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Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO₂ Reduction Reactions

Wu, Yueshen and Liang, Yongye and Wang, Hailiang (2021) Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO₂ Reduction Reactions. Accounts of Chemical Research, 54 (16). pp. 3149-3159. ISSN 0001-4842. doi:10.1021/acs.accounts.1c00200. https://resolver.caltech.edu/CaltechAUTHORS:20210825-141534166

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Abstract

Molecular catalysts, often deployed in homogeneous conditions, are favorable systems for structure–reactivity correlation studies of electrochemical reactions because of their well-defined active site structures and ease of mechanistic investigation. In pursuit of selective and active electrocatalysts for the CO₂ reduction reactions which are promising for converting carbon emissions to useful fuels and chemical products, it is desirable to support molecular catalysts on substrates because heterogeneous catalysts can afford the high current density and operational convenience that practical electrolyzers require. Herein, we share our understanding in the development of heterogenized metal phthalocyanine catalysts for the electrochemical reduction of CO₂. From the optimization of preparation methods and material structures for the electrocatalytic activity toward CO₂ reduction to CO, we find that molecular-level dispersion of the active material and high electrical conductivity of the support are among the most important factors controlling the activity. The molecular nature of the active site enables mechanism-based optimization. We demonstrate how electron-withdrawing and -donating ligand substituents can be utilized to modify the redox property of the molecule and improve its catalytic activity and stability. Adjusting these factors further allows us to achieve electrochemical reduction of CO₂ to methanol with appreciable activity, which has not been attainable by conventional molecular catalysts. The six-electron reduction process goes through CO as the key intermediate. Rapid and continuous electron delivery to the active site favors further reduction of CO to methanol. We also point out that, in homogeneous electrocatalysis where the catalyst molecules are dissolved in the electrolyte solution, even if the molecular structure remains intact, the actual catalysis may be dominated by molecules permanently adsorbed on the electrode surface and is thus heterogeneous in nature. This account uses our research on CO₂ electroreduction reactions catalyzed by metal phthalocyanine molecules to illustrate our understanding about heterogeneous molecular electrocatalysis, which is also applicable to other electrochemical systems.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.accounts.1c00200DOIArticle
ORCID:
AuthorORCID
Wu, Yueshen0000-0002-3784-0594
Liang, Yongye0000-0002-7416-8792
Wang, Hailiang0000-0003-4409-2034
Alternate Title:Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO2 Reduction Reactions
Additional Information:© 2021 American Chemical Society. Received: March 26, 2021. The research at Yale was supported by the U.S. National Science Foundation (Grant CHE-1651717). The research at SUSTech was supported by the National Science Foundation of China (Grant 22075125) and the Guangdong Provincial Key Laboratory (Grant 2018B030322001). Y.W. acknowledges the Dox Fellowship by Yale University. H.W. acknowledges the Sloan Research Fellowship. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1651717
National Natural Science Foundation of China22075125
Guangdong Provincial Key Laboratory2018B030322001
Yale UniversityUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Subject Keywords:Molecules, Electrodes, Catalysts, Catalytic reactions, Carbon nanotubes
Issue or Number:16
DOI:10.1021/acs.accounts.1c00200
Record Number:CaltechAUTHORS:20210825-141534166
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210825-141534166
Official Citation:Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO2 Reduction Reactions. Yueshen Wu, Yongye Liang, and Hailiang Wang. Accounts of Chemical Research 2021 54 (16), 3149-3159; DOI: 10.1021/acs.accounts.1c00200
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110409
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Aug 2021 17:38
Last Modified:25 Aug 2021 17:38

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