Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction
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 spectrosc...
| Main Authors: | , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/115121 https://orcid.org/0000-0002-8980-5213 https://orcid.org/0000-0003-1016-3420 |
| Summary: | 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. |
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