skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on July 18, 2019

Title: Mechanistic aspects of CO 2 reduction catalysis with manganese-based molecular catalysts

One approach for the conversion of CO 2 into fuels or fuel precursors is the proton-coupled reduction of CO 2 to CO or formic acid, using transition metal complexes as catalysts in either electrocatalytic or photocatalytic processes. While a number of such molecular catalysts have been investigated over the years, many are based on expensive precious metals. However, a growing family of pre-catalysts based on the earth-abundant metal, manganese, originally with the generic formula, [Mn(α-diimine)(CO) 3L] +/0, but now expanded to also include non-α-diimine ligands, has recently emerged as a promising, cheaper alternative to the heavily-investigated rhenium-based analogues. In this paper, we discuss the current mechanistic understanding of Mn-based CO 2 reduction pre-catalysts, from the point of view of both computational modeling and experimental techniques. We also highlight the methods used to accurately determine catalytic figures of merit, such as overpotential and turnover frequency. In conclusion, we have summarized the major findings in both electrocatalytic and photocatalytic CO 2 reduction driven by Mn-based catalysts, including exciting new developments involving immobilization of the molecular catalysts on solid supports or electrodes, and also their use in photoelectrochemical CO 2 reduction where solar energy is used to overcome the demanding electrochemical overpotential.
Authors:
 [1] ;  [1] ;  [2] ;  [2] ;  [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  2. Univ. of Massachusetts, Boston, MA (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
BNL-207838-2018-JAAM
Journal ID: ISSN 0010-8545
Grant/Contract Number:
SC0012704; CHE-1301132
Type:
Accepted Manuscript
Journal Name:
Coordination Chemistry Reviews
Additional Journal Information:
Journal Volume: 374; Journal ID: ISSN 0010-8545
Publisher:
Elsevier
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Massachusetts, Boston, MA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1460701