Facile in situ growth of ZIF-8 films onto aluminum for applications requiring fast thermal response


In this work, we report a simple approach for the synthesis of highly crystalline films of ZIF-8 directly grown onto non-functionalized common aluminum substrates through an easy, short in situ solvothermal methodology. Through several techniques such as XRD, SEM, EDS, AFM and XPS, it is shown that a simple, short pretreatment of the substrate with a dilute hydrochloric acid solution promotes the subsequent solvothermal nucleation and growth of continuous, homogeneous micrometer thickness and very adherent ZIF-8 films. The robustness and usefulness of ZIF-8/aluminum are shown by testing it in the highly exothermic catalytic reaction of carbon monoxide oxidation, in which it presented a high performance and durability, preserving the metal–organic framework integrity during reaction time. This behavior demonstrates that the novel ZIF-8/aluminum systems have a high potential for use in applications at moderate temperatures demanding a fast heat exchange rate between the metal–organic framework (MOF) film and the substrate.

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  1. 1

    Phan A, Doonan C, Uribe-Romo F, Knobler C, O’Keeffe M, Yaghi O (2010) Synthesis, structure, and carbon dioxide capture properties of zeolitic imidazolate frameworks. Acc Chem Res 43:58–67

    CAS  Article  Google Scholar 

  2. 2

    Park K, Ni Z, Coté A, Choi J, Huang R, Uribe-Romo F, Chae H, O´Keeffe M, Yagui O, (2006) Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. PNAS 103:10186

    CAS  Article  Google Scholar 

  3. 3

    Yao J, Wang H (2014) Zeolitic imidazolate framework composite membranes and thin films: synthesis and applications. Chem Soc Rev 43(13):4470–4493

    CAS  Article  Google Scholar 

  4. 4

    Bux H, Feldhoff A, Cravillon J, Wiebcke M, Li Y-S, Caro J (2011) Oriented zeolitic imidazolate framework-8 membrane with sharp H2/C3H8 molecular sieve separation. Chem Mater 23:2262–2269

    CAS  Article  Google Scholar 

  5. 5

    Kwon H, Jeong H-K (2013) In Situ Synthesis of thin zeolitic-imidazolate framework ZIF-8 membranes exhibiting exceptionally high propylene/propane separation. J Am Chem Soc 135(29):10763–10768

    CAS  Article  Google Scholar 

  6. 6

    Venna S, Carreon M (2009) Highly Permeable zeolite imidazolate Framework-8 MEMBRANES for CO2/CH4 separation. J Am Chem Soc 132:76–78

    Article  Google Scholar 

  7. 7

    Betard A, Fischer R (2012) Metal-organic framework thin films: from fundamentals to applications. Chem Rev 112:1055–1083

    CAS  Article  Google Scholar 

  8. 8

    Kida K, Fujita K, Shimada T, Tanaka S, Miyake Y (2013) Layer-by-layer aqueous rapid synthesis of ZIF-8 films on a reactive surface. Dalt Trans 42(31):11128–11136

    CAS  Article  Google Scholar 

  9. 9

    Chen L-J, Luo B, Li W-S, Yang YT, Li S-S, Wang X-Z, Cui Y-J, Li H-Y, Qian G-D (2016) Growth and characterization of zeolitic imidazolate framework-8 nanocrystalline layers on microstructured surfaces for liquid crystal alignment. RSC Adv 6:7488

    CAS  Article  Google Scholar 

  10. 10

    He M, Yao J, Li L, Zhong Z, Chen F, Wang H (2013) Aqueous solution synthesis of ZIF-8 films on a porous nylon substrate by contra-diffusion method. Micropor Mesopor Mater 179:10–16

    CAS  Article  Google Scholar 

  11. 11

    Hamid M, Park S, Kim J, Lee Y, Jeong H-K (2019) In-Situ formation of Zeolitic-Imidazolate framework thin films and composites using modified polymer substrates. J Mater Chem A 7:9680–9689

    Article  Google Scholar 

  12. 12

    Dumée L, He L, Hill M, Zhu B, Duke M, Schütz J, She F, Wang H, Gray S, Hodgsona P, Kong L (2013) Seeded growth of ZIF-8 on the surface of carbon nanotubes towards self-supporting gas separation membranes. J Mater Chem A 1(32):9208–9214

    Article  Google Scholar 

  13. 13

    Bux H, Chmelik C, Krishna R, Caro J (2011) Ethene/ethane separation by the MOF membrane ZIF-8: Molecular correlation of permeation, adsorption, diffusion. J Memb Sci 369(1–2):284–289

    CAS  Article  Google Scholar 

  14. 14

    Tian F, Cerro AM, Mosier AM, Wayment-Steele HK, Shine RS, Park A, Webster ER, Johnson LE, Johal MS, Benz L (2014) Surface and stability characterization of a nanoporous ZIF-8 thin film. J Phys Chem C 118(26):14449–14456

    CAS  Article  Google Scholar 

  15. 15

    Chocarro-Ruiz B, Pérez-Carvajal P, Avci C, Calvo-Lozano O, Alonso M, Maspoch D, Lechuga L (2018) A CO2 optical sensor based on self-assembled metal–organic framework nanoparticles. J Mater Chem A 6:13171

    CAS  Article  Google Scholar 

  16. 16

    Segovia G, Tuninetti J, Moya S, Picco A, Ceolín M, Azzaroni O, Rafti M (2018) Cysteamine-modified ZIF-8 colloidal building blocks: direct assembly of nanoparticulate MOF films on gold surfaces via thiol chemistry. Mat Today Chem 8:29–35

    CAS  Article  Google Scholar 

  17. 17

    Makiura R, Motoyama S, Umemura Y, Yamanaka H, Sakata O, Kitagawa H (2010) Surface nano-architecture of a metal-organic framework. Nat Mater 9:565

    CAS  Article  Google Scholar 

  18. 18

    Stassen I, Styles M, Grenci G, Van Gorp H, Vanderlinden W, De Feyter S, Falcaro P, De Vos D, Vereecken P, Ameloot R (2016) Chemical vapour deposition of zeolitic imidazolate framework thin films. Nature Mater 15:304–310

    CAS  Article  Google Scholar 

  19. 19

    Kim D-Y, Joshi B, Lee J-G, Lee J-H, Lee J-S, Hwang Y, Chang J-S, Al-Deyab S, Tan J-C, Yoon S (2016) Supersonic cold spraying for zeolitic metal–organic framework films. Chem Eng J 295:49–56

    CAS  Article  Google Scholar 

  20. 20

    Fischer D, von Mankowski A, Ranft A, Vasa S, Linser R, Mannhart J, Lotsch B (2017) ZIF-8 films prepared by femtosecond pulsed-laser deposition. Chem Mater 29:5148–5155

    CAS  Article  Google Scholar 

  21. 21

    Huang A, Liu Q, Wang N, Caro J (2014) Highly hydrogen permselective ZIF-8 membranes supported on polydopamine functionalized macroporous stainless-steel nets. J Mater Chem A 2(22):8246–8251

    CAS  Article  Google Scholar 

  22. 22

    Ma Q, Li G, Liu X, Wang Z, Song Z, Wang H (2018) Zeolitic imidazolate framework-8 film coated stainless steel meshes for highly efficient oil/water separation. Chem Commun 54:5530–5533

    CAS  Article  Google Scholar 

  23. 23

    Ji H, Hwang S, Kim K, Kim C, Jeong N (2016) Direct in Situ conversion of metals into metal−organic frameworks: a strategy for the rapid growth of mof films on metal substrates. ACS Appl Mater Interfaces 8:32414–32420

    CAS  Article  Google Scholar 

  24. 24

    Papporello R, Miró E, Zamaro J (2015) Secondary growth of ZIF-8 films onto copper-based foils. Insight into surface interactions. Micropor Mesopor Mater 211:64–72

    CAS  Article  Google Scholar 

  25. 25

    Touloukian, Y.S., Powell, R.W., Ho, C.Y., Klemens, P.G.: Thermophysical properties of matter-the TPRC Data. In: Thermal Conductivity-Metallic Elements and Alloys, vol. 1, SBN 306–67021–6. IFI/Plenum, New York, Washington (1970)

  26. 26

    Boger T, Heibel AK (2005) Heat transfer in conductive monolith structures. Chem Eng Sci 60(7):1823–1835

    CAS  Article  Google Scholar 

  27. 27

    Papurello R, Fernández J, Miró E, Zamaro J (2017) Microreactor with silver-loaded metal-organic framework films for gas-phase reactions. Chem Eng J 313:1468–1476

    CAS  Article  Google Scholar 

  28. 28

    Cui B, Audu CO, Liao Y, Nguyen ST, Farha OK, Hupp JT, Grayson M (2017) Thermal conductivity of ZIF-8 thin-film under ambient gas pressure. ACS Appl Mater Interfaces 9:28139–28143

    CAS  Article  Google Scholar 

  29. 29

    Zhang J, Ramachandran PV, Gore JP, Mudawar I, Fisher TS (2005) A review of heat transfer issues in hydrogen storage technologies. J Heat Transfer 127(12):1391–1399

    CAS  Article  Google Scholar 

  30. 30

    Zhang M, Ma L, Wang L, Sun Y, Liu Y (2018) Insights into the use of metal−organic framework as high-performance anticorrosion coatings. ACS Appl Mater Interfaces 10:2259–2263

    CAS  Article  Google Scholar 

  31. 31

    Zhang M, Liu Y (2020) Enhancing the anti-corrosion performance of ZIF-8-based coatings via microstructural optimization. New J Chem 44:2941–2946

    CAS  Article  Google Scholar 

  32. 32

    Hernandez J, Choren E (1983) Thermal stability of some platinum complexes. Thermochim Acta 71(3):265–272

    CAS  Article  Google Scholar 

  33. 33

    Reddy N, Bera P, Reddy V, Sridhara N, Dey A, Anandan C, Sharma A (2015) XPS study of sputtered alumina thin films. Ceram Int 40(7):11099–11107

    Article  Google Scholar 

  34. 34

    Kaesche H (2003) Corrosion of metal. Springer-Verlag, Berlin Heidelberg, Physicochemical Principles and Current Problems

    Book  Google Scholar 

  35. 35

    Leygraf C, Graede T (2000) Atmospheric corrosion. Inc, New York

    Google Scholar 

  36. 36

    Fernández-Bertrán J, Castellanos-Serra L, Madeira H, Reguera E (1999) Proton transfer in solid state: mechanochemical reactions of imidazole with metallic oxides. J Solid State Chem 147:561–564

    Article  Google Scholar 

  37. 37

    Teagarden DL, Radavich JF, White J, Hem SL (1981) Aluminum chlorohydrate 11: physicochemical properties. J Pharm Sci 70(7):762–764

    CAS  Article  Google Scholar 

  38. 38

    Wang P, Liu J, Liu C, Zheng B, Zou X, Jia M, Zhu G (2016) Electrochemical synthesis and catalytic properties of encapsulated metal clusters within zeolitic imidazolate frameworks. Chem Eur J 122:16613–16620

    Article  Google Scholar 

  39. 39

    Jiang H, Liu B, Akita T, Haruta M, Sakurai H, Xu Q (2009) Au@ZIF-8: CO Oxidation over gold nanoparticles deposited to metal−organic framework. J Am Chem Soc 131:11302–11303

    CAS  Article  Google Scholar 

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The authors wish to express their gratitude to Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Thanks are given to Agencia Nacional de Promoción Científica y Tecnológica of Argentina (Project PICT 2241) and Universidad Nacional del Litoral (Project CAI+D 0071) for their financial support. Special thanks to ANPCyT for the purchase of the UHV Multi Analysis System (PME 8-2003) and to M. F. Mori for the XPS analyses.

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Complementary results of characterization related to this article by FTIR, SEM, EDS, TGA and catalytic assay are provided.

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Papurello, R.L., Zamaro, J.M. Facile in situ growth of ZIF-8 films onto aluminum for applications requiring fast thermal response. J Mater Sci 56, 9065–9078 (2021). https://doi.org/10.1007/s10853-021-05850-0

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