Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction
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ReGCC_Revision_Final.pdf
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1.97 MB
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Author(s)
Oh, Seokjoon
Gallagher, James R.
Miller, Jeffrey T.
Surendranath, Yogesh
Date Issued
January 2016
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Oh, Seokjoon et al. “Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction.” Journal of the American Chemical Society 138, 6 (February 2016): 1820–1823 © 2016 American Chemical Society
Version
Author's final manuscript
Abstract
ondensation of fac-Re(5,6-diamino-1,10-phenanthroline)(CO)₃Cl to o-quinone edge defects on graphitic carbon surfaces generates graphite-conjugated rhenium (GCC-Re) catalysts that are highly active for CO₂ reduction to CO in acetonitrile electrolyte. X-ray photoelectron and X-ray absorption spectroscopies establish the formation of surface-bound Re centers with well-defined coordination environments. GCC-Re species on glassy carbon surfaces display catalytic currents greater than 50 mA cm⁻² with 96 ± 3% Faradaic efficiency for CO production. Normalized for the number of Re active sites, GCC-Re catalysts exhibit higher turnover frequencies than that of a soluble molecular analogue, fac-Re(1,10-phenanthroline)(CO)₃Cl, and turnover numbers greater than 12,000. In contrast to the molecular analogue, GCC-Re surfaces display a Tafel slope of 150 mV/decade, indicative of a catalytic mechanism involving rate-limiting one-electron transfer. This work establishes graphite-conjugation as a powerful strategy for generating well-defined, tunable, heterogeneous electrocatalysts on ubiquitous graphitic carbon surfaces.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.5b13080
