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

1 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

Keywords

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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry (all)

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