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Title: Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5b13080· OSTI ID:1258611
 [1];  [2];  [3];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Purdue Univ., West Lafayette, IN (United States)
+ Show Author Affiliations

Condensation 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. Here, this work establishes graphite-conjugation as a powerful strategy for generating well-defined, tunable, heterogeneous electrocatalysts on ubiquitous graphitic carbon surfaces.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Massachusetts Institute of Technology (MIT); Purdue University; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1258611
Journal Information:
Journal of the American Chemical Society, Vol. 138, Issue 6; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 144 works
Citation information provided by
Web of Science

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Cited By (18)

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Synthesize and Characterization of 2‐Aminothiazole Monomer and Polymer‐based Bifunctional Fe/N/C Catalysts for Oxygen and Carbon Dioxide Reduction Reactions journal April 2019
Heterogeneous molecular catalysts for electrocatalytic CO2 reduction journal May 2019
Nucleophilic Additions to Coordinated 1,10-Phenanthroline: Intramolecular, Intermolecular, Reversible, and Irreversible journal October 2016
A 2,2′-bipyridine-containing covalent organic framework bearing rhenium( i ) tricarbonyl moieties for CO 2 reduction journal January 2018
Recent Advances in Metal–Organic Frameworks for Photo‐/Electrocatalytic CO 2 Reduction journal September 2019
Artificial photosynthesis by light absorption, charge separation, and multielectron catalysis journal January 2018
Fighting Deactivation: Classical and Emerging Strategies for Efficient Stabilization of Molecular Electrocatalysts journal January 2020
Metallic Cobalt-Carbon Composite as Recyclable and Robust Magnetic Photocatalyst for Efficient CO 2 Reduction journal July 2018
Mo-based 2D MOF as a highly efficient electrocatalyst for reduction of N 2 to NH 3 : a density functional theory study journal January 2019
Electrocatalytic Metal-Organic Frameworks for Energy Applications journal November 2017
Carbon nitride as a ligand: edge-site coordination of ReCl(CO) 3 -fragments to g-C 3 N 4 journal January 2019
Transition Metal Diborides: A New Type of High‐performance Electrocatalysts for Nitrogen Reduction journal May 2019
A Water-Soluble Cu Complex as Molecular Catalyst for Electrocatalytic CO 2 Reduction on Graphene-Based Electrodes journal November 2018
Rhenium is different: CO tetramerization induced by a divalent lanthanide complex in rhenium carbonyls text January 2019
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