Confined Water Cluster Formation in Water Harvesting by Metal–Organic Frameworks: CAU-10-H versus CAU-10-CH3

Monique A. van der Veen; Stefano Canossa; Mohammad Wahiduzzaman; Gwilherm Nenert; Dominik Frohlich; Davide Rega; Helge Reinsch; Leonid Shupletsov; Karen Markey; Dirk E. De Vos; Mischa Bonn; Norbert Stock; Guillaume Maurin; Ellen H.G. Backus

doi:10.1002/adma.202210050

Confined Water Cluster Formation in Water Harvesting by Metal–Organic Frameworks: CAU-10-H versus CAU-10-CH₃

Monique A. van der Veen (Corresponding author)
, Stefano Canossa
, Mohammad Wahiduzzaman
, Gwilherm Nenert
, Dominik Frohlich
, Davide Rega
, Helge Reinsch
, Leonid Shupletsov
, Karen Markey
, Dirk E. De Vos
, Mischa Bonn
, Norbert Stock
, Guillaume Maurin
, Ellen H.G. Backus

Department of Physical Chemistry

Publications: Contribution to journal › Article › Peer Reviewed

Abstract

Several metal–organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10–30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH₃ are studied with -H, -CH₃ corresponding to the functions grafted to the organic linker. CAU-10-H shows a steep water uptake ≈18 RH% of interest for water harvesting, yet the subtle replacement of -H by -CH₃ in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials’ structural deformation and water ordering during adsorption with in situ sum-frequency generation, in situ X-ray diffraction, and molecular simulations are unraveled. In CAU-10-H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H-bonds to the framework μ-OH groups, while for CAU-10-CH₃, such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible.

Original language	English
Article number	2210050
Journal	Advanced Materials
Volume	36
Issue number	12
Early online date	18 Jan 2023
DOIs	https://doi.org/10.1002/adma.202210050
Publication status	Published - 21 Mar 2024

Funding

The authors thank Martijn de Lange (MIL-100(Cr), NH2-MIL-125 and one of the CAU-10-H isotherms), Thais Gancha (BioMOF(Ba)) and Xuerui Wang (SIFSIX-3-Ni)\u00A0for providing previously unpublished water adsorption isotherm data. S.C. gratefully acknowledges Dr. Martin Lutz (Universiteit Utrecht) for introducing him to the use of the software Eval15 and for his kind help. The Elettra Synchrotron facility was acknowledged for granting the beamtime at the single-crystal diffraction beamline XRD1 (Proposal ID 20185483). M.A.v.d.V. and D.R. were grateful for funding from the European Research Council (Grant No. 759212) within the Horizon 2020 Framework Programme (H2020-EU.1.1). M.B. and E.H.G.B. acknowledge the financial support from the MaxWater Initiative from the Max Planck Society. M.A.v.d.V. also acknowledges FWO Vlaanderen (Flanders) for financial support. The computational work was performed using HPC resources from GENCI-CINES (Grant A0120907613). The authors thank Martijn de Lange (MIL\u2010100(Cr), NH2\u2010MIL\u2010125 and one of the CAU\u201010\u2010H isotherms), Thais Gancha (BioMOF(Ba)) and Xuerui Wang (SIFSIX\u20103\u2010Ni) for providing previously unpublished water adsorption isotherm data. S.C. gratefully acknowledges Dr. Martin Lutz (Universiteit Utrecht) for introducing him to the use of the software Eval15 and for his kind help. The Elettra Synchrotron facility was acknowledged for granting the beamtime at the single\u2010crystal diffraction beamline XRD1 (Proposal ID 20185483). M.A.v.d.V. and D.R. were grateful for funding from the European Research Council (Grant No. 759212) within the Horizon 2020 Framework Programme (H2020\u2010EU.1.1). M.B. and E.H.G.B. acknowledge the financial support from the MaxWater Initiative from the Max Planck Society. M.A.v.d.V. also acknowledges FWO Vlaanderen (Flanders) for financial support. The computational work was performed using HPC resources from GENCI\u2010CINES (Grant A0120907613).

Austrian Fields of Science 2012

104017 Physical chemistry
103018 Materials physics
205019 Material sciences

Keywords

metal–organic frameworks
sum-frequency generation
water clusters
water harvesting

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Cite this

van der Veen, M. A., Canossa, S., Wahiduzzaman, M., Nenert, G., Frohlich, D., Rega, D., Reinsch, H., Shupletsov, L., Markey, K., De Vos, D. E., Bonn, M., Stock, N., Maurin, G., & Backus, E. H. G. (2024). Confined Water Cluster Formation in Water Harvesting by Metal–Organic Frameworks: CAU-10-H versus CAU-10-CH₃. Advanced Materials, 36(12), Article 2210050. https://doi.org/10.1002/adma.202210050

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title = "Confined Water Cluster Formation in Water Harvesting by Metal–Organic Frameworks: CAU-10-H versus CAU-10-CH3",

abstract = "Several metal–organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10–30 \% relative humidity (RH\%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH3 are studied with -H, -CH3 corresponding to the functions grafted to the organic linker. CAU-10-H shows a steep water uptake ≈18 RH\% of interest for water harvesting, yet the subtle replacement of -H by -CH3 in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials{\textquoteright} structural deformation and water ordering during adsorption with in situ sum-frequency generation, in situ X-ray diffraction, and molecular simulations are unraveled. In CAU-10-H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H-bonds to the framework μ-OH groups, while for CAU-10-CH3, such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible.",

keywords = "metal–organic frameworks, sum-frequency generation, water clusters, water harvesting",

author = "\{van der Veen\}, \{Monique A.\} and Stefano Canossa and Mohammad Wahiduzzaman and Gwilherm Nenert and Dominik Frohlich and Davide Rega and Helge Reinsch and Leonid Shupletsov and Karen Markey and \{De Vos\}, \{Dirk E.\} and Mischa Bonn and Norbert Stock and Guillaume Maurin and Backus, \{Ellen H.G.\}",

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van der Veen, MA, Canossa, S, Wahiduzzaman, M, Nenert, G, Frohlich, D, Rega, D, Reinsch, H, Shupletsov, L, Markey, K, De Vos, DE, Bonn, M, Stock, N, Maurin, G & Backus, EHG 2024, 'Confined Water Cluster Formation in Water Harvesting by Metal–Organic Frameworks: CAU-10-H versus CAU-10-CH₃', Advanced Materials, vol. 36, no. 12, 2210050. https://doi.org/10.1002/adma.202210050

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AU - Nenert, Gwilherm

AU - Frohlich, Dominik

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AU - Shupletsov, Leonid

AU - Markey, Karen

AU - De Vos, Dirk E.

AU - Bonn, Mischa

AU - Stock, Norbert

AU - Maurin, Guillaume

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