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Title: Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction

Abstract

Condensation of fac-Re(5,6-diamino-1,10-phenanthroline)(CO)(3)Cl 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 photo-electron 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)(3)Cl, 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.

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Massachusetts Institute of Technology (MIT); Purdue University; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1258611
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 138; Journal Issue: 6
Country of Publication:
United States
Language:
English

Citation Formats

Oh, Seokjoon, Gallagher, James R., Miller, Jeffrey T., and Surendranath, Yogesh. Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction. United States: N. p., 2016. Web. doi:10.1021/jacs.5b13080.
Oh, Seokjoon, Gallagher, James R., Miller, Jeffrey T., & Surendranath, Yogesh. Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction. United States. doi:10.1021/jacs.5b13080.
Oh, Seokjoon, Gallagher, James R., Miller, Jeffrey T., and Surendranath, Yogesh. 2016. "Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction". United States. doi:10.1021/jacs.5b13080.
@article{osti_1258611,
title = {Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction},
author = {Oh, Seokjoon and Gallagher, James R. and Miller, Jeffrey T. and Surendranath, Yogesh},
abstractNote = {Condensation of fac-Re(5,6-diamino-1,10-phenanthroline)(CO)(3)Cl 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 photo-electron 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)(3)Cl, 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.},
doi = {10.1021/jacs.5b13080},
journal = {Journal of the American Chemical Society},
number = 6,
volume = 138,
place = {United States},
year = 2016,
month = 2
}
  • The study of the kinetics of the gasification of graphite and coal by carbon dioxide in a d.c. glow discharge has been continued. The carbon was placed on the anode. The concentrations of carbon monoxide proved to be significantly lower than those obtained with the carbon on the cathode. Under the conditions investigated, carbon monoxide is formed in the discharge mainly near and on the cathode. An ionic-heterogeneous mechanism of the formation of carbon monoxide, in which the positive ions CO/sub 2//sup +/ play an important role, has been examined.
  • A comparative study was made of the effect of catalysts on the reaction of carbon dioxide at 10/sup -2/ mm and 800 deg C with graphite powder and diamond dusts. These materials have surface areas, determined by the B.E.T. method with argon, of 2.5 and 22 m/sup 2/g/sup -1/, respectively. It is shown that all graphitization of the diamond during the reaction was less than the minimum detectable by photography of the powder with x rays. The velocity of the gasification per surface unit was, for the diamond, three times more than for the graphite. Iron that is 0.8% bymore » weight (C:Fe = 580:1), added in the form of ferric nitrate in solution, increases by 100 times the gasification velocity of the diamond and 324 times that of the graphite. A catalysis of the reaction of the diamond by sodium carbonate could not be shown because it seems that the sodium carbonate disappears during degassing. The importance of these results is discussed by reference to the theories of the catalysis of the oxidation of carbon and to the usual points of view on the structure of the diamond. (tr- auth)« less
  • Three synthetic paths have been used to prepare iron-based catalysts for the electrochemical reduction of oxygen in solid polymer fuel cells. The catalyst precursor used in the first synthetic path was a dispersion of Fe(OH){sub 2} on carbon black (Vulcan) that was reduced at 600 C in H{sub 2}. The second synthetic path involved a method to intercalate FeCl{sub 3} that was first used with graphite and then extended to Vulcan. The oxidized iron was reduced by either heating the resulting materials at 600 C in H{sub 2} or by reacting them at room temperature with K-naphthalene in a nonaqueousmore » solution. In the third synthetic path, Fe particles were generated directly on Vulcan by the reduction in a nonaqueous solution of FeCl{sub 2} with triethylborohydride. All these iron containing materials were then activated at 1,000 C in the presence of acetonitrile in order to transform them into active catalysts for O{sub 2} reduction. The best catalyst was obtained by extending the intercalation method of FeCl{sub 3} to carbon black (Vulcan) and then reducing the oxidized iron with K-naphthalene. Based on electrochemical and physicochemical analysis (mostly scanning electron microscopy and X-ray diffraction analysis) it is suggested that iron is included or intercalated in the carbon black particles. The higher catalytic activity of this material compared to the others is explained by the progressive release of the iron from the carbon black particles and its reaction with acetonitrile during the final thermal activation step at 1,000 C.« less