Electrostatic Secondary-Sphere Interactions That Facilitate Rapid and Selective Electrocatalytic CO2 Reduction in a Fe-Porphyrin-Based Metal–Organic Framework

Ran Shimoni, Zhuocheng Shi, Shahar Binyamin, Yang Yang, Itamar Liberman, Raya Ifraemov, Subhabrata Mukhopadhyay, Liwu Zhang, Idan Hod

Research output: Contribution to journalArticlepeer-review

54 Scopus citations

Abstract

Metal–organic frameworks (MOFs) are promising platforms for heterogeneous tethering of molecular CO2 reduction electrocatalysts. Yet, to further understand electrocatalytic MOF systems, one also needs to consider their capability to fine-tune the immediate chemical environment of the active site, and thus affect its overall catalytic operation. Here, we show that electrostatic secondary-sphere functionalities enable substantial improvement of CO2-to-CO conversion activity and selectivity. In situ Raman analysis reveal that immobilization of pendent positively-charged groups adjacent to MOF-residing Fe-porphyrin catalysts, stabilize weakly-bound CO intermediates, allowing their rapid release as catalytic products. Also, by varying the electrolyte's ionic strength, systematic regulation of electrostatic field magnitude was achieved, resulting in essentially 100 % CO selectivity. Thus, this concept provides a sensitive molecular-handle that adjust heterogeneous electrocatalysis on demand.

Original languageEnglish
Article numbere202206085
JournalAngewandte Chemie - International Edition
Volume61
Issue number32
DOIs
StatePublished - 8 Aug 2022
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2022 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 in material characterization. This research was supported by the Israel Science Foundation (ISF) (grant No. 306/18), and by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No. 947655). L. Zhang acknowledges financial support from National Natural Science Foundation of China (nos. 22176036, 21976030). R. Shimoni thanks the Kreitman's PhD. Fellowship. We thank the Ilse Katz Institute for Nanoscale Science and Technology for the technical support in material characterization. This research was supported by the Israel Science Foundation (ISF) (grant No. 306/18), and by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No. 947655). L. Zhang acknowledges financial support from National Natural Science Foundation of China (nos. 22176036, 21976030). R. Shimoni thanks the Kreitman's PhD. Fellowship.

FundersFunder number
Ilse Katz Institute for Nanoscale Science and Technology
Horizon 2020 Framework Programme
European Commission
National Natural Science Foundation of China22176036, 21976030
Israel Science Foundation306/18
Horizon 2020947655

    Keywords

    • CO Reduction
    • Electrocatalysts
    • Fe-Porphyrin
    • Metal–Organic Frameworks
    • Secondary-Sphere

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