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Title: Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO 2 Conversion to CO

Abstract

Photosynthetic CO 2 fixation is mediated by the enzyme RuBisCo, which employs a nonredox-active metal (Mg 2+) to bind CO 2 adjacent to an organic ligand that provides reducing equivalents for CO 2 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 CO 2 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/cm 2 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.

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Dept. of Chemistry; Yale Univ., West Haven, CT (United States). Energy Sciences Inst.
  2. North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (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 Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1543706
Grant/Contract Number:  
FG02-05ER15661; FG02-07ER15909
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; bacteriochlorin; Co2 conversion; electrocatalysis; hydrogenation; porphyrin

Citation Formats

Jiang, Jianbing, Matula, Adam J., Swierk, John R., Romano, Neyen, Wu, Yueshen, Batista, Victor S., Crabtree, Robert H., Lindsey, Jonathan S., Wang, Hailiang, and Brudvig, Gary W. Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO. United States: N. p., 2018. Web. doi: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. United States. 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, and Brudvig, Gary W. Thu . "Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO". United States. https://doi.org/10.1021/acscatal.8b02991. https://www.osti.gov/servlets/purl/1543706.
@article{osti_1543706,
title = {Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO},
author = {Jiang, Jianbing and Matula, Adam J. and Swierk, John R. and Romano, Neyen and Wu, Yueshen and Batista, Victor S. and Crabtree, Robert H. and Lindsey, Jonathan S. and Wang, Hailiang and Brudvig, Gary W.},
abstractNote = {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.},
doi = {10.1021/acscatal.8b02991},
url = {https://www.osti.gov/biblio/1543706}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 11,
volume = 8,
place = {United States},
year = {2018},
month = {9}
}

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Figures / Tables:

Chart 1 Chart 1: (A) Structure of a porphyrin framework. (B) Molecular design of a synthetic bacteriochlorin. (C) Chemical structure of the synthetic bacteriochlorin ( ZnBC) introduced in this work.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.