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Elucidating the Reactivity and Mechanism of CO₂ Electroreduction at Highly Dispersed Cobalt Phthalocyanine

Zhu, Minghui and Ye, Ruquan and Jin, Kyoungsuk and Lazouski, Nikifar and Manthiram, Karthish (2018) Elucidating the Reactivity and Mechanism of CO₂ Electroreduction at Highly Dispersed Cobalt Phthalocyanine. ACS Energy Letters, 3 (6). pp. 1381-1386. ISSN 2380-8195. doi:10.1021/acsenergylett.8b00519.

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Transforming carbon dioxide to carbon monoxide with electrochemical methods allows for small-scale, modular conversion of point sources of carbon dioxide. In this work, through the preparation of a well-dispersed cobalt phthalocyanine model catalyst immobilized on carbon paper, we revealed high turnover frequencies for reducing carbon dioxide at low catalyst loadings, which are obscured at higher loadings due to aggregation. The low catalyst loadings have also enabled mechanistic studies that provide a detailed understanding of the molecular-level picture of how cobalt phthalocyanine facilitates proton and electron transfers in the rate-limiting step. We are able to tune the rate-limiting step from electron transfer to concerted proton–electron transfer, enabling higher rates of carbon dioxide reduction. Our results highlight the significance of dispersion for understanding the intrinsic catalytic performance of metal phthalocyanines for electroreduction of CO₂.

Item Type:Article
Related URLs:
URLURL TypeDescription
Zhu, Minghui0000-0003-1593-9320
Ye, Ruquan0000-0002-2543-9090
Jin, Kyoungsuk0000-0003-3009-6691
Lazouski, Nikifar0000-0002-4655-2041
Manthiram, Karthish0000-0001-9260-3391
Additional Information:© 2018 American Chemical Society. Received 29 March 2018. Accepted 17 May 2018. Published online 17 May 2018. Published in issue 8 June 2018. We thank Subodh Gupta, Alan Hatton, Klavs Jensen, and Anamika Mukherjee for insightful discussions. We gratefully acknowledge financial support from Cenovus Energy and the MIT Energy Initiative Low Carbon Energy Center on Carbon Capture, Utilization, and Storage. Author Contributions: M.Z. and R.Y. contributed equally to this work. The authors declare no competing financial interest.
Funding AgencyGrant Number
Massachusetts Institute of Technology (MIT)UNSPECIFIED
Subject Keywords:Oxides, Inorganic carbon compounds, Cobalt, Redox reactions, Catalysts
Issue or Number:6
Record Number:CaltechAUTHORS:20220505-565417000
Persistent URL:
Official Citation:Elucidating the Reactivity and Mechanism of CO2 Electroreduction at Highly Dispersed Cobalt Phthalocyanine Minghui Zhu, Ruquan Ye, Kyoungsuk Jin, Nikifar Lazouski, and Karthish Manthiram ACS Energy Letters 2018 3 (6), 1381-1386 DOI: 10.1021/acsenergylett.8b00519
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114627
Deposited By: George Porter
Deposited On:06 May 2022 22:05
Last Modified:06 May 2022 22:05

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