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.

doi:10.1021/acscatal.8b02991

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

Journal Article · 19 September 2018 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.8b02991 · OSTI ID:1543706

Jiang, Jianbing ^[1]; Matula, Adam J. ^[1];

^[1]; Romano, Neyen ^[1]; Wu, Yueshen ^[1];

^[1];

^[2];

^[1];

^[1]

Yale Univ., New Haven, CT (United States). Dept. of Chemistry; Yale Univ., West Haven, CT (United States). Energy Sciences Inst.
North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry

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. Here, this bioinspired study opens avenues for the application of bacteriochlorin compounds for reductive electrocatalysis with extended life beyond that seen with porphyrin counterparts.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Washington Univ., St. Louis, MO (United States); Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-05ER15661; FG02-07ER15909

OSTI ID:: 1543706

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 11 Vol. 8; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemistry
bacteriochlorin
Co2 conversion
electrocatalysis
hydrogenation
porphyrin

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

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References (42)

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