Water cluster triggered vitrification in HKUST-1 MOF crystal under pressure

Abstract

Metal–organic framework (MOF) glasses feature several unique dynamic and thermodynamic properties that differentiate them from their crystalline counterparts. However, the formation of MOF glasses usually requires the melt-quenching of molten MOFs from relatively high temperatures. In practice, this approach is quite limited because most MOFs decompose below their melting points. Herein, we demonstrate a direct crystal-to-glass transition in HKUST-1 MOF that has been achieved at room temperature and a relatively low pressure of <1.0 GPa. The dramatic fall in the required pressure is shown to arise from the aggregation of coordinated polar water molecules to form water clusters that exhibit a pulling effect on the Cu–O_(ligand) bonds. Meanwhile, the departed fragment gets flipped unfavorably to prevent further regeneration of the bond. Accordingly, a grain boundary-free continuous porous framework in the glassy state is successfully formed and can be fabricated into membranes. Given their unique microporosity and grain boundary-free characteristics, such MOF glass membranes present new opportunities for chemical separation (both gases and liquids), electrochemistry, and catalysts, promising a new platform for MOF glasses.

Keywords

grain-boundary-free membrane / MOF glass / molecular separation / pressure-induced glass transition / water cluster

References

[1] Furukawa H, Cordova KE, O'Keeffe M, Yaghi OM. The chemistry and applications of metal-organic frameworks. Science. 2013; 341:1230444.

[2] Xue W-L, Kolodzeiski P, Aucharova H, et al. Highly porous metal-organic framework liquids and glasses via a solvent-assisted linker exchange strategy of ZIF-8. Nat Commun. 2024; 15(1): 4420.

[3] Kim M, Lee H-S, Seo D-H, Cho SJ, Jeon E, Moon HR. Melt-quenched carboxylate metal–organic framework glasses. Nat Commun. 2024; 15(1): 1174.

[4] Bennett TD, Cheetham AK. Amorphous metal–organic frameworks. Acc Chem Res. 2014; 47(5): 1555-1562.

[5] Bennett TD, Keen DA, Tan J, Barney ER, Goodwin AL, Cheetham AK. Thermal amorphization of zeolitic imidazolate frameworks. Angew Chem Int ed. 2011; 50(13): 3067.

[6] Bennett TD, Simoncic P, Moggach SA, et al. Reversible pressure-induced amorphization of a zeolitic imidazolate framework (ZIF-4). Chem Commun. 2011; 47(28): 7983-7985.

[7] Greaves GN, Meneau F, Sapelkin A, et al. The rheology of collapsing zeolites amorphized by temperature and pressure. Nat Mater. 2003; 2(9): 622-629.

[8] Chapman KW, Halder GJ, Chupas PJ. Pressure-induced amorphization and porosity modification in a metal−organic framework. J Am Chem Soc. 2009; 131(48): 17546-17547.

[9] Umeyama D, Horike S, Tassel C, et al. Pressure-induced amorphization of a dense coordination polymer and its impact on proton conductivity. APL Mater. 2014; 2:124401.

[10] Collings IE, Goodwin AL. Metal–organic frameworks under pressure. J Appl Phys. 2019; 126(18):181101.

[11] Bennett TD, Saines PJ, Keen DA, Tan J, Cheetham AK. Ball-milling-induced amorphization of zeolitic imidazolate frameworks (ZIFs) for the irreversible trapping of iodine. Chem A Eur J. 2013; 19(22): 7049.

[12] Baxter EF, Bennett TD, Cairns AB, et al. A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling. Dalton Trans. 2016; 45(10): 4258-4268.

[13] Castillo-Blas C, Chester AM, Keen DA, Bennett TD. Thermally activated structural phase transitions and processes in metal–organic frameworks. Chem Soc Rev. 2024; 53(7): 3606-3629.

[14] Widmer RN, Lampronti GI, Casati N, Farsang S, Bennett TD, Redfern SAT. X-ray radiation-induced amorphization of metal–organic frameworks. Phys Chem Chem Phys. 2019; 21(23): 12389-12395.

[15] Bennett TD, Horike S. Liquid, glass and amorphous solid states of coordination polymers and metal–organic frameworks. Nat Rev Mater. 2018; 3(11): 431-440.

[16] Huang W, Chan B, Yang Y, et al. Intermarrying MOF glass and Lead halide perovskites for artificial photosynthesis. J Am Chem Soc. 2025; 147(4): 3195-3205.

[17] Ao D, Yang Z, Chen A, et al. Effective C4Separation by zeolite metal–organic framework composite membranes. Angew Chem Int ed. 2024; 63(21):e202401118.

[18] Hou J, Chen P, Shukla A, et al. Liquid-phase sintering of lead halide perovskites and metal-organic framework glasses. Science. 2021; 374(6567): 621-625.

[19] Chen M, Li J, Liao S, et al. Multi-stage transformations of a cluster-based metal-organic framework: perturbing crystals to glass-forming liquids that re-crystallize at high temperature. Angew Chem Int Ed. 2023; 62:e202305942.

[20] Yin Z, Zhao Y, Wan S, et al. Synergistic stimulation of metal–organic frameworks for stable super-cooled liquid and quenched glass. J Am Chem Soc. 2022; 144(29): 13021-13025.

[21] Bennett TD, Tan J-C, Yue Y, et al. Hybrid glasses from strong and fragile metal-organic framework liquids. Nat Commun. 2015; 6:8079.

[22] Bennett TD, Yue Y, Li P, et al. Melt-quenched glasses of metal–organic frameworks. J Am Chem Soc. 2016; 138(10): 3484-3492.

[23] Widmer RN, Lampronti GI, Anzellini S, et al. Pressure promoted low-temperature melting of metal–organic frameworks. Nat Mater. 2019; 18(4): 370-376.

[24] Wei Y-S, Fan Z, Luo C, Horike S. Desolvation of metal complexes to construct metal–organic framework glasses. Nat Synth. 2023; 3(2): 214.

[25] Thorne MF, Sapnik AF, McHugh LN, et al. Glassy behaviour of mechanically amorphised ZIF-62 isomorphs. Chem Commun. 2021; 57(73): 9272-9275.

[26] Chui SS-Y, Lo SM-F, Charmant JPH, Orpen AG, Williams ID. A chemically functionalizable nanoporous material [Cu₃(TMA)₂(H₂O)₃]_n. Science. 1999; 283(5405): 1148-1150.

[27] Prestipino C, Regli L, Vitillo JG, et al. Local structure of framework Cu(II) in HKUST-1 Metallorganic framework:  spectroscopic characterization upon activation and interaction with adsorbates. Chem Mater. 2006; 18(5): 1337-1346.

[28] Chapman KW, Halder GJ, Chupas PJ. Guest-dependent high pressure phenomena in a nanoporous metal−organic framework material. J Am Chem Soc. 2008; 130(32): 10524-10526.

[29] Yu H-B, Wang W-H, Samwer K. The β relaxation in metallic glasses: an overview. Mater Today. 2013; 16(5): 183-191.

[30] Ma N, Ohtani R, Le HM, et al. Exploration of glassy state in Prussian blue analogues. Nat Commun. 2022; 13(1): 4023.

[31] Gholizadeh M. Effect of polymer (PE–EVA–PVC) structure on gas permision properties. Arab J Sic Eng. 2012; 37(4): 889-896.

[32] Schädle T, Pejcic B, Mizaikoff B. Monitoring dissolved carbon dioxide and methane in brine environments at high pressure using IR-ATR spectroscopy. Anal Methods. 2016; 8(4): 756-762.

[33] Ma X, Wang L, Wang H, et al. Insights into metal-organic frameworks HKUST-1 adsorption performance for natural organic matter removal from aqueous solution. J Hazard Mater. 2022; 424:126918.

[34] Todaro M, Alessi A, Sciortino L, et al. Investigation by Raman spectroscopy of the decomposition process of HKUST-1 upon exposure to air. J Spectrosc. 2016; 2016(1): 1-7.

[35] Li P, Sun Z. An innovative way to modulate the photoluminescence of carbonized polymer dots. Light Sci Appl. 2022; 11(1): 81.

[36] Xue W, Zhang Z, Huang H, Zhong C, Mei D. Theoretical insights into the initial hydrolytic breakdown of HKUST-1. J Phys Chem C. 2020; 124(3): 1991-2001.

[37] Todaro M, Buscarino G, Sciortino L, et al. Decomposition process of carboxylate MOF HKUST-1 unveiled at the atomic scale level. J Phys Chem C. 2016; 120(23): 12879-12889.

[38] Xue W, Wang J, Huang H, Mei D. Structural and hydrolytic stability of coordinatively unsaturated metal–organic frameworks M3(BTC)2(M = Cu, Co, Mn, Ni, and Zn): a combined DFT and experimental study. J Phys Chem C. 2021; 125(10): 5832-5847.

[39] Pereiro AB, Rodríguez A. Separation of ethanol−heptane azeotropic mixtures by solvent extraction with an ionic liquid. Ind Eng Chem Res. 2009; 48(3): 1579-1585.

[40] Domańska U, Wiśniewska A, Dąbrowski Z, Więckowski M. Ternary liquid–liquid phase equilibrium data. J Mol Liq. 2018; 255: 504.

[41] Zhong J, Cheng H, Dai Y, et al. Boiling water resistant fully bio-based adhesive made from maleated chitosan and glucose with excellent performance. ACS Sustain Chem Eng. 2023; 11:16849.

[42] Zulkifli MYB, Su K, Chen R, Hou J, Chen V. Future perspective on MOF glass composite thin films as selective and functional membranes for molecular separation. Adv Membr. 2022; 2:100036.

[43] Wang Y, Jin H, Ma Q, et al. A MOF glass membrane for gas separation. Angew Chem Int ed. 2020; 132(11): 4395-4399.

[44] McHugh LN, Bennett TD. Introducing porosity into metal–organic framework glasses. J Mater Chem A. 2022; 10(37): 19552-19559.

[45] Polotskaya G, Pulyalina A, Goikhman M, et al. Novel polyheteroarylene membranes for separation of methanol–hexane mixture by pervaporation. Sci Rep. 2018; 8(1):17849.

[46] Penkova AV, Kuzminova AI, Dmitrenko ME, et al. Novel pervaporation mixed matrix membranes based on polyphenylene isophtalamide modified by metal–organic framework UiO-66(NH2)-EDTA for highly efficient methanol isolation. Sep Purif Technol. 2021; 263:118370.

[47] Okada T, Matsuura T. Predictability of transport equations for pervaporation on the basis of pore-flow mechanism. J Membr Sci. 1992; 70(2–3): 163-175.

[48] Kühne TD, Iannuzzi M, Del Ben M, et al. CP2K: an electronic structure and molecular dynamics software package - quickstep: efficient and accurate electronic structure calculations. J Chem Phys. 2020; 152(19):194103.

[49] Perdew JP. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys Rev B. 1986; 33(12): 8822-8824.

[50] Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett. 1996; 77(18): 3865-3868.

[51] Grimme S, Antony J, Ehrlich S, Krieg H. A consistent and accurateab initioparametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104.

[52] VandeVondele J, Hutter J. Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J Chem Phys. 2007; 127(11):114105.

[53] Martyna GJ, Tobias DJ, Klein ML. Constant pressure molecular dynamics algorithms. J Chem Phys. 1994; 101(5): 4177-4189.

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