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Title: Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction

Abstract

Restructuring-induced catalytic activity is an intriguing phenomenon of fundamental importance to rational design of high-performance catalyst materials. We study three coppercomplex materials for electrocatalytic carbon dioxide reduction. Among them, the copper(II) phthalocyanine exhibits by far the highest activity for yielding methane with a Faradaic efficiency of 66% and a partial current density of 13 mA cm -2 at the potential of – 1.06 V versus the reversible hydrogen electrode. Utilizing in-situ and operando X-ray absorption spectroscopy, we find that under the working conditions copper(II) phthalocyanine undergoes reversible structural and oxidation state changes to form ~ 2 nm metallic copper clusters, which catalyzes the carbon dioxide-to-methane conversion. Density functional calculations rationalize the restructuring behavior and attribute the reversibility to the strong divalent metal ion–ligand coordination in the copper(II) phthalocyanine molecular structure and the small size of the generated copper clusters under the reaction conditions.

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [2];  [4];  [5];  [6];  [2];  [2];  [7];  [3]; ORCiD logo [2]
  1. South University of Science and Technology of China, Shenzhen (China); Yale Univ., New Haven, CT (United States)
  2. Yale Univ., New Haven, CT (United States)
  3. Oregon State Univ., Corvallis, OR (United States)
  4. Yale Univ., New Haven, CT (United States); Shanghai University (China)
  5. University of South China, Hengyang, Hunan (China)
  6. Northwestern Univ., Evanston, IL (United States)
  7. South University of Science and Technology of China, Shenzhen (China)
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1419868
Grant/Contract Number:  
FG02-07ER15909; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Weng, Zhe, Wu, Yueshen, Wang, Maoyu, Jiang, Jianbing, Yang, Ke, Huo, Shengjuan, Wang, Xiao-Feng, Ma, Qing, Brudvig, Gary W., Batista, Victor S., Liang, Yongye, Feng, Zhenxing, and Wang, Hailiang. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. United States: N. p., 2018. Web. doi:10.1038/s41467-018-02819-7.
Weng, Zhe, Wu, Yueshen, Wang, Maoyu, Jiang, Jianbing, Yang, Ke, Huo, Shengjuan, Wang, Xiao-Feng, Ma, Qing, Brudvig, Gary W., Batista, Victor S., Liang, Yongye, Feng, Zhenxing, & Wang, Hailiang. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. United States. doi:10.1038/s41467-018-02819-7.
Weng, Zhe, Wu, Yueshen, Wang, Maoyu, Jiang, Jianbing, Yang, Ke, Huo, Shengjuan, Wang, Xiao-Feng, Ma, Qing, Brudvig, Gary W., Batista, Victor S., Liang, Yongye, Feng, Zhenxing, and Wang, Hailiang. Mon . "Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction". United States. doi:10.1038/s41467-018-02819-7. https://www.osti.gov/servlets/purl/1419868.
@article{osti_1419868,
title = {Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction},
author = {Weng, Zhe and Wu, Yueshen and Wang, Maoyu and Jiang, Jianbing and Yang, Ke and Huo, Shengjuan and Wang, Xiao-Feng and Ma, Qing and Brudvig, Gary W. and Batista, Victor S. and Liang, Yongye and Feng, Zhenxing and Wang, Hailiang},
abstractNote = {Restructuring-induced catalytic activity is an intriguing phenomenon of fundamental importance to rational design of high-performance catalyst materials. We study three coppercomplex materials for electrocatalytic carbon dioxide reduction. Among them, the copper(II) phthalocyanine exhibits by far the highest activity for yielding methane with a Faradaic efficiency of 66% and a partial current density of 13 mA cm-2 at the potential of – 1.06 V versus the reversible hydrogen electrode. Utilizing in-situ and operando X-ray absorption spectroscopy, we find that under the working conditions copper(II) phthalocyanine undergoes reversible structural and oxidation state changes to form ~ 2 nm metallic copper clusters, which catalyzes the carbon dioxide-to-methane conversion. Density functional calculations rationalize the restructuring behavior and attribute the reversibility to the strong divalent metal ion–ligand coordination in the copper(II) phthalocyanine molecular structure and the small size of the generated copper clusters under the reaction conditions.},
doi = {10.1038/s41467-018-02819-7},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {1}
}

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