Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 1, Pages 272-280Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b09653
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Funding
- NSF [CHE-1214131, CHE-1112564, CNS-0821794, ACI-1053575]
- ACS PRF grant [54436-ND4]
- Arnold and Mabel Beckman Foundation
- NIH F32 Postdoctoral Fellowship [F32GM122392]
- University of Colorado Boulder
- CU Crowdfunding
- Ohio Supercomputer Center [PCS0201-5]
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We report a novel metal-free chemical reduction of CO2 by a recyclable benzimidazole-based organo-hydride, whose choice was guided by quantum chemical calculations. Notably, benzimidazole-based hydride donors rival the hydride-donating abilities of noble-metal-based hydrides such as [Ru(tpy)(bpy)H](+) and [Pt(depe)(2)H](+). Chemical CO2 reduction to the formate anion (HCOO-) was carried out in the absence of biological enzymes, a sacrificial Lewis acid, or a base to activate the substrate or reductant. (CO2)-C-13 experiments confirmed the formation of (HCOO-)-C-13 by CO, reduction with the formate product characterized by H-1 NMR and C-13 NMR spectroscopy and ESI-MS. The highest formate yield of 66% was obtained in the presence of potassium tetrafluoroborate under mild conditions. The likely role of exogenous salt additives in this reaction is to stabilize and shift the equilibrium toward the ionic products. After CO2 reduction, the benzimidazole-based hydride donor was quantitatively oxidized to its aromatic benzimidazolium cation, establishing its recyclability. In addition, we electrochemically reduced the benzimidazolium cation to its organo-hydride form in quantitative yield, demonstrating its potential for electrocatalytic CO2 reduction. These results serve as a proof of concept for the electrocatalytic reduction of CO2 by sustainable, recyclable, and metal-free organo-hydrides.
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