Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate

Charles Musgrave, Chern-Hooi Lim, Stefan Ilic, Abdulaziz Alherz, Brady Worrell, Samuel Bacon, James Hynes, Ksenija Glusac

Research output: Contribution to journalArticlepeer-review

61 Scopus Citations

Abstract

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)2H]+. 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. 13CO2 experiments confirmed the formation of H13COO- by CO2 reduction with the formate product characterized by 1H NMR and 13C 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.
Original languageAmerican English
Pages (from-to)272-280
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number1
DOIs
StatePublished - 2019

NREL Publication Number

  • NREL/JA-5K00-73077

Keywords

  • CO2
  • electrocatalysis
  • organo-hydrides

Fingerprint

Dive into the research topics of 'Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate'. Together they form a unique fingerprint.

Cite this