Metal–bipyridine complexes as electrocatalysts for the reduction of CO2: a density functional theory study. Issue 42 (22nd October 2019)

• Record Type: Journal Article
• Authors: Zhang, Peng; Yang, Xuejing; Hou, Xiuli; Xu, Xuejian; Xiao, Beibei; Huang, Jun; Stampfl, Catherine
• Is Part Of: Physical chemistry chemical physics. Volume 21:Issue 42(2019)
• Page Start: 23742
• Page End: 23748
• Publication Date: 2019-10-22
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp02916h
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The transition metal determines the catalytic activity of M(bpy)(CO)4 . Re(bpy)(CO)4 and Mn(bpy)(CO)4 exhibit better catalytic activity due to the weaker adsorption strength of CO. Abstract : Polypyridyl transition metal complexes are well-established homogeneous electrocatalysts for the reduction of CO2 . In this work, the relationship between the transition metal (including V, Cr, Mn, Nb, Mo, Ta, W, and Re) and the catalytic activity has been theoretically investigated using density functional theory. It is found that the transition metal center determines the catalytic activity of M(bpy)(CO)4 . Among the eight metal complexes, Re(bpy)(CO)4 and Mn(bpy)(CO)4 exhibit better catalytic activity due to the weaker adsorption strength of CO and lower d-band center, which makes it easier to activate the metal complex and results in a lower reaction free energy of the rate-determining step at the reduction potential. We believe that these results can provide guidelines for the design of novel electrocatalysts for CO2 reduction.