@article{198f1ddaaad04849b0637ba8fcd2c887,
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 cm2 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.",
author = "Zhe Weng and Yueshen Wu and Maoyu Wang and Jianbing Jiang and Ke Yang and Shengjuan Huo and Wang, {Xiao Feng} and Qing Ma and Brudvig, {Gary W.} and Batista, {Victor S.} and Yongye Liang and Zhenxing Feng and Hailiang Wang",
note = "Funding Information: The work is supported by the National Science Foundation (Grant CHE-1651717), the Doctoral New Investigator grant from the ACS Petroleum Research Fund, the Global Innovation Initiative from Institute of International Education, and the Callahan Faculty Scholar Endowment Fund from Oregon State University. The synthetic work was supported by the U.S. Department of Energy, Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science (Grant DEFG02-07ER15909). Additional support was provided by a generous donation from the TomKat Foundation. V.S.B. acknowledges support from the Air Force Office of Scientific Research grant FA9550-13-1-0020 and supercomputing time from the NERSC. Y.L. acknowledges financial support from Shenzhen Fundamental Research Funding (JCYJ20160608140827794) and Peacock Plan (KQTD20140630160825828). XAS measurements were done at 5-BM-D of DND-CAT at Advanced Photon Source (APS) of Argonne National Laboratory (ANL). DND-CAT is supported through E. I. duPont de Nemours &Co., Northwestern University, and The Dow Chemical Company. The use of APS of ANL is supported by DOE under Contract Number DE-AC02-06CH11357. Funding Information: The work is supported by the National Science Foundation (Grant CHE-1651717), the Doctoral New Investigator grant from the ACS Petroleum Research Fund, the Global Innovation Initiative from Institute of International Education, and the Callahan Faculty Scholar Endowment Fund from Oregon State University. The synthetic work was supported by the U.S. Department of Energy, Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science (Grant DEFG02-07ER15909). Additional support was provided by a generous donation from the TomKat Foundation. V.S.B. acknowledges support from the Air Force Office of Scientific Research grant FA9550-13-1-0020 and supercomputing time from the NERSC. Y.L. acknowledges financial support from Shenzhen Fundamental Research Funding (JCYJ20160608140827794) and Peacock Plan (KQTD20140630160825828). XAS measurements were done at 5-BM-D of DND-CAT at Advanced Photon Source (APS) of Argonne National Laboratory (ANL). DND-CAT is supported through E. I. duPont de Nemours & Co., Northwestern University, and The Dow Chemical Company. The use of APS of ANL is supported by DOE under Contract Number DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} The Author(s) 2018.",
year = "2018",
month = dec,
day = "1",
doi = "10.1038/s41467-018-02819-7",
language = "English",
volume = "9",
journal = "Nature Communications",
issn = "2041-1723",
publisher = "Nature Publishing Group",
number = "1",
}