (2020) Selective adsorption of CO 2 on zeolites NaK-ZK-4 with Si/Al of 1.8−2.8. ACS Omega 5:25371–25380

Bu X, Feng P, Stucky GD (1997) Large-cage zeolite structures with multidimensional 12-ring channels. Science 278:2080–2084

Venkatathri N (2002) Synthesis and characterization of AlPO-n molecular sieves from hexamethyleneimine template. Indian J Chem Sect A 41(11):2223

Corma A, Díaz-Cabañas MJ, Rey F, Nicolopoulus S, Boulahya K (2004) ITQ-15: the first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications. Chem Commun 10(12):1356

Li R, Wang S, Li D, Qin Y, Yu J (2017) Synthesis and biological evaluation of VPI-7 zeolite. Chem J Chin Univ 38(11):1935–1940

CAS   Google Scholar  

Chen S, Sorge LP, Seo DK (2017) Template-free synthesis and structural evolution of discrete hydroxycancrinite zeolite nanorods from high-concentration hydrogels. Nanoscale 9(47):18804–18811

McKeen CJ, Davis EM (2009) Conductivity of mono- and divalent cations in the microporous zincosilicate VPI-9. J Phys Chem C 113(22):9870–9877

Li Y, Li L, Yu J (2017) Applications of zeolites in sustainable chemistry. Chemistry 3(6):928–949

Lee S, Shantz FD (2005) Zeolite growth in nonionic microemulsions: synthesis of hierarchically structured zeolite particles. Chem Mater 17:409–417

Zhang Y, Jin C (2011) Rapid crystallization and morphological adjustment of zeolite ZSM-5 in nonionic emulsions. J Solid State Chem 184:1–6

Inui T, Numba S, Tatsumi T (1991) New families of M(III)X(V)O 4 -type microporous crystals and inclusion compounds. In: Chemistry of microporous crystals. Studies in surface science and catalysis, vol 60, pp 63–72

Liu QL, Cheung NCO, Garcia-Bennett AE, Hedin N (2011) Aluminophosphates for CO 2 separation. Chemsuschem 4:91–97

Wu T, Wang B, Lu ZH, Zhou RF, Chen XS (2014) Alumina-supported AlPO-18 membranes for CO 2 /CH 4 separation. J Membr Sci 471:338–346

Wang B, Hu N, Wang HM, Zheng YH, Zhou RF (2015) Improved AlPO-18 membranes for light gas separation. J Mater Chem A 3:12205–12212

Lohse U, Jancke K, Löffler E, Schaller T (1994) The influence of HF on the incorporation of silicon into the erionite-like AlPO4-17 molecular sieve. Cryst Res Technol 29:237–245

Lohse U, Loffler E, Kosche K, Janchen J, Parlitz B (1993) Isomorphous substitution of silicon in the erionite-like structure AlPO4-17 and acidity of SAPO-17. Zeolites 13:549–556

Lok BM, Messina CA, Patton RL, Gajek RT, Cannan TR, Flanigen EM (1984) Silicoaluminophosphate molecular-sieves—another new class of microporous crystalline inorganic solids. J Am Chem Soc 106:6092–6093

Ghorbani-Choghamarani A, Taherinia Z, Mohammadi M (2021) Facile synthesis of Fe 3 O 4 @GlcA@Ni-MOF composites as environmentally green catalyst in organic reactions. Environ Technol Innov 24:102050

Olmos A, Louis B, Pale P (2012) Scandium(III)-zeolites as new heterogeneous catalysts for Imino-Diels–Alder reactions. Chem A Eur J 18(16):4894–4901

Bernardon C, Louis B, Beneteau V, Pale P (2013) Diels–Alder reaction between isoprene and methyl acrylate over different zeolites: influence of pore topology and acidity. ChemPlusChem 78(9):1134–1141

Losch P, Kolb JF, Astafan A, Daou TJ, Pinard L, Pale P, Louis B (2016) Eco-compatible zeolite-catalysed continuous halogenation of aromatics. Green Chem 18:4714–4724

Liu J, Chen L, Cui H, Zhang J, Zhang L, Su CY (2014) Applications of metal-organic frameworks in heterogeneous supramolecular catalysis. Chem Soc Rev 43:6011–6061

Karmakar A, Desai AV, Ghosh SK (2016) Ionic metal-organic frameworks (iMOFs): design principles and applications. Coord Chem Rev 307:313–314

Wang C, Yang M, Li M, Xu S, Yang Y, Tian P, Liu Z (2016) A reconstruction strategy to synthesize mesoporous SAPO molecular sieve single crystals with high MTO catalytic activity. Chem Commun 52:6463–6466

Lopez RM, Barrios Y, Perez DL, Soto CYC, Sierra C (2022) Metal-Organic Framework (MOFs) tethered to cotton fibers display antimicrobial activity against relevant nosocomial bacteria. Inorg Chim Acta 537:120955

Butova VV, Soldatov MA, Guda A, Lomachenko KA, Lamberti C (2016) Metal-organic frameworks: structure properties, methods of synthesis and characterization. Russ Chem Rev 85(3):280–307

Martinez LMT, Ivanova S, Louis B, Odriozola AJ (2018) Zeolites and metal-organic frameworks. Amsterdam University Press, Amsterdam, pp 25–52

Trigueiro FE, Monteiro DFJ, Zotin EFS (2002) Thermal stability of Y zeolites containing different rare earth cations. J Alloy Compd 344:337–341

Mravec D, Hudec J, Janotka H (2005) Some possibilities of catalytic and noncatalytic utilization of zeolites. Chem Paper 59(1):62–69

Zhao Y, Liu Z, Li W, Zhao Y, Pan H, Liu Y, Li M, Kong L, He M (2013) Synthesis, characterization, and catalytic performance of high-silica Y zeolites with different crystallite size. Microporous Mesoporous Materials 167:102–108

Sani YM, Daud WMAW, Abdul-Aziz AR (2014) Activity of solid acid catalysts for biodiesel production: a critical review. Appl Catal A 470:140–161

Park H, Bang J, Han WS, Bera KR, Kim K, Ryoo R (2021) Synthesis of zeolite-templated carbons using oxygen-containing organic solvents. Microporous Mesoporous Mater 318:111038

Ronchi L, Ryzhikov A, Nouali H, Daou TJ, Albrecht S, Patarin J (2018) Extra large pore opening CFI and DON-type zeosils for mechanical energy storage. Microporous Mesoporous Mater 255:211–219

Burton A, Elomari S, Chen CY, Medrud RC, Chan IY, Bull LM, Kibby C, Harris TV, Zones SI, Vittoratos ES (2003) SSZ-53 and SSZ-59: two novel extra-large pore zeolites. Chem A Eur J 9:5737–5748

Kianfar E (2019) Comparison and assessment of zeolite catalysts performance dimethyl ether and light olefins production through methanol: a review. Rev Inorg Chem. https://doi.org/10.1515/revic-2019-0001

Mei C, Wen P, Liu Z, Liu H, Wang Y, Yang W, Xie Z, Hua W, Gao Z (2008) Selective production of propylene from methanol: mesoporosity development in high silica HZSM-5. J Catal 258:243–249

Li Z, Martinez-Triguero J, Yu J, Corma A (2015) Conversion of methanol to olefins: stabilization of nanosized SAPO-34 by hydrothermal treatment. J Catal 329:379–388

Yaripour F, Shariatinia Z, Sahebdelfar S, Irandoukht A (2015) Conventional hydrothermal synthesis of nanostructured H-ZSM-5 catalysts using various templates for light olefin production from methanol. J Nat Gas Sci Eng 22:260–269

Hassanpour S, Yaripour F, Taghizadeh M (2010) Performance of modified H-ZSM-5 zeolite for dehydration of methanol to dimethyl ether. Fuel Process Technol 91:1212–1221

Abu-Dahrieh J, Rooney D, Goguet A, Saih Y (2012) Activity and deactivation studies for direct dimethyl ether synthesis using CuO–ZnO–Al 2 O 3 with NH4ZSM-5, HZSM-5 or γ-Al2O3. Chem Eng J 203:201–211

Bleken FL, Chavan S, Olsbye U, Boltz M, Ocampo F, Louis B (2012) Conversion of methanol into light olefins over ZSM-5 zeolite: strategy to enhance propene selectivity. Appl Catal A Gen 447–448:178–185

Hosseini S, Taghizadeh M, Eliassi A (2012) Optimization of hydrothermal synthesis of H-ZSM-5 zeolite for dehydration of methanol to dimethyl ether using full factorial design. J Nat Gas Chem 21:344–351

Rownaghi AA, Rezaei F, Stante M, Hedlund J (2012) Selective dehydration of methanol to dimethyl ether on ZSM-5 nanocrystals. Appl Catal B Environ 119–120:56–61

Sabour B, Peyrovi MH, Hamoule T, Rashidzadeh M (2014) Catalytic dehydration of methanol to dimethyl ether (DME) over Al-HMS catalysts. J Ind Eng Chem 20:222–227

Jiao YL, Jiang CH, Yang ZM, Zhang JS (2012) Controllable synthesis of ZSM-5 coatings on SiC foam support for MTP application. Microporous Mesoporous Mater 162:152–158

Lefevere J, Mullens S, Meynen V, Van-Noyen J (2014) Structured catalysts for methanol-to-olefins conversion: a review. Chem Pap 68:1143–1153

Lee YJ, Kim YW, Viswanadham N, Jun KW, Bae JW (2010) Novel aluminophosphate (AlPO) bound ZSM-5 extrudates with improved catalytic properties for methanol to propylene (MTP) reaction. Appl Catal A Gen 374:18–25

Qi L, Li J, Wang L, Wang C, Xu L, Liu Z (2012) Comparative investigation of the deactivation behaviors over HZSM-5 and HSAPO-34 catalysts during low temperature methanol conversion. Catal Sci Technol 7:2022–2031

Dai W, Wang C, Dyballa M, Wu G, Guan N, Li L, Xie Z, Hunger M (2015) Understanding the early stages of the methanol-to-olefin conversion on H-SAPO-34. ACS Catal 5:317–326

Tian P, Wei Y, Ye M, Liu Z (2015) Methanol to olefins (MTO): from fundamentals to commercialization. ACS Catal 5:1922–1938

Chowdhury AD, Houben K, Whiting GT, Mokhtar M, Asiri AM, Al-Thabaiti SA, Basahel SN, Baldus M, Weckhuysen BM (2016) Initial carbonecarbon bond formation during the early stages of the methanol-to-olefin process proven by zeolite-trapped acetate and methyl acetate. Angew Chem Int Ed 55:15840–15845

Wang J, Yang M, Shang W, Su X, Hao Q, Chen H, Ma X (2017) Synthesis, characterization, and catalytic application of hierarchical SAPO-34 zeolite with three-dimensionally ordered mesoporous imprinted structure. Microporous Mesoporous Mater 252:10–16

Yuan X, Li H, Ye M, Liu Z (2017) Comparative study of MTO kinetics over SAPO-34 catalyst in fixed and fluidized bed reactors. Chem Eng J 329:35–44

Chen D, Moljord K, Fuglerud T, Holmen A (1999) The effect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction. Microporous Mesoporous Mater 29:191–203

Sun Q, Wang N, Xi D, Yang M, Yu J (2014) Organosilane surfactant-directed synthesis of hierarchical porous SAPO-34 catalysts with excellent MTO performance. Chem Commun 50:6502–6505

Sun Q, Wang N, Xi D, Yang M, Yu J (2015) Synthesis of tri-level hierarchical SAPO-34 zeolite with intracrystalline micro-meso-macroporosity showing superior MTO performance. J Mater Chem A 3:19783–19789

Chen X, Vicente A, Qin Z, Ruaux V, Gilson JP, Valtchev V (2016) The preparation of hierarchical SAPO-34 crystals via post-synthesis fluoride etching. Chem Commun 52:3512–3515

Sun MH, Huang SZ, Chen LH, Li Y, Yang XY, Yuan ZY, Su BL (2016) Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine. Chem Soc Rev 45:3479–3563

Varzaneh AZ, Towfighi J, Sahebdelfar S (2016) Carbon nanotube templated synthesis of metal containing hierarchical SAPO-34 catalysts: impact of the preparation method and metal avidities in the MTO reaction. Microporous Mesoporous Mater 236:1–12

Wang C, Yang M, Zhang W, Su X, Xu S, Tian P, Liu Z (2016) Organophosphorous surfactant-assistant synthesis of SAPO-34 molecular sieve with special morphology and improved MTO performance. RSC Adv 6:47864–47872

He Y, Tang S, Yin S, Li S (2021) Research progress on green synthesis of various high-purity zeolites from natural material-kaolin. J Clean Prod 306:127248

McCabe LW, Smith CJ, Harriott P (1993) Unit operations of chemical engineering, 5th edn. McGraw-Hill Inc, Singapore

Pei Y, Zhong Y, Xie Q, Chen N (2022) Two-step hydrothermal synthesis and conversion mechanism of zeolite X from stellerite zeolite. RSC Adv 12:3313

Santos BM, Vianna CK, Pastore OH, Andrade MCH, Mascarenhas JSA (2020) Studies on the synthesis of ZSM-5 by interzeolite transformation from zeolite Y without using organic structure directing agents. Microporous Mesoporous Mater 306:110413

Hu Z, Zhao B, Zhang S, Tan Z, Liu X, Cao J (2019) Rapid and high efficient synthesis of zeolite W by gel-like-solid phase method. Microporous Mesoporous Mater 281:75–83

Bok OT, Andriako PE, Knyazeva EE, Ivanova II (2019) Influence of synthesis conditions on the crystallization mechanism and properties of BEA zeolite. Pet Chem 59(3):354–361

Foroughi M, Salem A, Salem S (2021) Characterization of phase transformation from low grade kaolin to zeolite LTA in fusion technique: focus on quartz melting and crystallization in presence of NaAlO 2 . Mater Chem Phys 258:123892

Mei J, Duan A, Wang X (2021) A brief review on solvent-free synthesis of zeolites. Materials 14:788

Naik SP, Chiang AS, Thompson R (2003) Synthesis of zeolitic mesoporous materials by dry gel conversion under controlled humidity. J Phys Chem 107:7006–7014

Nishide T, Nakajima H, Kiyozumi Y, Mizukami F (2022) Effect of alkali metal ions on synthesis of zeolites and layered compounds by solid-state transformation. Stud Surf Sci Catal 142:239–246

Matsukata M, Ogura M, Osaki T, Rao PRHP, Nomura M, Kikuchi E (1999) Conversion of dry gel to microporous crystals in gas phase. Top Catal 9:77–92

Ji W, Feng N, Zhao PZ, Lan L, Huang H, Li K, Sun Y, Li Y, Ma Y (2020) Synthesis of single-phase zeolite A by coal gasification fine slag from Ningdong and its application as a high-efficiency adsorbent for Cu 2+ and Pb 2+ in simulated waste water. ChemEngineering 4:65

Nishide T, Nakajima H, Kiyozumi Y, Mizukami F (2002) Effect of alkali metal ions on synthesis of zeolites and layered compounds by solid-state transformation. Stud Surf Sci Catal 142:239–246

Tsai TR, Du JK, Cheng YT, Ho HG, Wu HP, Liu BS, Tsai CT (2013) Solid-state synthesis of mesoporous MFI zeolite from self-bonded silica pellets. Catal Today 204:30–37

Wanga Y, Song J, Baxter CN, Kuo TG, Wang S (2017) Synthesis of hierarchical ZSM-5 zeolites by solid-state crystallization and their catalytic properties. J Catal 349:53–65

Villa RW, Cuevas DJ, Ramirez S, Leguey S (2001) Zeolite formation during the alkaline reaction of bentonite. Eur J Mineral 13:635–644

Lee SR, Han YS, Choy JH (2002) 2D–3D transformation of layered aluminosilicate upon base treatment. Solid State Ionics 151:343–346

Mezni M, Hamzaoui A, Hamdi N, Srasra E (2011) Synthesis of zeolites from the low-grade Tunisian natural illite by two different methods. Appl Clay Sci 52(3):209–218

Jiang J, Feng L, Gu X, Qian Y, Gu Y, Duanmu C (2012) Synthesis of zeolite A from palygorskite via acid activation. Appl Clay Sci 55:108–113

Jiang J, Gu X, Feng L, Duanmu C, Jin Y, Hu T, Wu J (2012) Controllable synthesis of sodalite submicron crystals and microspheres from palygorskite clay using a twostep approach. Powder Technol 217:298–303

Aldahri T, Behin J, Kazemian H, Rohani S (2016) Synthesis of zeolite Na-P from coal fly ash by thermo-sonochemical treatment. Fuel 182:494–501

Belviso C, Cavalcante F, Niceforo G, Sodalite AL (2017) Faujasite and A-type zeolite from 2:1dioctahedral and 2:1:1 trioctahedral clay minerals. A singular review of synthesis methods through laboratory trials at a low incubation temperature. Powder Technol 320:483–497

Fukasawa T, Karisma AD, Shibata D, Fukui HAN, K, (2017) Synthesis of zeolite from coal fly ash by microwave hydrothermal treatment with pulverization process. Adv Powder Technol 28:798–804

Lee YR, Soe JT, Zhang S, Ahn JW, Park MB, Ahn WS (2017) Synthesis of nanoporous materials via recycling coal fly ash and other solid wastes: a mini review. Chem Eng J 317:821–843

Liu Y, Yan C, Zhang Z, Li L, Wang H, Pu S (2017) One-step fabrication of novel porous and permeable self-supporting zeolite block from fly ash. Mater Lett 196:328–331

Xinmei L, Zifeng Y, Huaiping W, Yantuo L (2003) In-situ synthesis of NaY zeolite with coal based kaolin. J Nat Gas Chem 12(1):63–70

Gandhi D, Bandyopadhyay R, Soni B (2021) Zeolite Y from kaolin clay of Kachchh, India: synthesis, characterization and catalytic application. J Indian Chem Soc 98(12):100246

Cejka J, Corma A, Zones S (2010) Zeolites and catalysis: synthesis, reactions and applications. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Rai P, Kwak WK, Yu YT (2013) Solvothermal synthesis of ZnO nanostructures and their morphology-dependent gas-sensing properties. Appl Mater Interfaces 5:3026–3032

Yu SH (2001) Hydrothermal/solvothermal processing of advanced ceramic materials. J Ceram Soc Jpn 109(5):S65–S75

Lia J, Wu Q, Wu J (2015) Synthesis of nanoparticles via solvothermal and hydrothermal methods. In: Aliofkhazraei M (ed) Handbook of nanoparticles. Springer, Switzerland

Sue K, Suzuki M, Arai K, Ohashi T, Ura H, Matsui K, Hakuta Y, Hayashi H, Watanabe M, Hiaki T (2006) Size-controlled synthesis of metal oxidenanoparticles with a flow-through supercritical water method. Green Chem 8:634–638

Niederberger M, Garnweitner G, Ba J, Polleux J, Pinna N (2007) Nonaqueous synthesis, assembly and formation mechanisms of metal oxide nanocrystals. Int J Nanotechnol 4(3):263–281

Hayashi H, Hakuta Y (2010) Hydrothermal synthesis of metal oxide nanoparticles in supercritical water. Materials 3(7):3794–3817

Luo HM, Baker GA, Dai S (2008) Isothermogravimetric determination of the enthalpies of vaporization of 1-alkyl-3-methylimidazolium ionic liquids. J Phys Chem B 112:10077–10081

Morris RE, Weigel SJ (1997) The synthesis of molecular sieves from non-aqueous solvents. Chem Soc Rev 26:309–317

Sindt M, Mieloszynski JL, Harmand J (2011) Ionic liquids from (Meth) acrylic compounds. In: Ionic liquids-classes and properties. InTech, Croatia

Wu Q, Hong X, Zhu L, Meng X, Han S, Zhang J, Liu X, Jin C, Xiao SF (2019) Generalized ionothermal synthesis of silica-based zeolites. Microporous Mesoporous Mater 286:163–168

Pan T, Wu Z, Yip ACK (2019) Advances in the green synthesis of microporous and hierarchical zeolites: a short review. Catalysts 9:274

Morris RE (2009) Ionothermal synthesis—ionic liquids as functional solvents in the preparation of crystalline materials. Chem Commun 21:2990–2998

Dupont H, Fouche C, Dourges MA, Schmitt V, Heroguez V (2020) Polymerization of cellulose nanocrystals-based Pickering HIPE towards green porous materials. Carbohydr Polym 243:116411

Zhu YF, Wang WB, Yu H, Wang AQ (2020) Preparation of porous adsorbent via Pickering emulsion template for water treatment: a review. J Environ Sci 88:217–236

Zhang Y, Shen Y, Jin C, Cao Y, Gao W, Cui L (2010) Synthesis of zeolite NaY in anionic, cationic and nonionic emulsions. Mater Res Bull 45:651–653

Gossard A, Fabrègue N, David T, Grandjean A (2021) Effects of the zeolite concentration on the microstructure of high internal phase emulsions stabilized by surfactant-coated zeolite particles. Colloids Surf A Physicochem Eng Asp 625:126853

Cheng J, Pei S, Yue B, Qian L, He C, Zhou Y, He H (2008) Synthesis and characterization of hollow zeolite microspheres with a mesoporous shell by O/W/O emulsion and vapor-phase transport method. Microporous Mesoporous Mater 115:383–388

Naskar MK, Das A, Kundu D, Chatterjee M (2011) Emulsion-based synthesis of NaA zeolite nanocrystals and its integration towards NaA membranes. Bull Mater Sci 34(4):651–659

Destree C, Nagy JB (2006) Mechanism of formation of inorganic and organic nanoparticles from microemulsions. Adv Colloid Interface Sci 123–126:353–367

Axnanda S, Shantz DF (2005) Cationic microemulsion-mediated synthesis of silicalite-1. Microporous Mesoporous Mater 84(1–3):236–246

Carr CS, Shantz DF (2005) Non-ionic-microemulsion mediated growth of zeolite A. Microporous Mesoporous Mater 85(3):284–292

Yates MZ, Ott KC, Birnbaum ER, McCleskey TM (2002) Hydrothermal synthesis of molecular sieve fibers: using microemulsions to control crystal morphology. Angew Chem Int Ed 41(3):476–478

Belviso C, Abdolrahimi M, Peddis D, Gagliano E, Sgroi M, Lettino A, Roccaro P, Vagliasindi AGF, Falciglia PP, Bella DG, Giustra GM, Cavalcante F (2021) Synthesis of zeolite from volcanic ash: characterization and application for cesium removal. Microporous Mesoporous Mater 319:111045

Probst J, Outram GJ, Couperthwaite JS, Millar JG, Kaparaju P (2021) Sustainable ammonium recovery from wastewater: Improved synthesis and performance of zeolite N made from kaolin. Microporous Mesoporous Mater 316:110918

Stafin G, Grzebielucka CE, Antunes MRS, Borges FPC, Andrade CVA, Alves AS, Souza FCE (2021) Synthesis of zeolites from residual diatomite using a microwave-assisted hydrothermal method. Waste Manag 126:853–860

Tran-Nguyen LP, Ly K-P, Thanh VHL, Angkawijaya EA, Santoso PS, Tran PN, Tsai M-L, Ju Y (2021) Facile synthesis of zeolite NaX using rice husk ash without pretreatment. J Taiwan Inst Chem Eng. https://doi.org/10.1016/j.jtice.2021.05.009 ( In Press )

Sang S, Chang F, Liu Z, He C, He Y, Xu L (2004) Difference of ZSM-5 zeolites synthesized with various templates. Catal Today 93–95:729–734

Bolshakov A, Romero-Hidalgo DE, van Hoof AJF, Kosinov N, Hensen EJM (2019) Mordenite nanorods prepared by an inexpensive pyrrolidine-based mesoporogen for alkane hydroisomerization. ChemCatChem 19:2803–2811

Chen H, Zhang YJ, He PY, Zhang Y (2019) Effective and eco-friendly seed-assisted synthesis of nanostructurally monolithic mordenite. Ferroelectrics 547:44–50

Abdelrahman EA, Hegazey RM, Alharbi A (2020) Facile synthesis of mordenite nanoparticles for efficient removal of Pb(II) ions from aqueous media. J Inorg Organomet Polym Mater 30:1369–1383

Gu Y, Wang X, Qin Z, Mintova S, Liu X (2020) Intra-crystalline mesoporous ZSM-5 zeolite by grinding synthesis method. Microporous Mesoporous Mater. https://doi.org/10.1016/j.micromeso.2020.110437 ( In Press )

Zubowa HL, Kosslick H, Müller D, Richter M, Wilde L, Fricke R (2008) Microporous Mesoporous Materials 19:542–548

Zeng X, Hu X, Song H, Xia G, Shen ZY, Yu R, Moskovits M (2021) Microwave synthesis of zeolites and their related applications. Microporous Mesoporous Mater 323:111262

Arafat A, Jansen JC, Ebaid AR, van Bekkum H (1993) Microwave preparation of zeolite Y and ZSM-5. Zeolites 13(3):162–165

Kunii K, Narahara K, Yamanaka S (2002) Template-free synthesis of AIPO 4 -H 1 , -H 2 , and -H 3 by microwave heating. Microporous Mesoporous Mater 52:159–167

Fan JX, Su G, Duan LH, Zhang XT, Song LJ, Sun ZL (2005) Application of microwave to zeolite research. Chem Ind Eng Prog 24:1244–1248

Shekara BMC, Prakash BSJ, Bhat YS (2011) Dealumination of zeolite BEA under microwave irradiation. ACS Catal 1(3):193–199

Venkatesha NJ, Bhat YS, Prakash BSJ (2016) Dealuminated BEA zeolite for selective synthesis of five-membered cyclic acetal from glycerol under ambient conditions. RSC Adv 6:18824–18833

Gonzalez MD, Cesteros Y, Salagre P, Francisco M, Sueiras JE (2009) Microporous Mesoporous Mater 118:341–347

Gonzalez MD, Cesteros Y, Salagre P (2010) Effect of microwaves on the surface and acidic properties of dealuminated zeolites. Phys Procedia 8:104–108

Gonzalez MD, Cesteros Y, Salagre P (2011) Comparison of dealumination of zeolites beta, mordenite and ZSM-5 by treatment with acid under microwave irradiation. Microporous Mesoporous Mater 144(1–3):162–170

Abello S, Perez-Ramírez J (2009) Accelerated generation of intracrystalline mesoporosity in zeolites by microwave-mediated desilication. Phys Chem Chem Phys 11:2959–2963

Hasan Z, Jun JW, Kim CU, Jeong KE, Jeong SY, Jhung SH (2015) Desilication of ZSM-5 zeolites for mesoporosity development using microwave irradiation. Mater Res Bull 61:469–474

Luo XL, Pei F, Wang W, Qian HM, Miao KK, Pan Z, Chen YS, Feng GD (2018) Microporous Mesoporous Mater 262:148–153

Bukhari SS, Behin J, Kazemian H, Rohani S (2015) Synthesis of zeolite NA-A using single mode microwave irradiation at atmospheric pressure: the effect of microwave power. Can J Chem Eng 93:1081–1090

Oyinade A, Kovo AS, Hill P (2016) Synthesis, characterization and ion exchange isotherm of zeolite Y using Box–Behnken design. Adv Powder Technol 27:750–755

Cecilia JA, Vilarrasa-García E, Morales-Ospino R, Finocchio E, Busca G, Sapag K, Villarroel-Rocha J, Bastos-Neto M, Azevedo DCS, Rodríguez-Castellon E (2022) Kaolinite-based zeolites synthesis and their application in CO 2 capture processes. Fuel 320:123953

Taufiqurrahmi N, Mohamed AR, Bhatia S (2011) Nanocrystalline Y: synthesis and characterization. IOP Conf Ser Mater Sci Eng 17:1–6. https://doi.org/10.1088/1757-899X/17/1/012030

Ghrib Y, Frini-Srasra N, Srasra E (2017) Synthesis of ZSM-5 zeolite from metakaolinite: effects of the SiO 2 /Al 2 O 3 molar ratio, the initial precursor and the presence of organic template agent. Surf Eng Appl Electrochem 53(1):64–70

Yin X, Long Z, Wang C, Li Z, Zhao M, Yang S (2019) A time-and-cost-effective synthesis of CHA zeolite with small size using ultrasonic-assisted method. Ultrason Sonochem 58:104679

Liu Y, Zhang H, Zhang F, Zhu M, Hu N, Chen X (2019) Facile synthesis of low-silica zeolite erionite by ultrasonic-assisted method. Mater Lett Accepted Manuscr. https://doi.org/10.1016/j.matlet.2019.126934

Zhang L, Yang CG, Meng XJ, Xie B, Wang L, Ren LM, Ma SJ, Xiao FS (2010) Organotemplate-free syntheses of ZSM-34 zeolite and its heteroatom-substituted analogues with good catalytic performance. Chem Mater 22:3099–3107

Wang R, Ma NK, Yan YS, Wang ZB (2018) Ultrasonic-assisted fabrication of high flux T-type zeolite membranes on alumina hollow fibers. J Membr Sci 548:676–684

Han J, Ha Y, Guo M, Zhao P, Liu Q, Liu C, Song C, Ji N, Lu X, Ma D, Li Z (2019) Synthesis of zeolite SSZ-13 from coal gangue via ultrasonic pretreatment combined with hydrothermal growth method. Ultrason Sonochem 59:104703

Kunecki P, Panek R, Wdowin M, Franus W (2017) Synthesis of faujasite (FAU) and tschernichite (LTA) type zeolites as a potential direction of the development of lime Class C fly ash. Int J Miner Process 166:69–78

Su X, Fang YJ, Gao P, Liu Y, Bai XF, Wu W (2020) In-situ microwave synthesis of nano-GaZSM-5 bifunctional catalysts with controllable location of active GaO +  species for olefins aromatization. Microporous Mesoporous Mater 306:110388

Akın SS, Kirdeciler Hou SK, Kazanc F, Akata B (2021) Critical analysis of zeolite 4A synthesis through one-pot fusion hydrothermal treatment approach for class F fly ash. Microporous Mesoporous Mater 325:111338

Kirdeciler SK, Akata B (2020) One pot fusion route for the synthesis of zeolite 4A using kaolin. Adv Powder Technol 31:4336–4343

Abukhadra MR, Ibrahima SM, Yakout SM, El-Zaidy ME, Abdeltawab AA (2019) Synthesis of Na+ trapped bentonite/zeolite-P composite as a novel catalyst for effective production of biodiesel from palm oil; effect of ultrasonic irradiation and mechanism. Energy Convers Manag 196:739–750

Dua Y, Shi S, Dai H (2011) Water-bathing synthesis of high-surface-area zeolite P from diatomite. Particuology 9:174–178

Narayanan S, Tamizhdurai P, Mangesh VL, Ragupathi C, Krishnan PS, Ramesh A (2021) Recent advances in the synthesis and applications of mordenite zeolite—review. RSC Adv 11:250–267

Aguado J, Serrano DP, Escola MJ, Rodríguez MJ (2005) Low temperature synthesis and properties of ZSM-5 aggregates formed by ultra-small nanocrystals. Microporous Mesoporous Mater 75(1–2):41–49

Aguado J, Serrano DP, Escola JM, Rodríguez JM (2004) Low temperature synthesis and properties of ZSM-5 aggregates formed by ultra-small nanocrystals. Microporous Mesoporous Mater 75:41–49

Li G, Li Z, Ren X, Zhang Y, Chen Z, Yu J (2019) A two-step crystallization route for hierarchical SAPO-34 molecular sieves: unique structural features and catalytic property for DTO. Mater Sci Appl 10(4):302–316

Download references

Author information

Authors and affiliations.

Department of Chemical and Petroleum Engineering, Bayero University, Kano, Nigeria

Nurudeen Salahudeen

You can also search for this author in PubMed   Google Scholar

Corresponding author

Correspondence to Nurudeen Salahudeen .

Ethics declarations

Conflict of interest.

The author declares that there is no conflict of interest in this work.

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Salahudeen, N. A Review on Zeolite: Application, Synthesis and Effect of Synthesis Parameters on Product Properties. Chemistry Africa 5 , 1889–1906 (2022). https://doi.org/10.1007/s42250-022-00471-9

Download citation

Received : 24 June 2022

Accepted : 31 August 2022

Published : 10 September 2022

Issue Date : December 2022

DOI : https://doi.org/10.1007/s42250-022-00471-9

Share this article

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

• Synthesis mechanisms
• Synthesis methods
• Framework type
• Synthesis parameters
• Product properties
• Find a journal
• Publish with us
• Track your research

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

• View all journals
• Explore content
• About the journal
• Publish with us
• Sign up for alerts
• Published: 21 September 2020

Looking deeper into zeolites

• Stephen Shevlin 1  

Nature Materials volume  19 ,  pages 1038–1039 ( 2020 ) Cite this article

8239 Accesses

7 Citations

6 Altmetric

Metrics details

Avelino Corma, professor at the Institute of Chemical Technology (ITQ-CSIC-Polytechnical University of Valencia), talks to Nature Materials about challenges facing zeolites, and issues faced in commercializing research.

Please tell us about your scientific background and why you research zeolites?

My scientific background is on heterogeneous catalysis. My objective has always been to understand the reaction mechanism and catalytic active sites, to progress catalyst synthesis, and to maximize well-defined single or multiple isolated sites. Starting from those premises, zeolites are a natural selection. They are crystalline materials with well-defined pores and cavities. By being crystalline, we can introduce well-defined single or multiple active sites in framework or extra framework positions. Furthermore, we can use a variety of physicochemical characterization and modelling techniques to visualize those sites and their interaction with the reactants, and to establish structure–reactivity correlations. Finally, since zeolites have pores that match the dimensions of reactants, we can take advantage of confinement effects and their impact on reactivity.

During my PhD, I was working with amorphous silica-alumina catalyst and it was at the end of the PhD when I started to look into zeolites. They are crystalline silicoaluminates, with all the advantages named above. At that time, besides some work in academia — such as Professor Barrer in the UK — the biggest research effort on zeolites was in industry, and it was their application for fluidized catalytic cracking that made this field explode. Several companies subsequently established research groups of extraordinary high quality. They started to produce new zeolites, which led to many new scientific questions arising and the opening of a new research field with substantial industrial impact that continues to be very relevant today.

Has the recent COVID-19 pandemic affected your research?

It has certainly affected our research. Though it has slowed down our research in the lab, it has given me some peace. I have more time to think and meditate, which means that some of the everyday pressure has been released. This favours the generation of new ideas. On the other hand, it was a bit frustrating not to be able to check right away these ideas.

For our PhD students it was very annoying to delay their work. However, they have had the opportunity to read and to generate their own ideas, which will inform their future research.

What do you think are the current challenges for the field?

Important challenges are to understand the fundamental mechanisms of how nucleation and crystallization occur in zeolites, and how we can control them. Up to now, most of the advances have been achieved by the slow accumulation of knowledge, chemical intuition, and trial and error.

Another challenge is how to locate active sites in specific pre-established positions within the zeolite. Imagine, for instance, that you have a zeolite with pores of different sizes. From the reactivity point of view, you may want to locate the catalytically active sites within one channel and not the other. You may even want to have one type of site in one channel and another site in the other channel to carry out tandem reactions. Going further, it is also challenging to control the sizes and chemical compositions of active species within the microporous zeolite environment. Locating active sites in preselected positions is certainly a fundamental and intellectual challenge, with important industrial implications.

A third challenge is to synthesize a predefined structure. Many thermodynamically feasible zeolites have been reported. The question now is how to synthesize a zeolite that does not exist. Here, we come back to the fundamental understanding of nucleation and crystallization.

For catalysis with zeolites, how we operate today is as follows. Imagine that you want to catalyse a reaction by using a zeolite. Then, we make use of accumulated knowledge and analogies, go into the toolbox of synthesized zeolite structures, and select several that look promising. Then, they will be tested to find the best candidate, and try to find an explanation on why that particular zeolite is the best. It appears to me that it would be more intellectually rewarding if one can perform the ab initio synthesis of a zeolite for a pre-established reaction, while locating the active site in the appropriate position within the framework.

To do that, one can look first into the reaction mechanism and find a potential transition state (TS). Since the desired zeolite catalyst should minimize the energy of the TS by optimizing its interactions with the framework, one can now prepare a mimic of the reaction TS and use it as a template or structure-directing agent (SDA) for zeolite synthesis. If a zeolite is synthesized with this mimic SDA, it does not matter if it is a new zeolite or an already existing one, it should maximize interactions between the framework and TS mimic. This will result in a decrease of the activation energy with an increase in reaction rate. Therefore, the zeolite obtained with the TS mimic acting as a zeolite template should be, in principle, adequate for catalysing the desired reaction. This is like if one would be doing an imprinting of the TS on a solid and the result would be analogous to producing solid catalytic antibodies.

Finally, achieving catalytic enantioselectivity with zeolites is also a challenge. In my opinion, even better than achieving chiral zeolite structures, the objective would be to produce chiral centres within the zeolite framework.

As you can see, we have very interesting challenges and to achieve these objectives will require teams able to develop and put together advanced synthesis, characterization, modelling and catalytic reactivity techniques.

You have successfully filed many patents. Is there a tension between publishing scientific research and submitting patent applications?

The main tension is that we cannot publish the results until the patent has been revised and, at least, filed. This increases the time of publication. Then, when the results are very new and with important implications, we start to get nervous. This is even more so when working with a company that wishes to further protect the discovery with additional patents.

I had some bad moments when the company wants to keep this knowledge and did not allow us to publish the work. Fortunately, this is not common.

What are the differences in writing for each format, and indeed what are the advantages and disadvantages in pursuing ‘commercial’ research versus ‘purely intellectual’ research?

You have to be much more detailed in the scientific paper, with an explanation of, the results obtained on the basis of an initial hypothesis. In the case of the patent, what matters is the result, no. explanation is required. In a patent one has to be careful what you write or how you write it to avoid conflicts with other patents or publications that can invalidate your claims.

Usually the companies we work with have very good patent lawyers. We give them a draft of the patent or a detailed report on the work. After the exchange back and forth of a few versions, they end up producing a very good and protective document.

With respect to industrial versus ‘intellectual’ research, I would not establish differences based on those terms. In our case, we first set scientific challenges. If we are successful, we try to go further and see how our findings, can be used to solve an industrial problem. Then we make a proof of principle and, if successful, we either apply for a patent or we approach a company and try to develop it further with them. In that sense, our collaboration with industry has been, for most of the time, rewarding. Companies have very good research teams from which we also learn when working together.

In many publications, the authors claim in the introduction that even if their work is of more fundamental interest, if successful, it can help solve an industrial problem. The philosophy established in our institute since its foundation was to cover from the ‘intellectual’ part to the proof of principle. Perhaps that is the reason why there are about ten processes in which the catalysts were conceived in our institute. Not too many can say that they publish the concept, got the patent, and that industrial plants use that research.

Are there any specific issues with the practical technological application of zeolites that are not faced by other materials? Are these issues that could be aided by theoretical or computational insight?

The scientific methodology used in zeolites research is not too different from that used for other catalysts. We have to synthesize the structure that maximizes the active sites required for the desired reaction, while avoiding the generation of sites that catalyse unwanted reactions. This is common for any catalyst. For zeolites, we have the added value of the porous structure with the corresponding shape selectivity and confinement effects. A tremendous advantage of zeolites is that, by being crystalline, you can model not only the structure but also the different elements that can be introduced in the framework or extra framework positions. Then, when combining modelling with operando spectroscopy and microkinetics we can study how the reaction occurs on the active sites and how we can also influence the reactivity by diffusion, adsorption and confinement. However, when approaching a catalyst manufacturer there are questions to be answered on how easy it is to implement zeolite synthesis with the tools they have, and how do the economics look taking into account technical benefits with respect to competing technologies and the manufacturing cost of these new zeolites.

This very cold exercise can be frustrating for a scientist that has a new zeolite that can do better than others used commercially, but cannot pay for the additional expenses in manufacturing. However, from time to time we can be close enough to pursue the objective. Moreover, what is not seen today as an opportunity can be seen tomorrow as a key technology for a different paradigm. This is the beauty of research: it increases human knowledge and so helps to solve present or future problems.

In our experience there is a continuous dialogue when working in with a company. You may come up with a new idea, but the material is too expensive, maybe because of the SDA used for synthesis. Then, you have to make an hypothesis on the synthesis in order to make it cheaper, and here comes again the research.

Zeolites are famous for having millions of potential structures but only 232 frameworks can be synthesized. Is this a limiting factor, or are there a vast amount of possibilities in the toolbox?

When I was talking about the zeolite toolbox, I referred to structures that have been already synthesized. There are many more thermodynamically feasible zeolites. Unfortunately, we still do not have the fundamental knowledge to synthesize any pre-established specific structure.

Do you think zeolitic catalysis of petrochemicals will have a long-term future? Are there breakthroughs in other areas (such as biomass reforming) that are coming, and will they have a great impact?

Zeolites are already very successful beyond making fuels from oils, they also make a large number of other chemicals. Certainly, we use oil and natural gas for making organic chemicals. Another source of carbon is biomass, and zeolites are playing their unique role in this field. We are also seeing zeolites in process for making chemicals from synthesis gas and even from CO 2 and H 2 through constructing bifunctional catalysts. Moreover, zeolites are very successful catalysts for the elimination of contaminants such as NO x . They are extremely stable materials, and if their pore size can be enlarged without compromising stability, their possibilities for adsorption and catalysis will be greatly expanded.

I believe zeolites will continue to play an important role for sustainable catalytic processes. Chemical selectivity is also a key word in the circular economy and zeolites can be constructed to achieve unprecedented selectivities in catalysis and separations.

What can young scientists look to gain from specializing in research on zeolites?

I would say that zeolites are ideal catalysts, from the point of view of learning. They bring together synthesis, characterization, reactivity, absorption and separation skills. It is an excellent field for enabling and young scientists to develop a strong foundation, since they will have to deal with physical chemistry, inorganic chemistry, organic chemistry and chemical engineering. Then, they can go into academia, but they will also be highly appreciated in industry.

Some of the PhDs and postdocs who have worked with me are now professors in universities or are working successfully in companies. A few are entrepreneurs, who started their own companies.

I always thought my role was to bring the students to the limit of their possibilities. It is not easy and it looks like I am sometimes a very tough guy, but later they appreciate what I am trying to do.

Author information

Authors and affiliations.

Nature Materials https://www.nature.com/naturematerials

Stephen Shevlin

You can also search for this author in PubMed   Google Scholar

Corresponding author

Correspondence to Stephen Shevlin .

Rights and permissions

Reprints and permissions

About this article

Cite this article.

Shevlin, S. Looking deeper into zeolites. Nat. Mater. 19 , 1038–1039 (2020). https://doi.org/10.1038/s41563-020-0787-4

Download citation

Published : 21 September 2020

Issue Date : October 2020

DOI : https://doi.org/10.1038/s41563-020-0787-4

Share this article

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

Quick links

• Explore articles by subject
• Guide to authors
• Editorial policies

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Information

• Author Services

Initiatives

You are accessing a machine-readable page. In order to be human-readable, please install an RSS reader.

All articles published by MDPI are made immediately available worldwide under an open access license. No special permission is required to reuse all or part of the article published by MDPI, including figures and tables. For articles published under an open access Creative Common CC BY license, any part of the article may be reused without permission provided that the original article is clearly cited. For more information, please refer to https://www.mdpi.com/openaccess .

Feature papers represent the most advanced research with significant potential for high impact in the field. A Feature Paper should be a substantial original Article that involves several techniques or approaches, provides an outlook for future research directions and describes possible research applications.

Feature papers are submitted upon individual invitation or recommendation by the scientific editors and must receive positive feedback from the reviewers.

Editor’s Choice articles are based on recommendations by the scientific editors of MDPI journals from around the world. Editors select a small number of articles recently published in the journal that they believe will be particularly interesting to readers, or important in the respective research area. The aim is to provide a snapshot of some of the most exciting work published in the various research areas of the journal.

Original Submission Date Received: .

• Active Journals
• Find a Journal
• Proceedings Series
• For Authors
• For Reviewers
• For Editors
• For Librarians
• For Publishers
• For Societies
• For Conference Organizers
• Open Access Policy
• Institutional Open Access Program
• Special Issues Guidelines
• Editorial Process
• Research and Publication Ethics
• Article Processing Charges
• Testimonials
• Preprints.org
• SciProfiles
• Encyclopedia

Article Menu

• Subscribe SciFeed
• Recommended Articles
• PubMed/Medline
• Google Scholar
• on Google Scholar
• Table of Contents

Find support for a specific problem in the support section of our website.

Please let us know what you think of our products and services.

Visit our dedicated information section to learn more about MDPI.

JSmol Viewer

Zeolite properties, methods of synthesis, and selected applications.

1. Introduction

2. properties and classification of zeolites.

Click here to enlarge figure

3. Zeolite Synthesis Methods

3.1. hydrothermal synthesis, 3.2. various techniques of hydrothermal synthesis, 3.2.1. alkali fusion, 3.2.2. alkaline activation, 3.3. molten salt method, 3.4. microwave assisted synthesis, 3.5. other methods, 4. applications of zeolites, 4.1. zeolite applications in agriculture, 4.1.1. soil amendment with multidirectional action, 4.1.2. crop protection, 4.1.3. heat stress and photosynthesis enhancement on crops, 4.1.4. aquaculture, 4.2. zeolites in environmental protection, 4.2.1. sorption of radionuclides, 4.2.2. immobilization of trace elements in the soil, 4.2.3. gas adsorption and catalysis, 4.2.4. wastewater treatment, 4.3. other applications of zeolites, 4.3.1. adsorption of harmful substances, 4.3.2. tissue engineering, 4.3.3. carriers of bioactive compounds, 5. conclusions, author contributions, institutional review board statement, informed consent statement, data availability statement, conflicts of interest.

• Jarosz, R.; Szerement, J.; Gondek, K.; Mierzwa-Hersztek, M. The use of zeolites as an addition to fertilisers—A review. CATENA 2022 , 213 , 106125. [ Google Scholar ] [ CrossRef ]
• Ahmadi, B.; Shekarchi, M. Use of natural zeolite as a supplementary cementitious material. Cem. Concr. Compos. 2010 , 32 , 134–141. [ Google Scholar ] [ CrossRef ]
• Hrachovcová, K.; Tišler, Z.; Svobodová, E.; Šafář, J. Modified alkali activated zeolite foams with improved textural and mechanical properties. Minerals 2020 , 10 , 483. [ Google Scholar ] [ CrossRef ]
• Larin, V.A. The Loewenstein rule: The increase in electron kinetic energy as the reason for instability of Al-O-Al linkage in aluminosilicate zeolites. Phys. Chem. Miner. 2013 , 40 , 771–780. [ Google Scholar ] [ CrossRef ]
• Wang, S.; Peng, Y. Natural zeolites as effective adsorbents in water and wastewater treatment. Chem. Eng. J. 2010 , 156 , 11–24. [ Google Scholar ] [ CrossRef ]
• de Magalhães, L.F.; da Silva, G.R.; Peres, A.E.C. Zeolite application in wastewater treatment. Adsorp. Sci. Technol. 2022 , 2022 , 4544104. [ Google Scholar ] [ CrossRef ]
• Bandura, L.; Białoszewska, M.; Leiviskä, T.; Franus, M. The Role of zeolite structure in its β-cyclodextrin modification and tetracycline adsorption from aqueous solution: Characteristics and sorption mechanism. Materials 2022 , 15 , 6317. [ Google Scholar ] [ CrossRef ]
• Kuldeyev, E.; Seitzhanova, M.; Tanirbergenova, S.; Tazhu, K.; Doszhanov, E.; Mansurov, Z.; Azat, S.; Nurlybaev, R.; Berndtsson, R. Modifying natural zeolites to improve heavy metal adsorption. Water 2023 , 15 , 2215. [ Google Scholar ] [ CrossRef ]
• Khaleque, A.; Alam, M.M.; Hoque, M.; Mondal, S.; Haider, J.B.; Xu, B.; Johir, M.A.H.; Karmakar, A.K.; Zhou, J.L.; Ahmed, M.B.; et al. Zeolite synthesis from low-cost materials and environmental applications: A review. Environ. Adv. 2020 , 2 , 100019. [ Google Scholar ] [ CrossRef ]
• Database of Zeolite Structures, International Zeolite Association. Available online: http://www.iza-structure.org/databases (accessed on 5 February 2024).
• Pérez-Botella, E.; Valencia, S.; Rey, F. Zeolites in adsorption processes: State of the art and future prospects. Chem. Rev. 2022 , 122 , 17647–17695. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Lima, R.C.; Bieseki, L.; Melguizo, P.V.; Pergher, S.B.C. Environmentally Friendly Zeolites—Synthesis and Source Materials ; Springer: Berlin/Heidelberg, Germany, 2019. [ Google Scholar ]
• Mijailović, N.R.; Nedić Vasiljević, B.; Ranković, M.; Milanović, V.; Uskoković-Marković, S. Environmental and pharmacokinetic aspects of zeolite/pharmaceuticals systems—Two facets of adsorption ability. Catalysts 2022 , 12 , 837. [ Google Scholar ] [ CrossRef ]
• Cataldo, E.; Salvi, L.; Paoli, F.; Fucile, M.; Masciandaro, G.; Manzi, D.; Massini, C.M.; Mattii, G.B. Application of zeolites in agriculture and other potential uses: A review. Agronomy 2021 , 11 , 1547. [ Google Scholar ] [ CrossRef ]
• De Souza, V.C.; Villarroel-Rocha, J.; De Araújo, M.J.G.; Sapag, K.; Pergher, S.B.C. Basic treatment in natural clinoptilolite for improvement of physicochemical properties. Minerals 2018 , 8 , 595. [ Google Scholar ] [ CrossRef ]
• Jiang, Z.; Yang, J.; Ma, H.; Ma, X.; Yuan, J. Synthesis of pure NaA zeolites from coal fly ashes for ammonium removal from aqueous solutions. Clean Technol. Environ. Policy 2016 , 18 , 629–637. [ Google Scholar ] [ CrossRef ]
• Längauer, D.; Čablík, V.; Hredzák, S.; Zubrik, A.; Matik, M.; Danková, Z. Preparation of synthetic zeolites from coal fly ash by hydrothermal synthesis. Materials 2021 , 14 , 1267. [ Google Scholar ] [ CrossRef ]
• Król, M. Natural vs. synthetic zeolites. Crystals 2020 , 10 , 622. [ Google Scholar ] [ CrossRef ]
• Schoonheydt, R.A.; Geerlings, P.; Pidko, E.A.; van Santen, R.A. The framework basicity of zeolites. J. Mater. Chem. 2012 , 22 , 18705–18717. [ Google Scholar ] [ CrossRef ]
• Walkowiak, A.; Wolska, J.; Wojtaszek-Gurdak, A.; Sobczak, I.; Wolski, L.; Ziolek, M. Modification of gold zeolitic supports for catalytic oxidation of glucose to gluconic acid. Materials 2021 , 14 , 5250. [ Google Scholar ] [ CrossRef ]
• Kulprathipanja, S. Zeolites in Industrial Separation and Catalysis ; Wiley VCH: Weinheim, Germany, 2010. [ Google Scholar ]
• Szostak, R. Molecular Sieves. Principles of Synthesis and Identififaction ; Springer: New York, NY, USA, 1989. [ Google Scholar ]
• Guisnet, M.; Gilson, J.P. Zeolites for Cleaner Technologies ; Catalytic Science Series; Imperial College Press: London, UK, 2002. [ Google Scholar ] [ CrossRef ]
• Payra, P.; Dutta, P. Zeolites: A Primer. In Handbook of Zeolites Science and Technology ; CRC Press: Boca Raton, FL, USA, 2003. [ Google Scholar ]
• Moshoeshoe, M.; Nadiye-Tabbiruka, M.S.; Obuseng, V. A Review of the chemistry, structure, properties and applications of zeolites. Am. J. Mater. Sci. 2017 , 7 , 196–221. [ Google Scholar ] [ CrossRef ]
• Ahmaruzzaman, M. A review on the utilization of fly ash. Prog. Energy Combust. Sci. 2010 , 36 , 327–363. [ Google Scholar ] [ CrossRef ]
• Ming, D.W.; Allen, E.R. Use of natural zeolites in agronomy, horticulture and environmental soil remediation. Rev. Mineral. Geochem. 2001 , 45 , 619–654. [ Google Scholar ] [ CrossRef ]
• Polat, E.; Karaca, M.; Demir, H.; Onus, A.N. Use of natural zeolite (clinoptilolite) in agriculture. J. Fruit Ornam. 2004 , 12 , 183–189. [ Google Scholar ]
• Ramesh, K.; Reddy, D.D. Zeolites and their potential uses in agriculture. Adv. Agron. 2011 , 113 , 219–240. [ Google Scholar ] [ CrossRef ]
• Sharma, V.; Javed, B.; Byrne, H.; Curtin, J.; Tian, F. Zeolites as carriers of nano-fertilizers: From structures and principles to prospects and challenges. Appl. Nano 2022 , 3 , 163–186. [ Google Scholar ] [ CrossRef ]
• Jakubowski, M.; Voelkel, A.; Sandomierski, M. Crystalline zeolite layers on the surface of titanium alloys in biomedical applications: Current knowledge and possible directions of development. Crystals 2022 , 12 , 1520. [ Google Scholar ] [ CrossRef ]
• Johnson, E.B.G.; Arshad, S.E. Hydrothermally synthesized zeolites based on kaolinite: A review. Appl. Clay Sci. 2014 , 97–98 , 215–221. [ Google Scholar ] [ CrossRef ]
• Cundy, C.S.; Cox, P.A. The hydrothermal synthesis of zeolites: History and development from the earliest days to the present time. Chem. Rev. 2003 , 103 , 663–702. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Vasconcelos, A.A.; Len, T.; de Oliveira, A.d.N.; Costa, A.A.F.d.; Souza, A.R.d.S.; Costa, C.E.F.d.; Luque, R.; Rocha Filho, G.N.d.; Noronha, R.C.R.; Nascimento, L.A.S.d. Zeolites: A theoretical and practical approach with uses in (bio)chemical processes. Appl. Sci. 2023 , 13 , 1897. [ Google Scholar ] [ CrossRef ]
• Grela, A.; Hebda, M.; Łach, M.; Mikuła, J. Thermal behavior and physical characteristic of synthetic zeolite from CFB-coal fly ash. Microporous Mesoporous Mater. 2016 , 220 , 155–162. [ Google Scholar ] [ CrossRef ]
• Khabuanchalad, S.; Khemthong, P.; Prayoonpokarach, S.; Wittayakun, J. Transformation of zeolite NaY synthesized from rice husk silica o NaP during hydrothermal synthesis. Suranaree J. Sci. Technol. 2008 , 15 , 225–231. [ Google Scholar ]
• Wajima, T.; Haga, M.; Kuzawa, K.; Ishimoto, H.; Tamada, O.; Ito, K.; Nishiyama Downs, R.T.; Rakovan, J.F. Zeolite synthesis from paper sludge ash at low temperature (90 °C) with addition of diatomite. J. Hazard. Mater. 2006 , 132 , 244–252. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Novembre, D.; Sabatino, B.D.; Gimeno, D.; Garcia-Vallès, M.; Martínez-Manent, S. Synthesis of Na-X zeolites from tripolaceous deposits (Crotone, Italy) and volcanic zeolitised rocks (Vico volcano, Italy). Microporous Mesoporous Mater. 2004 , 75 , 1–11. [ Google Scholar ] [ CrossRef ]
• Deng, L.; Xu, Q.; Wu, H. Synthesis of zeolite-like material by hydrothermal and fusion methods using municipal solid waste fly ash. Procedia Environ. Sci. 2016 , 13 , 662–667. [ Google Scholar ] [ CrossRef ]
• Zhang, X.; Tong, D.; Zhao, J.; Li, X. Synthesis of NaX zeolite at room temperature and its characterization. Mater. Lett. 2013 , 104 , 80–83. [ Google Scholar ] [ CrossRef ]
• Kustova, M.Y.; Kustov, A.L.; Christensen, C.H. Aluminum-rich mesoporous MFI-type zeolite single crystals. Stud. Surf. Sci. Catal. 2005 , 158 , 255–262. [ Google Scholar ] [ CrossRef ]
• Huang, Y.; Wang, K.; Dong, D.; Li, D.; Hill, M.R.; Hill, A.J.; Wang, H. Synthesis of hierarchical porous zeolite NaY particles with controllable particle size. Microporous Mesoporous Mater. 2010 , 127 , 167–175. [ Google Scholar ] [ CrossRef ]
• Aylele, L.; Pérez-Pariente, J.; Chebude, Y.; Díaz, I. Conventional versus alkali fusion synthesis of zeolite A from low grade kaolin. Appl. Clay Sci. 2016 , 132–133 , 485–490. [ Google Scholar ] [ CrossRef ]
• Lee, M.-G.; Park, J.-W.; Kam, S.-K.; Lee, C.-H. Synthesis of Na-A zeolite from Jeju Island Scoria using fusion/hydrothermal method. Chemosphere 2018 , 207 , 203–208. [ Google Scholar ] [ CrossRef ]
• Thuadaij, P.; Nuntiya, A. Effect of the SiO 2 /Al 2 O 3 ratio on the synthesis of Na-X zeolite from Mae Moh fly ash. Sci. Asia 2012 , 38 , 295–300. [ Google Scholar ] [ CrossRef ]
• Davidovits, J. Geopolymers: Ceramic-like inorganic polymers. J. Ceram. Sci. Technol. 2017 , 08 , 335–350. [ Google Scholar ] [ CrossRef ]
• Villa, C.; Pecina, E.T.; Torres, R.; Gómez, L. Geopolymer synthesis using alkaline activation of natural zeolite. Constr. Build. Mater. 2010 , 24 , 2084–2090. [ Google Scholar ] [ CrossRef ]
• Xu, H.; van Deventer, J.S.J. The geopolymerisation of alumino-silicate minerals. Int. J. Miner. Process. 2000 , 59 , 247–266. [ Google Scholar ] [ CrossRef ]
• Jwaida, Z.; Dulaimi, A.; Mashaan, N.; Othuman Mydin, M.A. Geopolymers: The green alternative to traditional materials for engineering applications. Infrastructures 2023 , 8 , 98. [ Google Scholar ] [ CrossRef ]
• Garcia-Lodeiro, J.; Maltceva, O.; Palomo, A.; Fernandes-Jiménez, A. Hybrid alkaline cements: Part I. Fundamentals. Rom. J. Mater. 2012 , 42 , 330–335. [ Google Scholar ]
• Cong, P.; Chen, Y. Advances in geopolymer materials: A comprehensive review. J. Traffic Transp. Eng. (Engl. Ed.) 2021 , 8 , 283–314. [ Google Scholar ] [ CrossRef ]
• Król, M.; Rożek, P.; Chlebda, D.; Mozgawa, W. ATR/FT-IR studies of zeolite formation during alkali-activation of metakaolin. Solid State Sci. 2019 , 94 , 114–119. [ Google Scholar ] [ CrossRef ]
• van Jaarsveld, J.G.S.; van Deventer, J.S.J. Effect of the alkali metal activator on the properties of fly ash-based geopolymers. Ind. Eng. Chem. Res. 1999 , 38 , 3932–3941. [ Google Scholar ] [ CrossRef ]
• Vegere, K.; Vitola, L.; Argalis, P.P.; Bajare, D.; Krauklis, A.E. Alkali-activated metakaolin as a zeolite-like binder for the production of adsorbents. Inorganics 2019 , 7 , 141. [ Google Scholar ] [ CrossRef ]
• Park, M.; Choi, J. Molten-salt method for the synthesis of zeolitic materials I. Zeolite formation in alkaline molten-salt system. Microporous Mesoporous Mater. 2000 , 37 , 9. [ Google Scholar ] [ CrossRef ]
• Zhang, X.; Li, C.; Zheng, S.; Di, Y.; Sun, Z. A Review of the synthesis and application of zeolites from coal-based solid wastes. Int. J. Miner. Metall. Mater. 2022 , 29 , 1–21. [ Google Scholar ] [ CrossRef ]
• Yoo, Y.-S.; Cheon, K.-H.; Lee, J.-I.; Kim, B.-S.; Shin, W.-S.; Seo, G.-T. Zeolite synthesis using sewage sludge by molten-salt method. Mater. Sci. Forum 2008 , 569 , 329–332. [ Google Scholar ] [ CrossRef ]
• Zeng, X.; Hu, X.; Song, H.; Xia, G.; Shen, Z.-Y.; Yu, R.; Moskovits, M. Microwave synthesis of zeolites and their related applications. Microporous Mesoporous Mater. 2021 , 323 , 111262. [ Google Scholar ] [ CrossRef ]
• Panzarella, B.; Tompsett, G.A.; Ynqvesson, K.S.; Conner, W.C. Microwave synthesis of zeolites. 2. Effect of vessel size, precursor volume, and irradiation method. J. Phys. Chem. B 2007 , 111 , 12657–12667. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Tompsett, G.A.; Conner, W.C.; Yngvesson, K.S. Microwave synthesis of nanoporous materials. ChemPhysChem 2006 , 7 , 296–319. [ Google Scholar ] [ CrossRef ]
• Li, Y.; Yang, W. Microwave synthesis of zeolite membranes: A review. J. Membr. Sci. 2008 , 316 , 3–17. [ Google Scholar ] [ CrossRef ]
• Conner, W.C.; Tompsett, G.; Lee, K.-H.; Yngvesson, K.S. Microwave synthesis of zeolites: 1. Reactor engineering. J. Phys. Chem. B 2004 , 108 , 13913–13920. [ Google Scholar ] [ CrossRef ]
• Anuwattana, R.; Balkus, K.J., Jr.; Asavapisit, S.; Khummongkol, P. Conventional and microwave hydrothermal synthesis of zeolite ZSM-5 from the cupola slag. Microporous Mesoporous Mater. 2008 , 111 , 260–266. [ Google Scholar ] [ CrossRef ]
• Serrano, D.P.; Uguina, M.A.; Sanz, R.; Castillo, E.; Rodríguez, A.; Sánchez, P. Synthesis and crystallization mechanism of zeolite TS-2 by microwave and conventional heating. Microporous Mesoporous Mater. 2004 , 69 , 197–208. [ Google Scholar ] [ CrossRef ]
• Jacobsen, C.J.H.; Madsen, C.; Janssens, T.V.W.; Jakobsen, H.; Skibsted, J. Zeolites by confined space synthesis—Characterization of the acid sites in nanosized ZSM-5 by ammonia desorption and 27Al/29Si-MAS NMR spectroscopy. Microporous Mesoporous Mater. 2000 , 39 , 393–401. [ Google Scholar ] [ CrossRef ]
• Madsen, C.; Jacobsen, C.J.H. Nanosized zeolite crystals—Convenient control of crystal size distribution by confined space synthesis. Chem. Commun. 1999 , 8 , 673–674. [ Google Scholar ] [ CrossRef ]
• Schmidt, I.; Madsen, C.; Jacobsen, C.J.H. Confined space synthesis. A novel route to nanosized zeolites. Inorg. Chem. 2000 , 39 , 2279–2283. [ Google Scholar ] [ CrossRef ]
• Jacobsen, C.J.H.; Madsen, C.; Houzvicka, J.; Schmidt, I.; Carlsson, A. Mesoporous zeolite single crystals. J. Am. Chem. Soc. 2000 , 122 , 7116–7117. [ Google Scholar ] [ CrossRef ]
• Matsukata, M.; Nishiyama, N.; Ueyama, K. Crystallization of FER and MFI zeolites by a vapor-phase transport method. Micropor. Mater. 1996 , 7 , 109–117. [ Google Scholar ] [ CrossRef ]
• Thoma, S.G.; Nenoff, T.M. Vapor phase transport synthesis of zeolites from sol—Gel precursors. Microporous Mesoporous Mater. 2000 , 41 , 295–305. [ Google Scholar ] [ CrossRef ]
• Kim, M.-H.; Li, H.-X.; Davis, M.E. Synthesis of zeolites by water-organic vapor-phase transport. Micropor. Mater. 1993 , 1 , 191–200. [ Google Scholar ] [ CrossRef ]
• Niu, T.; Li, Y.; Li, J.; Chen, B. Synthesis of zeolite beta by the vapour-phase transport method using tetraethylammonium bromide as the organic template. Chin. J. Catal. 2009 , 30 , 191–195. [ Google Scholar ] [ CrossRef ]
• Liu, X.; Li, Y.; Chen, B.; Wang, Y. Cleaner process for synthesis of zeolite MCM-22 by vapor-phase transport method. Asia-Pac. J. Chem. Eng. 2009 , 4 , 607–611. [ Google Scholar ] [ CrossRef ]
• Rainer, D.N.; Morris, R.E. New avenues for mechanochemistry in zeolite science. Dalton Trans. 2021 , 50 , 8995–9009. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Majano, G.; Borchardt, L.; Mitchell, S.; Valtchev, V.; Pérez-Ramírez, J. Rediscovering zeolite mechanochemistry—A pathway beyond current synthesis and modification boundaries. Microporous Mesoporous Mater. 2014 , 194 , 106–114. [ Google Scholar ] [ CrossRef ]
• Wu, Q.; Liu, X.; Zhu, L.; Ding, L.; Gao, P.; Wang, X.; Pan, S.; Bian, C.; Meng, X.; Xu, J.; et al. Solvent-free synthesis of zeolites from anhydrous starting raw solids. J. Am. Chem. Soc. 2015 , 137 , 1052–1055. [ Google Scholar ] [ CrossRef ]
• Ren, L.; Wu, Q.; Yang, C.; Zhu, L.; Li, C.; Zhang, P.; Zhang, H.; Meng, X.; Xiao, F.-S. Solvent-free synthesis of zeolites from solid raw materials. J. Am. Chem. Soc. 2012 , 134 , 15173–15176. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Nada, M.H.; Larsen, S.C.; Gillan, E.G. Mechanochemically-assisted solvent-free and template-free synthesis of zeolites ZSM-5 and mordenite. Nanoscale Adv. 2019 , 1 , 3918–3928. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Cadar, O.; Stupar, Z.; Senila, M.; Levei, L.; Moldovan, A.; Becze, A.; Ozunu, A.; Levei, E.A. Zeolites reduce the transfer of potentially toxic elements from soil to leafy vegetables. Materials 2022 , 15 , 5657. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Rhodes, C.J. Properties and applications of zeolites. Sci. Prog. 2010 , 93 , 223–284. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Leung, S.; Barrington, S.; Zhao, X.; El-Husseini, B. Effect of particle size on physio-chemical properties of clinoptilolite as feed additive. Microporous Mesoporous Mater. 2006 , 95 , 48–56. [ Google Scholar ] [ CrossRef ]
• Li, Y.; Yu, J. Emerging applications of zeolites in catalysis, separation and host-guest assembly. Nat. Rev. Mater. 2021 , 6 , 1156–1174. [ Google Scholar ] [ CrossRef ]
• Bai, P.; Etim, U.J.; Yan, Z.; Mintova, S.; Zhang, Z.; Zhong, Z.; Gao, X. Fluid catalytic cracking technology: Current status and recent discoveries on catalyst contamination. Cat. Rev. 2019 , 61 , 333–405. [ Google Scholar ] [ CrossRef ]
• Oliveira, D.S.; Lima, R.B.; Pergher, S.B.C.; Caldeira, V.P.S. Hierarchical zeolite synthesis by alkaline treatment: Advantages and applications. Catalysts 2023 , 13 , 316. [ Google Scholar ] [ CrossRef ]
• Jung, J.; Jo, C.; Mota, F.M.; Cho, J.; Ryoo, R. Acid Catalytic Function of Mesopore Walls Generated by MFI zeolite desilication in comparison with external surfaces of MFI zeolite nanosheet. Appl. Catal. A Gen. 2015 , 492 , 68–75. [ Google Scholar ] [ CrossRef ]
• Khan, W.; Jia, X.; Wu, Z.; Choi, J.; Yip, A.C.K. Incorporating hierarchy into conventional zeolites for catalytic biomass conversions: A review. Catalysts 2019 , 9 , 127. [ Google Scholar ] [ CrossRef ]
• Feliczak-Guzik, A. Hierarchical Zeolites: Synthesis and Catalytic Properties. Microporous Mesoporous Mater. 2018 , 259 , 33–45. [ Google Scholar ] [ CrossRef ]
• Szatanik-Kloc, A.; Szerement, J.; Adamczuk, A.; Józefaciuk, G. Effect of low zeolite doses on plants and soil physicochemical properties. Materials 2021 , 14 , 2617. [ Google Scholar ] [ CrossRef ]
• Nakhli, S.A.A.; Delkash, M.; Bakhshayesh, B.E.; Kazemian, H. Application of zeolites for sustainable agriculture: A review on water and nutrient retention. Water Air Soil Pollut. 2017 , 228 , 464. [ Google Scholar ] [ CrossRef ]
• Mondal, M.; Biswas, B.; Garai, S.; Sarkar, S.; Banerjee, H.; Brahmachari, K.; Bandyopadhyay, P.K.; Maitra, S.; Brestic, M.; Skalicky, M.; et al. Zeolites enhance soil health, crop productivity and environmental safety. Agronomy 2021 , 11 , 448. [ Google Scholar ] [ CrossRef ]
• Xiubin, H.; Zhanbin, H. Zeolite application for enhancing water infiltration and retention in loess soil. Resour. Conserv. Recycl. 2001 , 34 , 45–52. [ Google Scholar ] [ CrossRef ]
• Gholizadeh-Sarabi, S.; Sepaskhah, A.R. Effect of zeolite and saline water application on saturated hydraulic conductivity and infiltration in different soil textures. Arch. Agron. Soil Sci. 2013 , 59 , 753–764. [ Google Scholar ] [ CrossRef ]
• Chmielewska, E. Zeolitic adsorption in course of pollutants mitigation and environmental control. J. Radioanal. Nucl. Chem. 2014 , 299 , 255–260. [ Google Scholar ] [ CrossRef ]
• Belviso, C.; Satriani, A.; Lovelli, S.; Comegna, A.; Coppola, A.; Dragonetti, G.; Cavalcante, F.; Rivelli, A.R. Impact of zeolite from coal fly ash on soil hydrophysical properties and plant growth. Agriculture 2022 , 12 , 356. [ Google Scholar ] [ CrossRef ]
• Bikkinina, L.M.-H.; Ezhkov, V.O.; Faizrakhmanov, R.N.; Gazizov, R.R.; Ezhkova, A.M. Effect of zeolites on soil modification and productivity. BIO Web Conf. 2020 , 17 , 00117. [ Google Scholar ] [ CrossRef ]
• Allen, E.R.; Hossner, L.R.; Ming, D.W.; Henninger, D.L. Solubility and cation exchange in phosphate rock and saturated clinoptilolite mixtures. Soil Sci. Soc. Am. J. 1993 , 57 , 1368–1374. [ Google Scholar ] [ CrossRef ]
• Campisi, T.; Abbondanzi, F.; Faccini, B.; Di Giuseppe, D.; Malferrari, D.; Coltorti, M.; Laurora, A.; Passaglia, E. Ammonium-charged zeolitite effects on crop growth and nutrient leaching: Greenhouse experiments on maize ( Zea mays ). Catena 2016 , 140 , 66–76. [ Google Scholar ] [ CrossRef ]
• Torma, S.; Vilcek, J.; Adamisin, P.; Huttmanova, E.; Hronec, O. Influence of natural zeolite on nitrogen dynamics in soil. Turk. J. Agric. For. 2014 , 38 , 739–744. [ Google Scholar ] [ CrossRef ]
• Aiyuk, S.; Xu, H.; van Haandel, A.; Verstraete, W. Removal of ammonium nitrogen from pretreated domestic sewage using a natural ion exchanger. Environ. Technol. 2004 , 25 , 1321–1330. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Englert, A.H.; Rubio, J. Characterization and environmental application of a Chilean natural zeolite. Int. J. Miner. Process. 2005 , 75 , 21–29. [ Google Scholar ] [ CrossRef ]
• Kavoosi, M. Effects of zeolite application on rice yield, nitrogen recovery, and nitrogen use efficiency. Commun. Soil Sci. Plant Anal. 2007 , 38 , 69–76. [ Google Scholar ] [ CrossRef ]
• Ahmed, O.H.; Sumalatha, G.; Muhamad, A.N. Use of zeolite in maize ( Zea mays ) cultivation on nitrogen, potassium and phosphorus uptake and use efficiency. Int. J. Phys. Sci. 2010 , 5 , 2393–2401. [ Google Scholar ]
• Li, Z.; Zhang, Y.; Li, Y. Zeolite as slow release fertilizer on spinach yields and quality in a greenhouse test. J. Plant Nutr. 2013 , 36 , 1496–1505. [ Google Scholar ] [ CrossRef ]
• Shirvani, M.; Farajollahi, E.; Bakhtiari, S.; Ogunseitan, O.A. Mobility and efficacy of 2,4-D herbicide from slow-release delivery systems based on organo-zeolite and organo-bentonite complexes. J. Environ. Health Part B 2014 , 49 , 255–262. [ Google Scholar ] [ CrossRef ]
• Bakhtiary, S.; Shirvani, M.; Shariatmadari, H. Adsorption-desorption behavior of 2,4-D on NCP-modified bentonite and zeolite: Implications for slow-release herbicide formulations. Chemosphere 2013 , 90 , 699–705. [ Google Scholar ] [ CrossRef ]
• Calzarano, F.; Seghetti, L.; Pagnani, G.; Di Marco, S. Italian zeolitites in the control of grey mould and sour rot and their effect on leaf reflectance, grape and wine. Agriculture 2020 , 10 , 580. [ Google Scholar ] [ CrossRef ]
• Prisa, D. Chabazitic zeolite in the cultivation and spray protection of Vitis vinifera . Int. J. Sci. Res. Arch. 2023 , 09 , 630–638. [ Google Scholar ] [ CrossRef ]
• De Smedt, C.; Steppe, K.; Spanoghe, P. Beneficial effects of zeolites on plant photosynthesis. Adv. Mater. Sci. 2017 , 2 , 1–11. [ Google Scholar ] [ CrossRef ]
• Montanari, T.; Busca, G. On the mechanism of adsorption and separation of CO 2 on LTA zeolites: An IR investigation. Vib. Spectrosc. 2008 , 46 , 45–51. [ Google Scholar ] [ CrossRef ]
• Bhargava, S.; Mitra, S. Elevated atmospheric CO 2 and the future of crop plants. Plant Breed. 2021 , 140 , 1–11. [ Google Scholar ] [ CrossRef ]
• Long, S.P.; Ainsworth, E.A.; Rogers, A.; Ort, D.R. Rising atmospheric carbon dioxide: Plants FACE the future. Annu. Rev. Plant Biol. 2004 , 55 , 591–628. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Asgharimoghadam, A.; Gharedaashi, E.; Montajami, S.; Nekoubin, H.; Salamroudi, M.; Jafariyan, H. Effect of clinoptilolite zeolite to prevent mortality of beluga ( Huso huso ) by total ammonia concentration. Glob. Vet. 2012 , 9 , 80–84. [ Google Scholar ]
• Ghasemi, Z.; Sourinejad, I.; Kazemian, H.; Rohani, S. Application of zeolites in aquaculture industry: A review. Aquaculture 2018 , 10 , 75–95. [ Google Scholar ] [ CrossRef ]
• Misaelides, P. Application of natural zeolites in environmental remediation: A short review. Microporous Mesoporous Mater. 2011 , 144 , 15–18. [ Google Scholar ] [ CrossRef ]
• Zagho, M.M.; Hassan, M.K.; Khraisheh, M.; Al-Maadeed, M.A.A.; Nazarenko, S. A review on recent advances in CO 2 separation using zeolite and zeolite-like materials as adsorbents and fillers in mixed matrix membranes (MMMs). Chem. Eng. J. Adv. 2021 , 6 , 100091. [ Google Scholar ] [ CrossRef ]
• Osmanlioglu, A.E. Treatment of radioactive liquid waste by sorption on natural zeolite in Turkey. J. Hazard. Mater. 2006 , 137 , 332–335. [ Google Scholar ] [ CrossRef ]
• Lihareva, N.; Petrov, O.; Dimowa, L.; Tzvetanova, Y.; Piroeva, I.; Ublekov, F.; Nikolov, A. Ion exchange of Cs + and Sr 2+ by natural clinoptilolite from bi-cationic solutions and XRD control of their structural positioning. J. Radioanal. Nucl. Chem. 2020 , 323 , 1093–1102. [ Google Scholar ] [ CrossRef ]
• Borai, E.H.; Harjula, R.; Malinen, L.; Paajanen, A. Efficient removal of cesium from low-level radioactive liquid waste using natural and impregnated zeolite minerals. J. Hazard Mater. 2009 , 172 , 416–422. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Chałupnik, S.; Franus, W.; Wysocka, M.; Gzyl, G. Application of zeolites for radium removal from mine water. Environ. Sci. Pollut. Res. 2013 , 20 , 7900–7906. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Inazumi, S.; Shishido, K.I.; Nontananandh, S.; Moriiwa, K. Remediation of heavy metals polluted soil using metal insolubilizing materials. J. Environ. Prot. 2018 , 9 , 770–789. [ Google Scholar ] [ CrossRef ]
• Ukalska-Jaruga, A.; Siebielec, G.; Siebielec, S.; Pecio, M. The effect of soil amendments on trace elements’ bioavailability and toxicity to earthworms in contaminated soils. Appl. Sci. 2022 , 12 , 6280. [ Google Scholar ] [ CrossRef ]
• Rahimi, M.; Mahmoudi, J. Heavy metals removal from aqueous solution by modified natural zeolites using central composite design. Period. Polytech. Chem. Eng. 2019 , 64 , 106–115. [ Google Scholar ] [ CrossRef ]
• Valarde, L.; Nabavi, M.S.; Escalera, E.; Anti, M.-L.; Akhtar, F. Adsorption of heavy metals on natural zeolites: A review. Chemosphere 2023 , 328 , 138508. [ Google Scholar ] [ CrossRef ]
• Lihareva, N.; Dimova, L.; Petrov, O.; Tzvetanova, Y. Ag + sorption on natural and Na-exchanged clinoptilolite from Eastern Rhodopes, Bulgaria. Microporous Mesoporous Mater. 2010 , 130 , 32–37. [ Google Scholar ] [ CrossRef ]
• Belviso, C. Zeolite for Potential Toxic Metal Uptake from Contaminated Soil: A Brief Review. Processes 2020 , 8 , 820. [ Google Scholar ] [ CrossRef ]
• Kumpiene, J. Trace elements immobilization in soil using amendments. In Trace Elements in Soil ; Hooda, P.S., Ed.; John Wiley and Sons, Ltd.: Hoboken, NJ, USA, 2010. [ Google Scholar ]
• Żołnowski, A.C.; Wyszkowski, M. Mineral neutralizers as a tool for improving the properties of soil contaminated with copper. Minerals 2022 , 12 , 895. [ Google Scholar ] [ CrossRef ]
• Wyszkowski, M.; Wyszkowska, J.; Kordala, N.; Zaborowska, M. Molecular sieve, halloysite, sepiolite and expanded clay as a tool in reducing the content of trace elements in Helianthus annuus L. on copper-contaminated soil. Materials 2023 , 16 , 1827. [ Google Scholar ] [ CrossRef ]
• Sivitskaya, V.; Wyszkowski, M. Effect of heating oil and neutralizing substances on the content of some trace elements in maize ( Zea mays L.). Ecol. Chem. Eng. A 2013 , 20 , 323–331. [ Google Scholar ] [ CrossRef ]
• Li, H.; Shi, W.-Y.; Shao, H.-B.; Shao, M.-A. The remediation of the lead-polluted garden soil by natural zeolite. J. Hazard. Mater. 2009 , 169 , 1106–1111. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Wyszkowski, M.; Brodowska, M.S. Phytoextraction with maize of soil contaminated with copper after application of mineral and organic amendments. Agronomy 2020 , 10 , 1597. [ Google Scholar ] [ CrossRef ]
• Kosiorek, M.; Wyszkowski, M. Remediation of cobalt-polluted soil after application of selected substances and using oat ( Avena sativa L.). Environ. Sci. Pollut. Res. 2019 , 26 , 16762–16780. [ Google Scholar ] [ CrossRef ]
• Garau, G.; Castaldi, P.; Santona, L.; Deiana, P.; Melis, P. Influence of red mud, zeolite and lime on heavy metal immobilization, culturable heterotophic microbial populations and enzyme activities in a contaminated soil. Geoderma 2007 , 142 , 47–57. [ Google Scholar ] [ CrossRef ]
• Schneider, A.F.; Zimmermann, O.F.; Gewehr, C.E. Zeolites in poultry and swine production. Ciência Rural 2017 , 47 , 1–8. [ Google Scholar ] [ CrossRef ]
• Fuss, V.L.B.; Bruj, G.; Dordai, L.; Roman, M.; Cadar, O.; Becze, A. Evaluation of the impact of different natural zeolite treatments on the capacity of eliminating/reducing odors and toxic compounds. Materials 2021 , 14 , 3724. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Bernal, M.P.; Lopez-Real, J.M. Natural zeolites and sepiolite as ammonium and ammonia adsorbent materials. Bioresour. Technol. 1993 , 43 , 27–33. [ Google Scholar ] [ CrossRef ]
• Awasthi, M.K.; Wang, Q.; Ren, X.; Zhao, J.; Huang, H.; Awasthi, S.K.; Lahori, A.H.; Li, R.; Zhou, L.; Zhang, Z. Role of biochar amendment in mitigation of nitrogen loss and greenhouse gas emission during sewage sludge composting. Bioresour. Technol. 2016 , 219 , 270–280. [ Google Scholar ] [ CrossRef ]
• Chan, M.T.; Selvam, A.; Wong, J.W. Reducing nitrogen loss and salinity during ‘struvite’ food waste composting by zeolite amendment. Bioresour. Technol. 2016 , 200 , 838–844. [ Google Scholar ] [ CrossRef ]
• Wang, Q.; Awasthi, M.K.; Ren, X.; Zhao, J.; Li, R.; Wang, Z.; Wang, M.; Chen, H.; Zhang, Z. Combining biochar, zeolite and wood vinegar for composting of pig manure: The effect on greenhouse gas emission and nitrogen conservation. Waste Manag. 2018 , 74 , 221–230. [ Google Scholar ] [ CrossRef ]
• Akyalcin, S.; Akyalcin, L.; Ertugrul, E. Modification of natural clinoptilolite zeolite to enhance its hydrogen adsorption capacity. Res. Chem. Intermed. 2024 , 1–19. [ Google Scholar ] [ CrossRef ]
• Allen, S.J.; Ivanova, E.; Koumanova, B. Adsorption of sulfur dioxide on chemically modified natural clinoptilolite. Acid modification. Chem. Eng. J. 2009 , 152 , 389–395. [ Google Scholar ] [ CrossRef ]
• Cheng, H.; Ren, X.; Yao, Y.; Tang, X.; Yi, H.; Gao, F.; Zhou, Y.; Yu, Q. Application of unconventional external-field treatments in air pollutants removal over zeolite-based adsorbents/catalysts. Catalysts 2023 , 13 , 1461. [ Google Scholar ] [ CrossRef ]
• Li, J.; Meng, X.; Xiao, F.-S. Zeolites for control of NO x emissions: Opportunities and challenges. ChemCatalysis 2022 , 2 , 253–261. [ Google Scholar ] [ CrossRef ]
• Saramok, M.; Inger, M.; Antoniak-Jurak, K.; Szymaszek-Wawryca, A.; Samojeden, B.; Motak, M. Physicochemical features and NH 3 -SCR catalytic performance of natural zeolite modified with iron—The effect of Fe loading. Catalysts 2022 , 12 , 731. [ Google Scholar ] [ CrossRef ]
• Święs, A.; Kowalczyk, A.; Rutkowska, M.; Díaz, U.; Palomares, A.E.; Chmielarz, L. Ferrierite and its delaminated and silica-intercalated forms modified with copper as effective catalysts for NH 3 -SCR process. Catalysts 2020 , 10 , 734. [ Google Scholar ] [ CrossRef ]
• Chen, C.; Cao, Y.; Liu, S.; Chen, J.; Jia, W. Review on the latest developments in modified vanadium-titanium-based SCR catalysts. Chin. J. Catal. 2018 , 39 , 1347–1365. [ Google Scholar ] [ CrossRef ]
• Ferella, F. A review on management and recycling of spent selective catalytic reduction catalysts. J. Clean. Prod. 2020 , 246 , 118990. [ Google Scholar ] [ CrossRef ]
• Tran, T.; Yu, J.; Gan, L.; Guo, F.; Phan, D.; Xu, G. Upgrading V 2 O 5 -WO 3 /TiO 2 deNO x catalyst with TiO 2 -SiO 2 support prepared from Ti-bearing blast furnace slag. Catalysts 2016 , 6 , 56. [ Google Scholar ] [ CrossRef ]
• Wang, X.; Xu, Y.; Zhao, Z.; Liao, J.; Chen, C.; Li, Q. Recent progress of metal-exchanged zeolites for selective catalytic reduction of NO x with NH 3 in diesel exhaust. Fuel 2021 , 305 , 121482. [ Google Scholar ] [ CrossRef ]
• Han, L.; Cai, S.; Gao, M.; Hasegawa, J.Y.; Wang, P.; Zhang, J.; Shi, L.; Zhang, D. Selective catalytic reduction of NO x with NH 3 by using novel catalysts: State of the art and future prospects. Chem. Rev. 2019 , 119 , 10916–10976. [ Google Scholar ] [ CrossRef ]
• Wang, H.; Huang, B.; Yu, C.; Lu, M.; Huang, H.; Zhou, J. Research progress, challenges and perspectives on the sulfur and water resistance of catalysts for low temperature selective catalytic reduction of NO x by NH 3 . Appl. Catal. A Gen. 2019 , 88 , 117207. [ Google Scholar ] [ CrossRef ]
• Du, J.; Shi, X.; Shan, Y.; Zhang, W.; Yu, Y.; Shan, W.; He, H. Investigation of suitable templates for one-pot-synthesized CuSAPO-34 in NO x abatement from diesel vehicle exhaust. Environ. Sci. Technol. 2020 , 54 , 7870–7878. [ Google Scholar ] [ CrossRef ]
• Shi, X.; Liu, F.; Xie, L.; Shan, W.; He, H. NH 3 -SCR performance of fresh and hydrothermally aged Fe-ZSM-5 in standard and fast selective catalytic reduction reactions. Environ. Sci. Technol. 2013 , 47 , 3293–3298. [ Google Scholar ] [ CrossRef ]
• Zhong, C.; Wu, C.; Zuo, H.; Gu, Z. Theoretical analyses of NH 3 -SCR reaction-mass transfer over Cu-ZSM-5. Can. J. Chem. Eng. 2022 , 100 , 3263–3269. [ Google Scholar ] [ CrossRef ]
• Liu, X.; Sui, Z.; Chen, Z.; Chen, Y.; Liu, H.; Jiang, P.; Shen, Z.; Linghu, W.; Wu, X. Structures and catalytic performances of Me/SAPO-34 (Me = Mn, Ni, Co) catalysts for low-tem perature SCR of NO x by ammonia. J. Environ. Sci. 2021 , 104 , 137–149. [ Google Scholar ] [ CrossRef ]
• Zhu, N.; Lian, Z.; Zhang, Y.; Shan, W.; He, H. Improvement of low-temperature catalytic activity over hierarchical Fe-Beta catalysts for selective catalytic reduction of NO x with NH 3 . Chin. Chem. Lett. 2019 , 30 , 867–870. [ Google Scholar ] [ CrossRef ]
• Hui, K.; Yuan, Y.; Xi, B.; Tan, W. A review of the factors affecting the emission of the ozone chemical precursors VOCs and NO x from the soil. Environ. Int. 2023 , 172 , 107799. [ Google Scholar ] [ CrossRef ]
• Kumar, M.S.; Alphin, M.S.; Manigandan, S.; Vignesh, S.; Vigneshwaran, S.; Subash, T. A review of comparison between the traditional catalyst and zeolite catalyst for ammonia-selective catalytic reduction of NO x . Fuel 2023 , 344 , 128125. [ Google Scholar ] [ CrossRef ]
• Xin, Y.; Li, Q.; Zhang, Z. Zeolitic Materials for DeNO x Selective Catalytic Reduction. ChemCatChem 2018 , 10 , 29–41. [ Google Scholar ] [ CrossRef ]
• Li, P.; Xin, Y.; Zhang, H.; Yang, F.; Tang, A.; Han, D.; Jia, J.; Wang, J.; Li, Z.; Zhang, Z. Recent progress in performance optimization of Cu-SSZ-13 catalyst for selective catalytic reduction of NO x . Front. Chem. 2022 , 10 , 1033255. [ Google Scholar ] [ CrossRef ]
• Paolucci, C.; Verma, A.A.; Bates, S.A.; Kispersky, V.F.; Miller, J.T.; Gounder, R.; Delgass, W.N.; Ribeiro, F.H.; Schneider, W.F. Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13. Angew. Chem. 2014 , 53 , 11828–11833. [ Google Scholar ] [ CrossRef ]
• Song, J.; Wang, Z.; Cheng, X.; Wang, X. State-of-Art Review of NO Reduction Technologies by CO, CH 4 and H 2 . Processes 2021 , 9 , 563. [ Google Scholar ] [ CrossRef ]
• Resini, C.; Montanari, T.; Nappi, L.; Bagnasco, G.; Turco, M.; Busea, G.; Bregani, F.; Notaro, M.; Rocchini, G. Selective catalytic reduction of NO x by methane over Co-H-MFI and Co-H-FER zeolite catalysts: Characterization and catalytic activity. J. Catal. 2003 , 214 , 179–190. [ Google Scholar ] [ CrossRef ]
• Ferriera, A.P.; Henriques, C.; Ribeiro, M.F. SCR of NO with methane over Co-HBEA and PdCo-HBEA catalysts: The promoting effect of steaming over bimetallic catalysts. Catal. Today 2005 , 107 , 181–192. [ Google Scholar ] [ CrossRef ]
• Ferriera, A.P.; Capela, S.; Da Costa, P.; Henriques, C.; Ribeiro, M.F.; Ramoa, R. CH 4 -SCR of NO over Co and Pd ferrierite catalysts: Effect of preoaration on catalytic performance. Catal. Today 2007 , 119 , 156–165. [ Google Scholar ] [ CrossRef ]
• Lee, T.J.; Nam, I.S.; Ham, S.W.; Baek, Y.S.; Shin, K.H. Effect on Pd of the wather tolerance of Co-ferrierite catalysts for NO reduction by CH 4 . Appl. Catal. B 2003 , 4 , 115–129. [ Google Scholar ] [ CrossRef ]
• De Lucas, A.; Valverde, J.L.; Dorado, F.; Romero, A.; Asencio, I. Influence of the ion exchanged metal (Cu, Co, Ni and Mn) on the selective catalytic reduction of NO x over mordenite and ZSM-5. J. Mol. Catal. A Chem. 2005 , 225 , 47–58. [ Google Scholar ] [ CrossRef ]
• Ogura, M.; Kage, S.; Shimojo, T.; Oba, J.; Hayashi, M.; Matsukata, M. Co Cation Effects on Activity and Stability of Isolated Pd(II) Cations in Zeolite Matrices for Selective Catalytic Reduction of Nitric Oxide with Methane. J. Catal. 2002 , 211 , 75–84. [ Google Scholar ] [ CrossRef ]
• Gao, W.; Tang, X.; Yi, H.; Jiang, S.; Yu, Q.; Xie, X.; Zhuang, R. Mesoporous molecular sieve-based materials for catalytic oxidation of VOC: A review. J. Environ. Sci. 2023 , 125 , 112–134. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Wojcik, A.M.; Jansen, J.C.; Maschmeyer, T. Regarding pressure in the adsorber of an adsorption heat pump with thin synthesized zeolite layers on heat exchangers. Microporous Mesoporous Mater. 2001 , 3 , 313–317. [ Google Scholar ] [ CrossRef ]
• Fukai, J.; Wijayanta, A.T. Potential ability of zeolite to generate high-temperature vapor using waste heat. AIP Conf. Proc. 2018 , 1931 , 020001. [ Google Scholar ] [ CrossRef ]
• Tasić, Ž.Z.; Bogdanović, G.D.; Antonijević, M.M. Application of natural zeolite in wastewater treatment—A review. J. Min. Metall. 2019 , 55A , 67–79. [ Google Scholar ] [ CrossRef ]
• El-Shafey, O.; Fathy, N.A.; El-Nabarawy, T. Sorption of ammonium ions onto natural and modified Egyptian kaolinites: Kintic and equilibrium studies. Adv. Phys. Chem. 2014 , 2014 , 935854. [ Google Scholar ] [ CrossRef ]
• Gupta, V.K.; Sadegh, H.; Yari, M.; Shahryari Ghoshekandi, R.; Maazinejad, B.; Chahardori, M. Removal of ammonium ions from wastewater a short review in development of efficient methods. Glob. J. Environ. Sci. Manag. 2015 , 1 , 149–158. [ Google Scholar ] [ CrossRef ]
• Huang, H.; Xiao, X.; Yan, B.; Yang, L. Ammonium removal from aqueous solutions by using natural Chinese (Chende) zeolite as adsorbent. J. Hazard. Mater. 2010 , 175 , 247–252. [ Google Scholar ] [ CrossRef ]
• Liang, Z.; Ni, J. Improving the ammonium ion uptake onto natural zeolite by using an integrated modification process. J. Hazard. Mater. 2009 , 166 , 52–60. [ Google Scholar ] [ CrossRef ]
• Jahani, F.; Sadeghi, R.; Shakeri, M. Ultrasonic-assisted chemical modification of a natural clinoptilolite zeolite: Enhanced ammonium adsorption rate and resistance to disturbing ions. J. Environ. Chem. Eng. 2023 , 11 , 110354. [ Google Scholar ] [ CrossRef ]
• Babel, S.; Kurniawan, T.A. Low-cost adsorbents for heavy metals uptake from contaminated water: A review. J. Hazard. Mater. 2003 , B97 , 219–243. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Galletti, C.; Dosa, M.; Russo, N.; Fino, D. Zn 2+ and Cd 2+ removal from wastewater using clinoptilolite as adsorbent. Environ. Sci. Pollut. Res. 2021 , 28 , 24355–24361. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Senila, L.; Hoaghia, A.; Moldovan, A.; Török, I.A.; Kovacs, D.; Simedru, D.; Tomoiag, C.H.; Senila, M. The potential application of natural clinoptilolite-rich zeolite as support for bacterial community formation for wastewater treatment. Materials 2022 , 15 , 3685. [ Google Scholar ] [ CrossRef ]
• Panayotova, M. Removal of Cr(VI) from wastewater by silver-loaded natural clinoptilolite. E3S Web Conf. 2021 , 280 , 06008. [ Google Scholar ] [ CrossRef ]
• Zhang, Y.; Kou, X.; Lu, H.; Lv, X. The feasibility of adopting zeolite in phosphorus removal from aqueous solutions. Desalin. Water Treat. 2013 , 52 , 4298–4304. [ Google Scholar ] [ CrossRef ]
• Goscianska, J.; Ptaszkowska-Koniarz, M.; Frankowski, M.; Franus, M.; Panek, R.; Franus, W. Removal of phosphate from water by lanthanum-modified zeolites obtained from fly ash. J. Colloid Interface Sci. 2018 , 513 , 72–81. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Koohsaryan, E.; Anbia, M.; Heydar, K.T. Mo-modified hierarchical fau zeolite: A catalyst-adsorbent for oxidative desulfurization of fuel oil. J. Solid State Chem. 2022 , 312 , 123218. [ Google Scholar ] [ CrossRef ]
• Ouyang, W.; Zheng, S.; Wu, C.; Hu, X.; Chen, R.; Zhuo, L.; Wang, Z. Dynamic Ammonia Adsorption by FAU Zeolites to below 0.1 Ppm for Hydrogen Energy Applications. Int. J. Hydrogen Energy 2021 , 46 , 32559–32569. [ Google Scholar ] [ CrossRef ]
• Mofarahi, M.; Gholipour, F. Gas adsorption separation of CO 2 /CH 4 system using zeolite 5A. Microporous Mesoporous Mater. 2014 , 200 , 1–10. [ Google Scholar ] [ CrossRef ]
• Garshasbi, V.; Jahangiri, M.; Anbia, M. Separation of Hydrogen Sulfide from Butane Gas Mixture by Zeolite 13X. Iran. J. Chem. Chem. Eng. 2022 , 41 , 3786–3797. [ Google Scholar ] [ CrossRef ]
• Erdem, E.; Karapinar, N.; Dona, R. The removal of heavy metal cations by natural zeolites. J. Colloid Interface Sci. 2004 , 280 , 309–314. [ Google Scholar ] [ CrossRef ]
• Hashemi, M.S.H.; Eslami, F.; Karimzadeh, R. Organic contaminants removal from industrial wastewater by CTAB treated synthetic zeolite Y. J. Environ. Manag. 2019 , 233 , 785–792. [ Google Scholar ] [ CrossRef ]
• Fu, J.; Ding, C. Study on alkylation of benzene with propylene over MCM-22 zeolite catalyst by in situ IR. Catal. Commun. 2005 , 6 , 770–776. [ Google Scholar ] [ CrossRef ]
• Gerasimov, D.; Kashin, E.V.; Pigoleva, I.V.; Maslov, I.A.; Fadeev, V.V.; Zaglyadova, S.V. Effect of Zeolite Properties on Dewaxing by Isomerization of Different Hydrocarbon Feedstocks. Energy Fuels 2019 , 33 , 3492–3503. [ Google Scholar ] [ CrossRef ]
• Zhang, H.; Kim, Y.; Dutt, P.K. Controlled release of paraquat from surface-modified zeolite Y. Microporous Mesoporous Mater. 2006 , 88 , 312–318. [ Google Scholar ] [ CrossRef ]
• Arruebo, M.; Fernández-Pacheco, R.; Irusta, S.; Arbiol, J.; Ibarra, M.R.; Santamaría, J. Sustained release of doxorubicin from zeolite-magnetite nanocomposites prepared by mechanical activation. Nanotechnology 2006 , 17 , 4057–4064. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Neidrauer, M.; Ercan, U.K.; Bhattacharyya, A.; Samuels, J.; Sedlak, J.; Trikha, R.; Barbee, K.A.; Weingarten, M.S.; Joshi, S.G. Antimicrobial efficacy and wound-healing property of a topical ointment containing nitric-oxide-loaded zeolites. J. Med. Microbiol. 2014 , 63 , 203–209. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Bedi, R.S.; Beving, D.E.; Zanello, L.P.; Yan, Y. Biocompatibility of corrosion-resistant zeolite coatings for titanium alloy biomedical implants. Acta Biomater. 2009 , 5 , 3265–3271. [ Google Scholar ] [ CrossRef ]
• Pavelić, K.; Hadžija, M. Medical Application of Zeolites. In Handbook of Zeolites Science and Technology ; CRC Press: Boca Raton, FL, USA, 2003. [ Google Scholar ]
• Servatan, M.; Zarrintaj, P.; Mahmodi, G.; Kim, S.-J.; Ganjali, M.R.; Saeb, M.R.; Mozafari, M. Zeolites in drug delivery: Progress, challenges and opportunities. Drug Discov. Today 2020 , 4 , 642–656. [ Google Scholar ] [ CrossRef ]
• Bonferoni, M.C.; Cerri, G.; Gennaro, M.; Juliano, C.; Caramella, C. Zn 2+ -exchanged clinoptilolite-rich rock as active carrier for antibiotics in anti-acne topical therapy: In-vitro characterization and preliminary formulation studies. Appl. Clay Sci. 2007 , 36 , 95–102. [ Google Scholar ] [ CrossRef ]
• Suresh, S.; Ragula, U.B.R. A regenerative adsorption technique for removal of uremic toxins: An alternative to conventional haemodialysis. Mater. Today Proc. 2020 , 24 , 714–723. [ Google Scholar ] [ CrossRef ]
• Deshpande, S.; Kheur, S.; Kheur, M.; Eyüboğlu, T.F.; Özcan, M. A Review on Zeolites and Their Applications in Dentistry. Curr. Oral Health Rep. 2023 , 10 , 36–42. [ Google Scholar ] [ CrossRef ]
• Rodríguez-Fuentes, G.; Barrios, M.A.; Cedré, B.; Perdomo, I. Enterex: Anti-diarrheic drug based on purified natural clinoptilolite. Zeolites 1997 , 19 , 441–448. [ Google Scholar ] [ CrossRef ]
• Rodríguez-Fuentes, G.; Denis, A.R.; Barrios Álvarez, M.A.; Colarte, A.I. Antacid drug based on purified natural clinoptilolite. Microporous Mesoporous Mater. 2006 , 94 , 200–207. [ Google Scholar ] [ CrossRef ]
• Basha, M.P.; Begum, S.; Mir, B.A. Neuroprotective actions of clinoptilolite and ethylenediaminetetraacetic acid against lead-introduced toxicity in mice Mus musculus . Toxicol. Int. 2013 , 20 , 201–207. [ Google Scholar ] [ CrossRef ]
• Li, Y.; Cai, Y.; Chen, T.; Bao, X. Zeolites: A series of promising biomaterials in bone tissue engineering. Front. Bioeng. Biotechnol. 2022 , 10 , 1066552. [ Google Scholar ] [ CrossRef ]
• Zarrintaj, P.; Mahmodi, G.; Manouchehri, S.; Mashhadzadeh, A.H.; Khodadadi, M.; Servatan, M.; Ganjali, M.R.; Azambre, B.; Kim, S.-J.; Ramsey, J.D.; et al. Zeolite in tissue engineering: Opportunities and challenges. MedComm 2020 , 1 , 5–34. [ Google Scholar ] [ CrossRef ]
• Banu, J.; Varela, E.; Guerra, J.M.; Halade, G.; Williams, P.J.; Bahadur, A.N.; Hanaoka, K.; Fernandes, G. Dietary coral calcium and zeolite protects bone in a mouse model for postmenopausal bone loss. Nutr. Res. 2012 , 32 , 965–975. [ Google Scholar ] [ CrossRef ]
• Serati-Nouri, H.; Jafari, A.; Roshangar, L.; Cadashpour, M.; Pilehvar-Soltanahmadi, Y.; Zarghami, N. Biomedical applications of zeolite-based materials: A review. Mater. Sci. Eng. C 2020 , 116 , 111225. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Linares, C.F.; Solano, S.; Infante, G. The influence of hydrotalcite and cancrinite-type zeolite in acidic aspirin solutions. Microporous Mesoporous Mater. 2004 , 74 , 105–110. [ Google Scholar ] [ CrossRef ]
• Shan, W.; Yu, T.; Wang, B.; Hu, J.; Zhang, Y.; Wang, X.; Tang, Y. Magnetically separable nanozeolites: Promising candidates for bio-applications. Chem. Mater. 2006 , 18 , 3169–3172. [ Google Scholar ] [ CrossRef ]
• Matusiak, J.; Przekora, A.; Franus, W. Zeolites and zeolite imidazolate frameworks on a quest to obtain the ideal biomaterial for biomedical applications: A review. Mater. Today 2023 , 67 , 495–517. [ Google Scholar ] [ CrossRef ]
• Kubota, M.; Nakabayashi, T.; Matsumoto, Y.; Shiomi, T.; Yamada, Y.; Ino, K.; Yamanokuchi, H.; Matsui, M.; Tsunoda, T.; Mizukami, F.; et al. Selective adsorption of bacterial cells onto zeolites. Colloids Surf. B Biointerfaces 2008 , 64 , 88–97. [ Google Scholar ] [ CrossRef ] [ PubMed ]
• Chen, S.; Popovich, J.; Zhang, W.; Ganser, C.; Haydel, S.E.; Seo, D.-K. Superior ion release properties and antibacterial efficacy of nanostructured zeolites ion-exchanged with zinc, copper, and iron. RSC Adv. 2018 , 8 , 37949. [ Google Scholar ] [ CrossRef ]
• Inoue, Y.; Hoshino, M.; Takahashi, H.; Noguchi, T.; Murata, T.; Kanzaki, Y.; Hamashima, H.; Sasatsu, M. Bactericidal activity of Ag-zeolite mediated by reactive oxygen species under aerated conditions. J. Inorg. Biochem. 2002 , 92 , 37–42. [ Google Scholar ] [ CrossRef ]

Share and Cite

Kordala, N.; Wyszkowski, M. Zeolite Properties, Methods of Synthesis, and Selected Applications. Molecules 2024 , 29 , 1069. https://doi.org/10.3390/molecules29051069

Kordala N, Wyszkowski M. Zeolite Properties, Methods of Synthesis, and Selected Applications. Molecules . 2024; 29(5):1069. https://doi.org/10.3390/molecules29051069

Kordala, Natalia, and Mirosław Wyszkowski. 2024. "Zeolite Properties, Methods of Synthesis, and Selected Applications" Molecules 29, no. 5: 1069. https://doi.org/10.3390/molecules29051069

Article Metrics

Article access statistics, further information, mdpi initiatives, follow mdpi.

Subscribe to receive issue release notifications and newsletters from MDPI journals

• Search Menu
• Sign in through your institution
• Computer Science
• Earth Sciences
• Information Science
• Life Sciences
• Materials Science
• Science Policy
• Advance Access
• Special Topics
• Author Guidelines
• Submission Site
• Open Access Options
• Self-Archiving Policy
• Reasons to submit
• About National Science Review
• Editorial Board
• Advertising and Corporate Services
• Journals Career Network
• Dispatch Dates
• Journals on Oxford Academic
• Books on Oxford Academic

Article Contents

Preface to special topic on new era of zeolite science.

Guest Editor of Special Topic

Editorial Board Member for NSR

Associate Editor-in-Chief for Materials Science for NSR

• Article contents
• Figures & tables
• Supplementary Data

Jihong Yu, Dongyuan Zhao, Preface to special topic on new era of zeolite science, National Science Review , Volume 9, Issue 9, September 2022, nwac157, https://doi.org/10.1093/nsr/nwac157

• Permissions Icon Permissions

Zeolites are crystalline microporous solids whose frameworks are composed of corner-sharing tetrahedral TO 4 units (T = Si, Al, P, etc.), forming periodic one-dimensional (1D) to three-dimensional (3D) channels with an aperture size of typically <2 nm. Because of their unique pore structures, large specific surface area, strong acid sites, high thermal/hydrothermal stability and molecular-level shape selectivity, zeolites are widely used as catalysts, adsorbents and ion exchangers in the fields of oil refining, petrochemical industry, coal chemical industry and daily chemical industry.

Almost 60 years have passed since the first industrial application of Y zeolite in oil cracking, which caused the ‘technical revolution in the refinery industry’. To date, the Structure Committee of the International Zeolite Association has certified over 250 types of zeolite structures, of which nearly 20 have achieved industrial application, leading to a series of milestone technological revolutions in energy, chemical and environmental fields, as well as other fields, in the past few decades. For example, titanium silicalite (TS-1) zeolites can catalyze propylene epoxidation directly to propylene oxide under mild conditions, which promotes the generation and development of green chemistry and atomic economy processes and is known as a ‘green catalytic milestone’; zeolite Cu-SSZ-13 can efficiently catalyze selective reduction of NO x in heavy duty diesel vehicle exhaust, which can significantly reduce exhaust emissions; highly efficient catalytic conversion of methanol to ethylene and propylene by zeolite SAPO-34 makes coal an important raw material for the production of bulk basic organic chemicals; the lithium-ion-exchanged low-silica X zeolite has greatly improved oxygen production efficiency via pressure swing adsorption (PSA), which provides support for low-cost oxygen use in many arenas, such as the chemical industry and steel, cement and medical treatment fields; a composite of partially reduced oxide (ZnCrOx) and mesoporous SAPO-34 zeolite (MSAPO) broke the Anderson-Schulz-Flory (ASF) limit in a direct synthesis gas (syngas) conversion to light olefins (C 2 = –C 4 = ) via Fischer-Tropsch synthesis (FTS); and very recently, ultrathin membranes of Li-exchanged X zeolites were used as chemically stable solid electrolytes, which gave the resultant solid-state Li–air battery a greater cycle life than batteries based on conventional solid electrolytes and organic electrolytes under the same conditions.

In recent years, with the progress of synthetic chemistry, the development of characterization technologies and theoretical calculations, and interdisciplinary integration, global zeolite research has experienced a new upsurge. Breakthrough progress has been made in the discovery of new zeolites, zeolite structure characterization, theoretical simulations, efficient catalysis and adsorptive separation. Progress has also been made with regard to new applications in energy storage, optoelectronic devices, biomedicine and biomass conversion. To highlight recent developments and crucial issues for future research in zeolite science, we have organized this special-topic issue, ‘New Era of Zeolite Science’.

This special topic includes one perspective, four research articles, five reviews and one interview. In the perspective, Mintova et al . show the exploration, explanation and exploitation of hydroxyls in zeolites.

In the research articles, Corma et al. illustrate the enzymatic and chemo-enzymatic strategies of producing highly valuable chiral amines from biomass with ω-transaminases on 2D zeolites; Yu et al. unravel the templated-regulated distribution of isolated SiO 4 tetrahedra in silicoaluminophosphate zeolites with high-throughput computations; Liu et al. present the multiscale dynamical cross-talk in zeolite-catalyzed methanol and dimethyl ether conversions; and Bao et al. show the dynamic confinement of SAPO-17 cages on the selectivity control of syngas conversion.

In the reviews, Weckhuysen et al. review emerging analytical methods of characterizing zeolite-based materials; Xiao et al. summarize the targeted synthesis of zeolites from calculated interaction between zeolite structure and organic template; Deng et al. give an overview of recent advances in solid-state NMR of zeolite catalysts; Wu et al. present new progress in zeolite synthesis and catalysis; and Yu et al. review low-energy adsorptive separation by zeolites.

In the interview, Prof. Ruren Xu, an early leader within Chinese, Asian and worldwide zeolite communities, the founder of the inorganic synthesis discipline in China and the first proposer of the scientific discipline of modern inorganic synthetic chemistry in the world, highlights frontiers in zeolites towards establishing a new discipline of condensed matter chemistry.

We thank all the authors and editorial staff for their efforts in making this theme possible. Special thanks goes to Prof. Ruren Xu and Prof. Wenfu Yan for the interview. Zeolite is an old material, however, its application has been extended to many sustainable processes, which promises a brilliant new future.

Author notes

Email alerts

Citing articles via.

• Recommend to Your Librarian

Affiliations

• Online ISSN 2053-714X
• Print ISSN 2095-5138
• Copyright © 2024 China Science Publishing & Media Ltd. (Science Press)
• About Oxford Academic
• Publish journals with us
• University press partners
• What we publish
• New features  
• Open access
• Institutional account management
• Rights and permissions
• Get help with access
• Accessibility
• Advertising
• Media enquiries
• Oxford University Press
• Oxford Languages
• University of Oxford

Oxford University Press is a department of the University of Oxford. It furthers the University's objective of excellence in research, scholarship, and education by publishing worldwide

• Copyright © 2024 Oxford University Press
• Cookie settings
• Cookie policy
• Privacy policy
• Legal notice

This Feature Is Available To Subscribers Only

Sign In or Create an Account

This PDF is available to Subscribers Only

For full access to this pdf, sign in to an existing account, or purchase an annual subscription.

Suggestions or feedback?

MIT News | Massachusetts Institute of Technology

• Machine learning
• Sustainability
• Black holes
• Classes and programs

Departments

• Aeronautics and Astronautics
• Brain and Cognitive Sciences
• Architecture
• Political Science
• Mechanical Engineering

Centers, Labs, & Programs

• Abdul Latif Jameel Poverty Action Lab (J-PAL)
• Picower Institute for Learning and Memory
• Lincoln Laboratory
• School of Architecture + Planning
• School of Engineering
• School of Humanities, Arts, and Social Sciences
• Sloan School of Management
• School of Science
• MIT Schwarzman College of Computing

A new mathematical approach to understanding zeolites

Press contact :.

Previous image Next image

Zeolites are a class of natural or manufactured minerals with a sponge-like structure, riddled with tiny pores that make them useful as catalysts or ultrafine filters. But of the millions of zeolite compositions that are theoretically possible, so far only about 248 have ever been discovered or made. Now, research from MIT helps explain why only this small subset has been found, and could help scientists find or produce more zeolites with desired properties.

The new findings are being reported this week in the journal Nature Materials , in a paper by MIT graduate students Daniel Schwalbe-Koda and Zach Jensen, and professors Elsa Olivetti and Rafael Gomez-Bombarelli.

Previous attempts to figure out why only this small group of possible zeolite compositions has been identified, and to explain why certain types of zeolites can be transformed into specific other types, have failed to come up with a theory that matches the observed data. Now, the MIT team has developed a mathematical approach to describing the different molecular structures. The approach is based on graph theory, which can predict which pairs of zeolite types can be transformed from one to the other.

This could be an important step toward finding ways of making zeolites tailored for specific purposes. It could also lead to new pathways for production, since it predicts certain transformations that have not been previously observed. And, it suggests the possibility of producing zeolites that have never been seen before, since some of the predicted pairings would lead to transformations into new types of zeolite structures.

Interzeolite tranformations

Zeolites are widely used today in applications as varied as catalyzing the “cracking” of petroleum in refineries and absorbing odors as components in cat litterbox filler. Even more applications may become possible if researchers can create new types of zeolites, for example with pore sizes suited to specific types of filtration.

All kinds of zeolites are silicate minerals, similar in chemical composition to quartz. In fact, over geological timescales, they will all eventually turn into quartz — a much denser form of the mineral — explains Gomez-Bombarelli, who is the Toyota Assistant Professor in Materials Processing. But in the meantime, they are in a “metastable” form, which can sometimes be transformed into a different metastable form by applying heat or pressure or both. Some of these transformations are well-known and already used to produce desired zeolite varieties from more readily available natural forms.

Currently, many zeolites are produced by using chemical compounds known as OSDAs (organic structure-directing agents), which provide a kind of template for their crystallization. But Gomez-Bombarelli says that if instead they can be produced through the transformation of another, readily available form of zeolite, “that’s really exciting. If we don’t need to use OSDAs, then it’s much cheaper [to produce the material].The organic material is pricey. Anything we can make to avoid the organics gets us closer to industrial-scale production.”

Traditional chemical modeling of the structure of different zeolite compounds, researchers have found, provides no real clue to finding the pairs of zeolites that can readily transform from one to the other. Compounds that appear structurally similar sometimes are not subject to such transformations, and other pairs that are quite dissimilar turn out to easily interchange. To guide their research, the team used an artificial intelligence system previously developed by the Olivetti group to “read” more than 70,000 research papers on zeolites and select those that specifically identify interzeolite transformations. They then studied those pairs in detail to try to identify common characteristics.

What they found was that a topological description based on graph theory, rather than traditional structural modeling, clearly identified the relevant pairings. These graph-based descriptions, based on the number and locations of chemical bonds in the solids rather than their actual physical arrangement, showed that all the known pairings had nearly identical graphs. No such identical graphs were found among pairs that were not subject to transformation.

The finding revealed a few previously unknown pairings, some of which turned out to match with preliminary laboratory observations that had not previously been identified as such, thus helping to validate the new model. The system also was successful at predicting which forms of zeolites can intergrow — forming combinations of two types that are interleaved like the fingers on two clasped hands. Such combinations are also commercially useful, for example for sequential catalysis steps using different zeolite materials.

Ripe for further research  

The new findings might also help explain why many of the theoretically possible zeolite formations don’t seem to actually exist. Since some forms readily transform into others, it may be that some of them transform so quickly that they are never observed on their own. Screening using the graph-based approach may reveal some of these unknown pairings and show why those short-lived forms are not seen.

Some zeolites, according to the graph model, “have no hypothetical partners with the same graph, so it doesn’t make sense to try to transform them, but some have thousands of partners” and thus are ripe for further research, Gomez-Bombarelli says.

In principle, the new findings could lead to the development of a variety of new catalysts, tuned to the exact chemical reactions they are intended to promote. Gomez-Bombarelli says that almost any desired reaction could hypothetically find an appropriate zeolite material to promote it.

“Experimentalists are very excited to find a language to describe their transformations that is predictive,” he says.

This work is “a major advancement in the understanding of interzeolite transformations, which has become an increasingly important topic owing to the potential for using these processes to improve the efficiency and economics of commercial zeolite production,” says Jeffrey Rimer, an associate professor of chemical and biomolecular engineering at the University of Houston, who was not involved in this research.

Manuel Moliner, a tenured scientist at the Technical University of Valencia, in Spain, who also was not connected to this research, says: “Understanding the pairs involved in particular interzeolite transformations, considering not only known zeolites but also hundreds of hypothetical zeolites that have not ever been synthesized, opens extraordinary practical opportunities to rationalize and direct the synthesis of target zeolites with potential interest as industrial catalysts.”

This research was supported, in part, by the National Science Foundation and the Office of Naval Research.

Share this news article on:

Related links.

• Rafael Gomez-Bombarelli
• Elsa Olivetti
• Daniel Schwalbe-Koda
• Materials Research Laboratory
• Department of Materials Science and Engineering

Related Topics

• Materials science and engineering
• Nanoscience and nanotechnology
• Energy storage
• Artificial intelligence
• National Science Foundation (NSF)

Related Articles

Can computers help us synthesize new materials?

Artificial intelligence aids materials fabrication

Opportunities for materials innovation abound

Previous item Next item

More MIT News

President Kornbluth welcomes the Class of 2028

Read full story →

Scientists find neurons that process language on different timescales

Pursuing the secrets of a stealthy parasite

Study of disordered rock salts leads to battery breakthrough

Toward a code-breaking quantum computer

Uphill battles: Across the country in 75 days

• More news on MIT News homepage →

Massachusetts Institute of Technology 77 Massachusetts Avenue, Cambridge, MA, USA

• Map (opens in new window)
• Events (opens in new window)
• People (opens in new window)
• Careers (opens in new window)
• Accessibility
• Social Media Hub
• MIT on Facebook
• MIT on YouTube
• MIT on Instagram

An official website of the United States government

The .gov means it’s official. Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

The site is secure. The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

• Publications
• Account settings
• My Bibliography
• Collections
• Citation manager

Save citation to file

Email citation, add to collections.

• Create a new collection
• Add to an existing collection

Add to My Bibliography

Your saved search, create a file for external citation management software, your rss feed.

• Search in PubMed
• Search in NLM Catalog
• Add to Search

Properties and applications of zeolites

Affiliation.

• 1 University of Reading. [email protected]
• PMID: 21047018
• PMCID: PMC10365492
• DOI: 10.3184/003685010X12800828155007

Zeolites are aluminosilicate solids bearing a negatively charged honeycomb framework of micropores into which molecules may be adsorbed for environmental decontamination, and to catalyse chemical reactions. They are central to green-chemistry since the necessity for organic solvents is minimised. Proton-exchanged (H) zeolites are extensively employed in the petrochemical industry for cracking crude oil fractions into fuels and chemical feedstocks for other industrial processes. Due to their ability to perform cation-exchange, in which the cations that are originally present to counterbalance the framework negative charge may be exchanged out of the zeolite by cations present in aqueous solution, zeolites are useful as industrial water-softeners, in the removal of radioactive Cs+ and Sr2+ cations from liquid nuclear waste and in the removal of toxic heavy metal cations from groundwaters and run-off waters. Surfactant-modified zeolites (SMZ) find particular application in the co-removal of both toxic anions and organic pollutants. Toxic anions such as arsenite, arsenate, chromate, cyanide and radioactive iodide can also be removed by adsorption into zeolites that have been previously loaded with co-precipitating metal cations such as Ag+ and Pb2+ which form practically insoluble complexes that are contained within the zeolite matrix.

PubMed Disclaimer

Similar articles

• Adsorption of chromate by clinoptilolite exchanged with various metal cations. Faghihian H, Bowman RS. Faghihian H, et al. Water Res. 2005 Mar;39(6):1099-104. doi: 10.1016/j.watres.2004.12.010. Water Res. 2005. PMID: 15766964
• Preparation and application of organo-modified zeolitic material in the removal of chromates and iodides. Warchoł J, Misaelides P, Petrus R, Zamboulis D. Warchoł J, et al. J Hazard Mater. 2006 Oct 11;137(3):1410-6. doi: 10.1016/j.jhazmat.2006.04.028. Epub 2006 Apr 27. J Hazard Mater. 2006. PMID: 16716505
• Studies of anions sorption on natural zeolites. Barczyk K, Mozgawa W, Król M. Barczyk K, et al. Spectrochim Acta A Mol Biomol Spectrosc. 2014 Dec 10;133:876-82. doi: 10.1016/j.saa.2014.06.065. Epub 2014 Jun 19. Spectrochim Acta A Mol Biomol Spectrosc. 2014. PMID: 25002191
• Synthesis of zeolite from industrial wastes: a review on characterization and heavy metal and dye removal. Eren S, Türk FN, Arslanoğlu H. Eren S, et al. Environ Sci Pollut Res Int. 2024 Jun;31(29):41791-41823. doi: 10.1007/s11356-024-33863-0. Epub 2024 Jun 11. Environ Sci Pollut Res Int. 2024. PMID: 38861062 Free PMC article. Review.
• Effects of zeolites on cultures of marine micro-algae: A brief review. Fachini A, Vasconcelos MT. Fachini A, et al. Environ Sci Pollut Res Int. 2006 Oct;13(6):414-7. doi: 10.1065/espr2006.01.293. Environ Sci Pollut Res Int. 2006. PMID: 17120832 Review.
• Description and management of Aspergillus section Nigri causing post-harvest bulbs rot of onion. El-Dawy EGAM, Hussein MA, El-Nahas S. El-Dawy EGAM, et al. Sci Rep. 2024 Mar 13;14(1):6076. doi: 10.1038/s41598-024-53849-9. Sci Rep. 2024. PMID: 38480751 Free PMC article.
• Zeolite Properties, Methods of Synthesis, and Selected Applications. Kordala N, Wyszkowski M. Kordala N, et al. Molecules. 2024 Feb 29;29(5):1069. doi: 10.3390/molecules29051069. Molecules. 2024. PMID: 38474578 Free PMC article. Review.
• Elucidated potential of immobilized Janibacter sp. for saline wastewater phenol removal. Vanak Z, Asad S, Dastgheib SMM. Vanak Z, et al. Appl Microbiol Biotechnol. 2023 Nov;107(22):6999-7011. doi: 10.1007/s00253-023-12760-5. Epub 2023 Sep 15. Appl Microbiol Biotechnol. 2023. PMID: 37713116
• A Comprehensive Review on Zeolite Chemistry for Catalytic Conversion of Biomass/Waste into Green Fuels. Qazi UY, Javaid R, Ikhlaq A, Khoja AH, Saleem F. Qazi UY, et al. Molecules. 2022 Dec 5;27(23):8578. doi: 10.3390/molecules27238578. Molecules. 2022. PMID: 36500669 Free PMC article. Review.
• Surface Modification of Synthetic Zeolites with Ca and HDTMA Compounds with Determination of Their Phytoavailability and Comparison of CEC and AEC Parameters. Łach M, Grela A, Pławecka K, Guigou MD, Mikuła J, Komar N, Bajda T, Korniejenko K. Łach M, et al. Materials (Basel). 2022 Jun 8;15(12):4083. doi: 10.3390/ma15124083. Materials (Basel). 2022. PMID: 35744143 Free PMC article.
• Mumpton F.A. (1999) Proc. Natl. Acad. Sci. USA, 96, 3463. - PMC - PubMed
• Barrer R.M. (1978) Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Academic Press, London.
• http://en.wikipedia.org/wiki/Zeolite and links therein.
• Cronstedt A.F. (1756) Kongl. Vetenskaps Akad. Handl. Stockholm, 17, 120.
• Rhodes C.J. (2007) Annu. Rep. Prog. Chem., Sect. C: Phys. Chem., 103, 287.

Publication types

• Search in MeSH

Related information

• PubChem Compound (MeSH Keyword)

LinkOut - more resources

Full text sources.

• Europe PubMed Central
• PubMed Central

Other Literature Sources

• The Lens - Patent Citations

• Citation Manager

NCBI Literature Resources

MeSH PMC Bookshelf Disclaimer

The PubMed wordmark and PubMed logo are registered trademarks of the U.S. Department of Health and Human Services (HHS). Unauthorized use of these marks is strictly prohibited.

arXiv's Accessibility Forum starts next month!

Help | Advanced Search

Computer Science > Computation and Language

Title: coderefine: a pipeline for enhancing llm-generated code implementations of research papers.

Abstract: This paper presents CodeRefine, a novel framework for automatically transforming research paper methodologies into functional code using Large Language Models (LLMs). Our multi-step approach first extracts and summarizes key text chunks from papers, analyzes their code relevance, and creates a knowledge graph using a predefined ontology. Code is then generated from this structured representation and enhanced through a proposed retrospective retrieval-augmented generation approach. CodeRefine addresses the challenge of bridging theoretical research and practical implementation, offering a more accurate alternative to LLM zero-shot prompting. Evaluations on diverse scientific papers demonstrate CodeRefine's ability to improve code implementation from the paper, potentially accelerating the adoption of cutting-edge algorithms in real-world applications.

Submission history

Access paper:.

• HTML (experimental)
• Other Formats

References & Citations

• Google Scholar
• Semantic Scholar

BibTeX formatted citation

Bibliographic and Citation Tools

Code, data and media associated with this article, recommenders and search tools.

• Institution

arXivLabs: experimental projects with community collaborators

arXivLabs is a framework that allows collaborators to develop and share new arXiv features directly on our website.

Both individuals and organizations that work with arXivLabs have embraced and accepted our values of openness, community, excellence, and user data privacy. arXiv is committed to these values and only works with partners that adhere to them.

Have an idea for a project that will add value for arXiv's community? Learn more about arXivLabs .

An official website of the United States government

The .gov means it’s official. Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

The site is secure. The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

• Publications
• Account settings

Preview improvements coming to the PMC website in October 2024. Learn More or Try it out now .

• Advanced Search
• Journal List
• Biology (Basel)

The Impact of Long-Term Clinoptilolite Administration on the Concentration Profile of Metals in Rodent Organisms

Ivan dolanc.

1 Centre for Applied Bioanthropology, Institute for Anthropological Research, 10000 Zagreb, Croatia

Lejla Ferhatović Hamzić

Tatjana orct.

2 Institute for Medical Research and Occupational Health, 10000 Zagreb, Croatia

Vedran Micek

Iva Šunić, antonija jonjić, jasna jurasović, saša missoni.

3 Institute for Anthropological Research, 10000 Zagreb, Croatia

4 Faculty of Dental Medicine and Health, University of Osijek, 31000 Osijek, Croatia

Miran Čoklo

Sandra kraljević pavelić.

5 Faculty of Health Studies, University of Rijeka, Viktora Cara Emina 5, 51000 Rijeka, Croatia

Associated Data

Not applicable.

Simple Summary

Human activities such as heavy industry and transport have significantly increased the levels of many poisonous chemicals in the human environment. Among these chemicals are heavy metals, which pose a great risk to human health because they cannot decompose and cannot be eliminated from the human body by metabolic processes. Volcanic stone called clinoptilolite is inert and extremely porous, and can capture heavy metals into its meshed structure. Therefore, it can be used as a food supplement for detox purposes. Several clinical studies have already indicated its detoxifying, antioxidant and anti-inflammatory effects. In our experiment, we fed healthy rats with clinoptilolite, which was milled to fine dust to improve performance, for three months. Two forms were used: tribomechanically activated zeolite and Panaceo-Micro-Activated zeolite. Upon completion of the administration period, we observed the impact of clinoptilolite dust on the metallic composition in different rat tissues and bloodstream. Our results showed that this activated natural stone had indeed released metallic toxicants from the rat organs to the bloodstream, which indicates a detoxification process.

Heavy metals are dangerous systemic toxicants that can induce multiple organ damage, primarily by inducing oxidative stress and mitochondrial damage. Clinoptilolite is a highly porous natural mineral with a magnificent capacity to eliminate metals from living organisms, mainly by ion-exchange and adsorption, thus providing detoxifying, antioxidant and anti-inflammatory medicinal effects. The in vivo efficiency and safety of the oral administration of clinoptilolite in its activated forms, tribomechanically activated zeolite (TMAZ) and Panaceo-Micro-Activated (PMA) zeolite, as well as the impact on the metallic biodistribution, was examined in healthy female rats. Concentration profiles of Al, As, Cd, Co, Pb, Ni and Sr were measured in rat blood, serum, femur, liver, kidney, small and large intestine, and brain using inductively coupled plasma mass spectrometry (ICP-MS) after a 12-week administration period. Our results point to a beneficial effect of clinoptilolite materials on the concentration profile of metals in female rats supplemented with the corresponding natural clinoptilolite materials, TMAZ and PMA zeolite. The observed decrease of measured toxicants in the kidney, femur, and small and large intestine after three months of oral intake occurred concomitantly with their most likely transient release into the bloodstream (serum) indicative of a detoxification process.

1. Introduction

Metals are ubiquitous and naturally occurring in the Earth’s crust and atmosphere, but their concentrations have recently risen to extreme levels in the environment. This is to a great extent a byproduct of human activities such as agriculture, heavy industry, transport, cosmetics, natural medicaments and the beauty industry [ 1 , 2 , 3 ]. Of particular concern is the highly increased abundancy of heavy metals, characterized by high atomic weight and a density of at least 5 g/cm 3 . These metals adversely affect the environment and living organisms. Generally, they are considered toxic, depending on the chemical species, dose and route of exposure, as well as on the age, gender, pharmacogenetics and nutritional status of exposed persons. Of the metals, arsenic (As), cadmium (Cd), chromium (Cr) and lead (Pb) are highly dangerous [ 4 ]. Considered as systemic toxicants, they are capable of inducing multiple organ damage even at low concentrations, primarily by the induction of oxidative stress and mitochondrial damage [ 4 , 5 ].

Metal toxicity can be acute or chronic, depending on the absorbed dose, and the route and duration of exposure. Even though prolonged exposure to low quantities of heavy metals and even aluminum (Al), classified as a light metal, in the short-term are not considered to be generally noxious (e.g., via cosmetics), various toxic effects including allergic contact dermatitis or systemic toxicity have been documented [ 6 ]. A few metals can be removed from living organisms by metabolic elimination (e.g., Al), but the majority of metals accumulate in the body, imposing a long-term health risk. Mechanistically, they bind to proteins by displacing original metals from their natural bidding sites and cause the malfunctioning of proteins, cells and tissues. The oxidative deterioration of biomolecules is primarily due to the binding of metals to DNA and nucleic proteins [ 7 ]. Consequential health perturbations may include osteoporosis, carcinogenesis, neurodegeneration, oxidative stress, endocrine disruption, DNA damage and immune system deterioration, organ failure and disturbances in reproduction [ 2 , 8 , 9 , 10 ].

Although the individual health hazards of Pb, Cd and mercury (Hg) exposure are extensively studied, more attention should be given to the examination of their synergistic effect, since combined exposure to these toxicants in environmentally relevant concentrations causes damage to multiple organs as well as impairment of the neurobehavioral functions of rats [ 11 , 12 ].

Several metals are considered essential and nutritionally valuable, since they play an important role in human physiology. Other metals, often referred to as heavy metals, such as As, Cd and Pb, are common food contaminants, with unknown biological functions and considerable negative impact on human health [ 1 , 13 , 14 ]. Some biological consequences documented for heavy metals include inflammation, oxidative stress, endocrine disruption and intestinal disorders correlated with gut microflora perturbations, and compositional and metabolic profile changes. Probiotic strains and their enzymes may help in the alleviation of these effects [ 15 ]. Some trace minerals (also belonging to metals) exhibit beneficial effects in vivo and may ameliorate metallic toxicity. One such element is selenium (Se), which sequesters As and Cd and incorporates them into inert complexes. Moreover, Se induces the erythroid 2-related factor 2 (Nrf2) pathway. This highly biologically active protein is a potent regulator of metallic toxicity. It triggers protective oxidative stress mechanisms through the release of antioxidants [ 16 , 17 ].

Importantly, the basic harmfulness to health of Al mainly arises from its pro-oxidant activity and consequential oxidative stress that leads to degradation of cellular proteins and lipids. Chronic excessive exposure to Al may provoke oxidative stress, tissue inflammation, genotoxicity, carcinogenesis, teratogenesis, tissue necrosis, endocrine disruption, diabetes onset, obesity, inhibition of cartilage and bone formation, hypertension, ischemic stroke and thrombosis [ 18 ]. Circulating Al is usually bound to transferrin, which seems to potentiate Al entrance in the central nervous system in a manner similar to iron [ 19 ]. Accordingly, increased Al levels in the brain are detrimental, and high interconnections of Al deposition in the brain are in correlation with neurotoxic effects, pathogenesis of Alzheimer disease [ 20 , 21 ] and autism spectrum disorders [ 22 ]. Thus, Al detoxification might be considered as a possible therapeutic approach in these conditions, as already seen in patients with Alzheimer’s disease [ 23 ].

Arsenic toxicity emerges from its extensive binding affinity and inhibition of selenoenzymes, which are known scavengers of reactive oxygen species [ 24 ]. This causes multiple changes in cell behavior through alterations in signaling pathways and epigenetic modifications, as well as direct oxidative damage to proteins and lipids [ 25 ]. Acute As poisoning causes abdominal pain and gastrointestinal problems [ 26 ]. Prolonged As exposure may cause skin lesions, development of neoplasms, peripheral neuropathy, cardiovascular disease and neurodevelopmental problems [ 24 ]. However, in addition to its toxic effect, As has certain beneficial medical properties. Specifically, As trioxide greatly improves the survival of patients suffering from acute promyelocytic leukemia [ 27 ]. Such applications fall into a specific and controlled medical therapy field.

Cadmium possesses no known biological function in humans, but has a very low rate of excretion and tends to accumulate in organs (e.g., brain, liver, kidney and testes), causing their impairment. It reduces the reproduction of both sexes even at low doses [ 28 ]. Its strongest toxic effects are seen in kidneys. Cd tends to accumulate in this organ as a result of its preferential uptake by receptor-mediated endocytosis in the proximal tubules. This triggers proteinuria, which can progress to renal Fanconi syndrome and eventually renal failure [ 29 , 30 ]. To exert the toxic effect, Cd must enter the intracellular space [ 31 ], where it triggers oxidative, apoptotic, spermal and steroidogenic toxicity [ 32 ]. Moreover, this metal exerts immunomodulatory function, and can trigger the release of chemokines, regulate gene expression and attenuate inflammation [ 33 ]. Although extensive research is being conducted, no efficient Cd antidotes are available for clinical application so far [ 34 ].

Cobalt (Co) is biologically relevant for the formation of vitamin B-12, but excessive exposure to this metal correlates with some pathological conditions such as the development of reduced thyroid activity, interstitial pulmonary fibrosis and cardiomyopathy [ 35 ]. Humans are usually exposed to Co via four distinct routes: occupational, environmental, dietary and medical. Of these, oral intake and internal exposure through hip implants are the most common medical hazards for the development of Co systemic toxicity. The release of free ionic Co 2+ upon prolonged excessive exposure to this element seems to underlie cobalt-induced chronic poisoning [ 36 ]. In microorganisms, Co is highly receptive to iron sulfur proteins, and, perturbing iron homeostasis, it incites oxidative stress [ 37 ].

Lead is not biodegradable, and when absorbed in organisms, it accumulates in blood, bones, liver, kidney, brain and skin. Negative effects on the reproductive, hepatic, endocrine, immune and gastrointestinal systems have been reported in humans [ 38 ]. Pb possesses strong affinity for sulfhydryl groups and electron donor groups. Thus, it tightly binds to various proteins, causing multiple harms to the affected individuals. It also competes with nutrients such as calcium (Ca) or zinc (Zn) in various important mechanisms which are usually mediated by their ions. Pb easily crosses cell membranes, exerts redox reactions and induces the formations of reactive oxygen species [ 39 ]. Thus, the toxic effects of Pb are quite complex and affect virtually all organs [ 40 ]. In adults, it can increase blood pressure, slow nerve conduction or induce fatigue, mood swings, drowsiness, impaired concentration, infertility, decreased libido, headaches, constipation or encephalopathy, or even cause death in severe cases [ 41 ]. Chronic exposure in early childhood causes adverse neurodevelopmental consequences even at low levels [ 42 ], and multi-organ damage or even death at high doses [ 43 , 44 ].

The hazard posed by nickel (Ni) to human health originates primarily from the production of free radicals, generation of the superoxide anion and reactive oxygen species. The consequential oxidative stress triggers genotoxicity, carcinogenicity and immunotoxicity [ 45 ]. Additional hazard mechanisms of Ni toxicity include competition with essential metals in metalloproteins or binding to enzymes and inhibition of their activity [ 46 ]. Ni is shown to induce various pathophysiological processes in humans, including those involved in the development of allergy, cardiovascular and kidney diseases, lung fibrosis, and pulmonary, nasal and sinus cancer. This metal is associated with epigenetic effects, namely DNA hypermethylation and histone ubiquitination, which are the key mechanisms associated with tumor initiation, cancer progression and metastasis [ 47 ].

Strontium (Sr) is a trace element in the human body but has never been proved to be essential. Interestingly, the toxic effects of Sr overdose have not been reported in humans [ 48 ]. This mineral naturally accumulates in mineralized tissues by surface exchange or ionic substitution mechanisms. However, the exaggerated accumulation of Sr in bone is shown to be associated with development of osteomalacia in dialysis patients [ 49 ]. This element exerts remarkable osteogenic potential since it promotes bone formation and inhibits bone resorption. Thus, it has been incorporated in various orthopedic devices to enhance bone regeneration, especially in osteoporotic patients, where it improves bone mineral density [ 50 , 51 , 52 , 53 ].

Special consideration has to be given to the potential of zeolites’ usage for the removal of metal pollutants. These naturally occurring, highly-porous minerals, also known as molecular sieves, show enormous capacity to eliminate metals from polluted environments, mainly by mechanisms known as ion-exchange and adsorption [ 54 , 55 ]. This property has been proved for zeolite clinoptilolite in both animals and humans [ 56 ]. The crystalline structure of these aluminosilicates has cavities filled with cations and polar molecules, such as water. These chemical entities are released from the structure and simultaneously substituted by chemical species from the environment, depending on their zeolite binding affinity [ 57 ]. Moreover, zeolite clinoptilolite is highly inert and safe for human utilization [ 58 ]. Both the preclinical and clinical literature imply the great medical potential of this material in the treatment of various diseases [ 58 , 59 , 60 ]. The volcanic mineral zeolite clinoptilolite is the most widely used natural zeolite in medicine. Prior to usage, it is usually activated by grinding into fine powder. In this process, its active surface and activity increase substantially [ 61 ]. Certain types of clinoptilolites have already been certified for clinical usage [ 56 ]. One such certified material, therefore determined as safe for oral human applications, is PMA (Panaceo-Micro-Activated) zeolite, with its detoxifying, antioxidant and anti-inflammatory properties [ 62 ].

In this work, we examined the in vivo efficiency and safety of the long-term oral administration of zeolite clinoptilolite materials in natural and activated forms. We intentionally used an excessively high dose of this zeolite (8 g/kg) to examine its effect on high metallic biodistribution in vivo. Our focus was on the measurement of the concentration profiles of Al and several contaminants (As, Cd, Co, Pb, Ni and Sr) in healthy rats fed with zeolite clinoptilolite materials. Metal concentrations were measured in the brain, gastrointestinal and excretory systems, bones and circulation systems of the animals.

2. Materials and Methods

2.1. zeolites.

Clinoptilolite materials were obtained from Panaceo International Gmbh (Villach/Gödersdorf, Austria). The same natural clinoptilolite tuff was used in the form of tribomechanically activated zeolite (TMAZ), milled using a standard tribomechanical micronization, and double tribomechanically activated zeolite clinoptilolite, processed using a patented tribomechanical micronization production method (PMA zeolite). The latter patented technology for double activation uses multiple high-speed particle collision through whirlwinds that are generated by seven circular rows of blades fixed on two counter-rotating discs, wherein the counter-rotating discs are arranged such that the particles have to pass all seven circular rows of blades by centrifugal force. The velocity of the blades is 145 m/s. The above-described activation process is executed two consecutive times (‘double-activation’). It is aimed at increasing the particle temperature and particle collisions, giving rise to new surface properties described in more detail in Kraljevic Pavelic et al. [ 61 ]. The detailed physical–chemical properties and preparation of PMA zeolite are also presented in Kraljevic Pavelic et al. [ 61 ]. Ludox AS-40 colloidal silica was purchased from Sigma-Aldrich chemicals Co. (St. Louis, MO, USA).

2.2. Animals

The experiment was conducted at the Institute for Medical Research and Occupational Health in Zagreb. Female HsdBrlHan: Wistar rats (200–220 g) were bred and maintained under pathogen-free conditions in a steady-state microenvironment and fed with a standard GLP certified laboratory chow Mucedola 4RF21 (Mucedola, Settimo Milanese, Italy) and tap water ad libitum. Additionally, the rats were exposed to a 12/12 h light schedule. All the experimental procedures were performed following the Guide for the Care and Use of Laboratory Animals: Eighth Edition (National Academies Press, 2010).

2.3. Drugs and Treatment Schedule

Clinoptilolite and Ludox suspensions were prepared fresh daily prior to oral administration (gavage). Two different forms of clinoptilolite were daily administered by gavage as water suspension at a dose of 8 g/kg of body weight. Colloidal silica was also administered daily at a dose of 2 g/kg of body weight. The study was carried out for a period of three months (12 weeks). The rats were randomly assigned to four different experimental groups:

• Group 1 (n = 10): I (received drinking water);
• Group 2 (n = 10): TMAZ;
• Group 3 (n = 10): PMA zeolite;
• Group 4 (n = 10): colloidal silica (Ludox AS-40).

2.4. Tissue Sampling

After the three-month administration protocol, the rats were anesthetized with intraperitoneal injections of Narketan (80 mg/kg of body mass) and Xylapan (12 mg/kg of body mass) (Chassot AG, Bern, Switzerland) and sacrificed by exsanguination. Blood, serum, femur, liver, kidney, small and large intestine, and brain were harvested for further analysis by ICP-MS.

2.5. Inductively Coupled Plasma Mass Spectrometry (ICP-MS)

The presence of metals (Al, As, Cd, Co, Ni, Pb and Sr) was analyzed in the blood, serum and harvested tissues at the Analytical Toxicology and Mineral Metabolism Unit of the Institute for Medical Research and Occupational Health in Zagreb, using inductively coupled plasma mass spectrometry (ICP-MS) on the Agilent 7500cx Series (Agilent Technologies, Waldbronn, Germany). A mixture of nitric acid (65%, purity, m.p., Merck, Germany) and deionized water in equal volumes (2 mL) was added to 0.5 g of tissue samples and mixed vigorously. The obtained suspension was microwaved under high pressure in the UltraCLAVE IV high-pressure microwave device (Milestone, S.r.l. Italy) following the program for biological samples. The calibration curves of standards prepared in 1% HNO3 ( v / v ) from the mono-element standard solution (PlasmaCAL, CP Science, Canada) were used for the quantification of the elements. The sensitivity of the ICP-MS instrument was adjusted by a solution containing 1 μg/L of lithium (Li), magnesium (Mg), cobalt (Co), yttrium (Y), cerium (Ce), thallium (Tl) and selenium (Se). The response of detectors at masses 7 (Li), 89 (Y) and 205 (T1) was monitored, at the same time the ratios of doubly charged ions ( 140 Ce 2+ / 140 Ce + ) and the oxides of the elements ( 140 Ce 16 O + / 140 Ce + ) were compared with the single-charged ions. Optimal conditions are achieved when satisfactory sensitivity (by varying the voltage on the lens, the depth of the sample input and the gas flow rate of the carrier) is obtained, with minimal formation of doubly charged ions (<2.2%) and oxide ions (<1.4%). For the accuracy and precision of the ICP-MS method, the following commercially available reference blood materials were used: Recipe ClinChek ® Whole blood lyophilized Level I, II, III and SeronormTM Trace Element Whole Blood Level I, II for blood; Recipe ClinChek ® Serum Control lyophilized Level I, II, Plasma Control lyophilized Level I, II and SeronormTM Trace Elements Serum Level I, II for serum/plasma; and BRM-IAEA-H5 Animal Bone for bone. All the reference materials were reconstituted by the addition of ultrapure water according to the manufacturers’ protocols, and were used to confirm the accuracy and precision of the method. The bone material reference sample was prepared in the same way as the biological samples of the rat organs. The physiological levels of the measured metals and minerals in the rats are given in Supplementary Tables S1 and S2 .

2.6. Statistical Analysis

Statistical analysis was performed using GraphPad Prism 9 (GraphPad Software, San Diego, CA, USA). Statistical differences between groups were examined using a t -test ( t -test: two samples assuming equal variances). The data were presented as arithmetic mean ± standard deviation.

The long-term administration of TMAZ and PMA zeolite, as well as Ludox silica, induced distinct, statistically relevant changes in the concentrations of the examined metals, depending on the analyzed tissue. Overall, the majority of the significant changes in metal levels were observed in the serum, while no major changes were observed in the brain. The kidney and liver as major detoxification organs showed increased concentrations of Pb with a concomitant decrease of Pb levels in the large intestine upon PMA zeolite administration. In the kidney, small and large intestine, and femoral bone, the majority of the changes pointed to decreased levels of the analyzed metals. Specifically, Al levels were altered in the kidney, serum and femur ( Figure 1 ). TMAZ reduced this metal level in the kidney and serum. Both TMAZ and PMA zeolite, as well as Ludox, showed similar effects on the change in Al concentration profiles in the tested rats. These zeolites increased Al levels in the serum while concomitantly decreasing its levels in the femur. Ludox decreased Al levels in the kidney as well. This may be indicative of Al release from bone deposits.

Concentrations of aluminum in the brain, kidney, liver, small intestine, large intestine, serum, blood and femur after the three-month oral administration of silicates. C denotes the control group; T denotes the experimental group receiving tribomechanically activated zeolite clinoptilolite (TMAZ); P denotes the experimental group receiving the double tribomechanically activated zeolite clinoptilolite (PMA zeolite); and L denotes the experimental group receiving Ludox silica. Asterisk (*) denotes significant differences between the experimental groups, with control at p < 0.05.

As levels changed in the small intestine and serum ( Figure 2 ). TMAZ reduced the level of this metal in the small intestine, while both PMA zeolite and Ludox increased its levels in serum. Overall, Cd levels were reduced in the presented experiment ( Figure 3 ). PMA zeolite reduced its levels in the small intestine and serum.

Concentrations of arsenic in the brain, kidney, liver, small intestine, large intestine, serum, blood and femur after the three-month oral administration of silicates. C denotes the control group; T denotes the experimental group receiving TMAZ; P denotes the experimental group receiving PMA; and L denotes the experimental group receiving Ludox silica. Asterisk (*) denotes significant differences between the experimental groups, with control at p < 0.05.

Concentrations of cadmium in the brain, kidney, liver, small intestine, large intestine, serum, blood and femur after the three-month oral administration of silicates. C denotes the control group; T denotes the experimental group receiving TMAZ; P denotes the experimental group receiving PMA; and L denotes the experimental group receiving Ludox silica. Asterisk (*) denotes significant differences between the experimental groups, with control at p < 0.05.

Of the analyzed metals, Co was the only metal which did not show any concentration changes in the experiment ( Figure 4 ). Ni was, however, the only metal whose levels were increased in the femur, as observed in all three experimental groups ( Figure 5 ). PMA zeolite reduced Ni levels in the kidney and blood, which was accompanied by an increase in levels in the serum. Ludox induced same changes, except for the kidney, where it did not cause significant changes in Ni levels.

Concentrations of cobalt in the brain, kidney, liver, small intestine, large intestine, serum, blood and femur after the three-month oral administration of silicates. C denotes the control group; T denotes the experimental group receiving TMAZ; P denotes the experimental group receiving PMA; and L denotes the experimental group receiving Ludox silica. Asterisk (*) denotes significant differences between the experimental groups, with control at p < 0.05.

Concentrations of nickel in the brain, kidney, liver, small intestine, large intestine, serum, blood and femur after the three-month oral administration of silicates. C denotes the control group; T denotes the experimental group receiving TMAZ; P denotes the experimental group receiving PMA; and L denotes the experimental group receiving Ludox silica. Asterisk (*) denotes significant differences between the experimental groups, with control at p < 0.05.

Pb levels changed upon treatments in the kidney, liver, large intestine, femur and blood ( Figure 6 ). TMAZ reduced its levels in the blood, while PMA zeolite increased its levels in the kidney and liver with a concomitant decrease in the large intestine. Ludox induced a decrease of Pb levels only in the femur.

Concentrations of lead in the brain, kidney, liver, small intestine, large intestine, serum, blood and femur after the three-month oral administration of silicates. C denotes the control group; T denotes the experimental group receiving TMAZ; P denotes the experimental group receiving PMA; and L denotes the experimental group receiving Ludox silica. Asterisk (*) denotes significant differences between the experimental groups, with control at p < 0.05.

Sr levels changed in the large intestine, serum and blood ( Figure 7 ). Its levels were increased in the serum in all three experimental groups. TMAZ increased its levels in the blood, while Ludox reduced its levels in the large intestine and the blood.

Concentrations of strontium in the brain, kidney, liver, small intestine, large intestine, serum, blood and femur after the three-month oral administration of silicates. C denotes the control group; T denotes the experimental group receiving TMAZ; P denotes the experimental group receiving PMA; and L denotes the experimental group receiving Ludox silica. Asterisk (*) denotes significant differences between the experimental groups, with control at p < 0.05.

4. Discussion

Zeolites are increasingly considered as an efficient approach in the fight against the toxicological burden of metallic pollution. Owing to their unique physicochemical characteristics, and most importantly, their ion-exchange and adsorption properties, zeolites possess magnificently powerful capabilities for decontamination and the reduction of metallic burden, either in industrial applications or in animals and humans. The first applications with zeolite clinoptilolite for decontamination were performed more than 30 years ago [ 63 , 64 ]. Since then, zeolite clinoptilolite has shown a high affinity with metallic pollutants in many studies [ 56 , 63 , 64 , 65 ], and has been extensively used for the elimination of Al, Pb, Cd, Sr, Co, Ni, Mg, Cr and As from contaminated areas. Besides industrial applications, zeolite clinoptilolite is increasingly used in veterinary and human medicine, as it has been proved to be safe, inert and resilient to metabolism [ 59 ]. Accordingly, diverse in vivo effects were documented as well, including antioxidant, hemostatic, anti-diarrhetic, immunomodulatory and detoxification properties [ 66 ]. More importantly, in several recent clinical trial studies on humans with a natural clinoptilolite material (PMA zeolite), it has been shown that preloaded metals do not enter the blood stream from the intestine, but that the observed fluctuations of metal levels in the blood are a consequence of the activation of detoxification processes from various body compartments [ 67 ]. The main mechanisms underlying these biological effects include incorporation of metallic ions within the zeolite clinoptilolite crystal lattice, but additional biological effects should be considered as well. For example, the zeolite clinoptilolite structure has been found to neutralize free radicals by trapping them within the complex structure, which leads to their chemical inactivation [ 66 ]. This is highly relevant, since metals exert their toxic effects in humans primarily through the massive induction of free radicals and triggering of oxidative stress processes. As clinoptilolite materials are zeolites of natural origin, they are mined as structures pre-loaded with a variety of elements, including metals. The pre-requisite for their in vivo oral application is, accordingly, strict material control [ 56 ].

In the presented paper, we obtained data that underlines previously observed PMA zeolite properties in Al elimination from the body [ 61 ]. Indeed, the Al levels in the femur of PMA zeolite-supplemented animals were significantly decreased, probably due to the bone remodeling process resulting in a transient increase in the serum. The same effect was observed in a pilot study in patients with irritable bowel syndrome [ 68 ]. The bone remodeling process has already been observed in clinoptilolite treatment—specifically with PMA zeolite treatment in vivo [ 69 ] —and is at least partially attributable to soluble silicon species release from the zeolite clinoptilolite material into the blood. This is in line with our results, which are comparable in animals treated only with colloidal silica. Furthermore, on the basis of data in the literature, activated bone remodeling process and high affinity of the clinoptilolite material towards Pb, we may hypothesize that Pb-detoxification process from the bone compartment has been triggered in rats supplemented with PMA zeolite. This process is usually very slow and may last for years [ 70 , 71 ]. Indeed, increased Pb levels were observed in the kidneys and liver of the TMAZ-supplemented animals as well, with the same trend but without significance. This is expected, as these organs represent the main detoxification routes for Pb. In the large intestine, Pb levels were statistically decreased in PMA zeolite-treated animals. The similarity of effects for TMAZ and PMA zeolite, but a stronger, statistically relevant change observed for PMA zeolite, may be attributable to the smaller particle size and larger active surface area in the PMA zeolite material [ 57 ]. Importantly, rats have a coprophage behavior [ 72 ], and serum Pb in our experiment may come both from body deposition departments such as bones but partially also from re-ingested feces.

Furthermore, the PMA zeolite material statically decreased the levels of Cd in the serum and in the small intestine, as well as the levels of Ni in the kidneys. Interestingly, PMA zeolite increased levels of Ni in the femur, but this increase did not exceed physiological levels observed in female rats [ 73 ]. In the context of previously observed bone remodeling process occurring in clinoptilolite treated animals and humans [ 69 ], this may be correlated with an anabolic effect of zeolite on bone tissue, as is the case for Zn and Co as well [ 74 ]. Moreover, levels in the femur were reduced only in the TMAZ-supplemented animals. The velocity of effects on the observed metal elimination from deposits in the body seems indeed to be correlated with the material’s physical–chemical properties. It was shown previously that in humans, for example, PMA zeolite significantly decreased As upon longer PMA zeolite intake, specifically a 12-week supplementation in the clinical trial Morbus Crohn study [ 67 ].

Finally, Sr levels increased in the serum of animals supplemented with TMAZ, PMA zeolite and Ludox. This might point to a connection or even increased uptake of Sr along with Si from the intestine owing to soluble silica forms released from the zeolites and present in Ludox in all the applied supplementations. Recently, Xing et al., for example, reported that Si and Sr ions released from bioceramic hydrogels synergistically stimulated cell proliferation and stimulate osteogenic differentiation [ 75 ]. However, further investigation of this phenomena possibility in vivo should be conducted in more detail.

5. Conclusions

Our results point to a beneficial effect of clinoptilolite materials on the concentration profile of metals in female rats supplemented with the corresponding natural clinoptilolite materials, TMAZ and PMA zeolite. The observed decrease of measured toxicants in the kidney, femur, and small and large intestine after three months of oral intake occurred concomitantly with their most likely transient release into the bloodstream (serum), indicative of a detoxification process. The similarity of effects for TMAZ and PMA zeolite, but with a stronger, statistically relevant change observed for PMA zeolite for Pb mobilization from the body compartments, may be attributable to the particle size and active surface increase in the PMA zeolite material. This phenomenon has been also observed in humans within a controlled clinical trial and merits further study, as it may be relevant for the improvement of bone quality.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/biology12020193/s1 . Table S1: Physiological levels of metals and minerals determined from rat plasma and organs as a measure of physiological concentrations of metals and minerals. Concentrations of measured elements in plasma are expressed as mg/L or µg/L, and concentrations of measured elements in organs are expressed as mg/kg or µg/kg. Table S2: Particle diameter size of different zeolites assessed by laser light scattering.

Funding Statement

This research was funded by research grant from Panaceo International GmbH, Villach, Austria (“Effect of PMA-Zeolite-Clinoptilolite on the mineral metabolism and selected blood parameters (MMBP Study)”). The Funder was not involved in the design of the study and decision on publication of results.

Author Contributions

Conceptualization, S.K.P. and M.Č.; methodology, S.K.P., M.Č. and I.D.; software, I.D., T.O., I.Š. and L.F.H.; validation, I.D. and L.F.H.; formal analysis, I.D., T.O. and V.M.; investigation, I.D., V.M., J.J. and T.O.; resources, S.K.P.; data curation, I.D., L.F.H., I.Š., S.K.P.; writing—original draft preparation, I.D. and L.F.H.; writing—review and editing, I.D., L.F.H., T.O., V.M., I.Š., A.J., J.J., S.M., M.Č. and S.K.P.; visualization, I.D. and L.F.H.; supervision, S.K.P. and M.Č.; funding acquisition and final revision, S.K.P. All authors have read and agreed to the published version of the manuscript.

Institutional Review Board Statement

The animal study protocol was approved by the Ethics Committee of the Institute for Medical Research and Occupational Health, Zagreb, Croatia (protocol code 01-18/22-02-2/1 on 8 February 2022). All procedures performed on animals have been approved by the Ethics Committee of the Ministry of Agriculture and Forestry of the Republic of Croatia UP/I322/01/22-01/25.

Informed Consent Statement

Data availability statement, conflicts of interest.

SKP is independent scientific advisor of Panaceo International Gmbh, Austria. Other authors do not have any conflict of interest to declare.

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

The Potential Long-Run Implications of a Permanently-Expanded Child Tax Credit

For many of those who worked to include an expanded Child Tax Credit in the 2021 American Rescue Plan, an important motivation was to test the feasibility and effectiveness of a permanent U.S. child allowance similar to those provided in other rich countries. Because this expansion was short-lived, however, evaluations of its effects cannot provide complete evidence on the long-run effects of a permanently expanded CTC. We leverage theoretical predictions from standard economic models, behavioral science, and child development frameworks, along with empirical evidence from literature evaluating previous long-term cash and quasi-cash transfers to families with children, to predict the likely long-run impacts of a permanent child allowance. We find that it would lead to increased future earnings and tax payments, improved health and longevity, and reduced health care, crime, and child protection costs; using conventional valuations, benefits to society outweigh costs nearly 10 to 1, with most benefits due to credit refundability.

There are no funding sources or material or relevant financial relationships to disclose. The views expressed herein are those of the authors and do not necessarily reflect the views of the National Bureau of Economic Research.

MARC RIS BibTeΧ

Download Citation Data

More from NBER

In addition to working papers , the NBER disseminates affiliates’ latest findings through a range of free periodicals — the NBER Reporter , the NBER Digest , the Bulletin on Retirement and Disability , the Bulletin on Health , and the Bulletin on Entrepreneurship  — as well as online conference reports , video lectures , and interviews .