@article{4a2adf04cd01408abc70cbfbe80912dd,
title = "Electroreduction of CO2 Catalyzed by a Heterogenized Zn-Porphyrin Complex with a Redox-Innocent Metal Center",
abstract = "Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc-porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site-1 s-1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at 1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc-porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions.",
author = "Yueshen Wu and Jianbing Jiang and Zhe Weng and Maoyu Wang and Broere, {Dani{\"e}l L.J.} and Yiren Zhong and Brudvig, {Gary W.} and Zhenxing Feng and Hailiang Wang",
note = "Funding Information: The work is supported by National Science Foundation (Grant CHE-1651717), American Chemical Society Petroleum Research Fund, and the Global Innovation Initiative from Institute of International Education. Funding was also provided by a generous donation from the TomKat Foundation. Additional support from the U.S. Department of Energy, Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science (DE-FG02-07ER15909), is gratefully acknowledged. The authors thank Interfacial Processes Group at Chemical Science and Engineering Division of Argonne National Lab for the onsite electrochemical instrument support. 5BM-D of DND-CAT was supported through E. I. duPont de Nemours & Co., Northwestern University, and The Dow Chemical Company. The use of Advanced Photon Source of Argonne National Laboratory was supported by Department of Energy under Contract No. DE-AC02-06CH11357. Z.F. thanks the Callahan Faculty Scholar Endowment Fund from Oregon State University. D.L.J. B. acknowledges the support from The Netherlands Organization for Scientific Research (Rubicon Postdoctoral Fellowship 680-50-1517). The authors also thank Jonas Karosas for assistance with ICP-MS measurements.",
year = "2017",
month = aug,
day = "23",
doi = "10.1021/acscentsci.7b00160",
language = "English",
volume = "3",
pages = "847--852",
journal = "ACS Central Science",
issn = "2374-7943",
publisher = "American Chemical Society",
number = "8",
}