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

Journal Article · · ACS Catalysis

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.

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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Cited By (4)

Artificial photosynthesis: opportunities and challenges of molecular catalysts journal January 2019
Heterogeneous molecular catalysts for electrocatalytic CO2 reduction journal May 2019
A bacteriochlorin-diketopyrrolopyrrole triad as a donor for solution-processed bulk heterojunction organic solar cells journal January 2019
A new polypyridyl‐based Ru (II) complex as a highly efficient electrocatalyst for CO 2 reduction journal January 2020