Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO

Jianbing Jiang, Adam J. Matula, John R. Swierk, Neyen Romano, Yueshen Wu, Victor S. Batista, Robert H. Crabtree, Jonathan S. Lindsey, Hailiang Wang, Gary W. Brudvig

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Photosynthetic CO2 fixation is mediated by the enzyme RuBisCo, which employs a nonredox-active metal (Mg2+) to bind CO2 adjacent to an organic ligand that provides reducing equivalents for CO2 fixation. Attempts to use porphyrins as ligands in reductive catalysis have typically encountered severe stability issues owing to ligand reduction. Here, a synthetic zinc-bacteriochlorin is reported as an effective and robust electrocatalyst for CO2 reduction to CO with an overpotential of 330 mV, without undergoing porphyrin-like ligand degradation (or demetalation) even after prolonged bulk electrolysis. The reaction has a CO Faradaic efficiency of 92% and sustains a total current density of 2.3 mA/cm2 at -1.9 V vs Ag/AgCl. DFT calculations highlight the molecular origin of the observed stability and provide insights into catalytic steps. This bioinspired study opens avenues for the application of bacteriochlorin compounds for reductive electrocatalysis with extended life beyond that seen with porphyrin counterparts.

Original languageEnglish
Pages (from-to)10131-10136
Number of pages6
JournalACS Catalysis
Volume8
Issue number11
DOIs
Publication statusPublished - Nov 2 2018

Keywords

  • CO conversion
  • bacteriochlorin
  • electrocatalysis
  • hydrogenation
  • porphyrin

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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    Jiang, J., Matula, A. J., Swierk, J. R., Romano, N., Wu, Y., Batista, V. S., Crabtree, R. H., Lindsey, J. S., Wang, H., & Brudvig, G. W. (2018). Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO. ACS Catalysis, 8(11), 10131-10136. https://doi.org/10.1021/acscatal.8b02991