Assembly of a Metal–Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO2 Reduction

Subhabrata Mukhopadhyay, Ran Shimoni, Itamar Liberman, Raya Ifraemov, Illya Rozenberg, Idan Hod

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

Electrochemically active Metal-Organic Frameworks (MOFs) have been progressively recognized for their use in solar fuel production schemes. Typically, they are utilized as platforms for heterogeneous tethering of exceptionally large concentration of molecular electrocatalysts onto electrodes. Yet so far, the potential influence of their extraordinary chemical modularity on electrocatalysis has been overlooked. Herein, we demonstrate that, when assembled on a solid Ag CO2 reduction electrocatalyst, a non-catalytic UiO-66 MOF acts as a porous membrane that systematically tunes the active site's immediate chemical environment, leading to a drastic enhancement of electrocatalytic activity and selectivity. Electrochemical analysis shows that the MOF membrane improves catalytic performance through physical and electrostatic regulation of reactants delivery towards the catalytic sites. The MOF also stabilizes catalytic intermediates via modulation of active site's secondary coordination sphere. This concept can be expanded to a wide range of proton-coupled electrochemical reactions, providing new means for precise, molecular-level manipulation of heterogeneous solar fuels systems.

Original languageEnglish
Pages (from-to)13423-13429
Number of pages7
JournalAngewandte Chemie - International Edition
Volume60
Issue number24
DOIs
StatePublished - 7 Jun 2021
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Funding

We thank the Ilse Katz Institute for Nanoscale Science and Technology for the technical support of material characterization. The project leading to this application has received funding from European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme under grant agreement No. 947655. This work was partially funded by the Israel Science Foundation (ISF) PAT Center of Excellence (grant No. 2171/17). S.M. is thankful for a Kreitman postdoctoral fellowship. R.S., and I.L. thank Kreitman Ph.D. fellowship. and R.I. thank the Rothschild Ph.D. fellowship. We thank the Ilse Katz Institute for Nanoscale Science and Technology for the technical support of material characterization. The project leading to this application has received funding from European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme under grant agreement No. 947655. This work was partially funded by the Israel Science Foundation (ISF) PAT Center of Excellence (grant No. 2171/17). S.M. is thankful for a Kreitman postdoctoral fellowship. R.S., and I.L. thank Kreitman Ph.D. fellowship. and R.I. thank the Rothschild Ph.D. fellowship.

FundersFunder number
Ilse Katz Institute for Nanoscale Science and Technology
PAT Center of Excellence2171/17
Horizon 2020 Framework Programme
European Research Council
Israel Science Foundation
Horizon 2020947655

    Keywords

    • CO reduction
    • UiO-66
    • electrocatalyst
    • mass Transport
    • metal–organic framework (MOF)

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