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

5 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
DOIs
Publication statusAccepted/In press - Jan 1 2018

Fingerprint

Electrocatalysts
Carbon Monoxide
Porphyrins
Ligands
Ribulose-Bisphosphate Carboxylase
Electrocatalysis
Electrolysis
Discrete Fourier transforms
Catalysis
Zinc
Current density
Enzymes
Metals
Degradation
bacteriochlorin

Keywords

  • bacteriochlorin
  • CO conversion
  • electrocatalysis
  • hydrogenation
  • porphyrin

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO. / Jiang, Jianbing; Matula, Adam J.; Swierk, John R.; Romano, Neyen; Wu, Yueshen; Batista, Victor S.; Crabtree, Robert H.; Lindsey, Jonathan S.; Wang, Hailiang; Brudvig, Gary W.

In: ACS Catalysis, 01.01.2018, p. 10131-10136.

Research output: Contribution to journalArticle

Jiang, J, Matula, AJ, Swierk, JR, Romano, N, Wu, Y, Batista, VS, Crabtree, RH, Lindsey, JS, Wang, H & Brudvig, GW 2018, 'Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO', ACS Catalysis, pp. 10131-10136. https://doi.org/10.1021/acscatal.8b02991
Jiang, Jianbing ; Matula, Adam J. ; Swierk, John R. ; Romano, Neyen ; Wu, Yueshen ; Batista, Victor S. ; Crabtree, Robert H. ; Lindsey, Jonathan S. ; Wang, Hailiang ; Brudvig, Gary W. / Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO. In: ACS Catalysis. 2018 ; pp. 10131-10136.
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