Effects of proton tunneling distance on CO₂ reduction by Mn terpyridine species

Abstract

Herein, we report two manganese terpyridine dicarbonyls complexes, covalently attached with a proximal (1) or distal (2) amide moiety on the ortho position of the pendent phenyl ring as proton...

Electrochemical CO2 Reduction by Urea Hangman Mn Terpyridine species

“…In situ conversion of coordination mode from k 2 À N; N 0 ; N 00 À tpy (k 2 À tpy) to k 3 À N; N 0 ; N 00 À tpy (k 3 À tpy) As reported by our previous studies, [10][11] mono-decarbonyl of the precursors promoted by the electric field (ca. À 1.5 V vs. Fc + /0 ) would in situ results in the target catalysts.…”

“…This new peak might be ascribed to the reduction of the solvent-coordinated complex [Mn-(L)(CO) 2 (MeCN)] + . [15] The differential pulse voltammogram (DPV) test of 1 p shows a weaker peak followed by one main (d) Catalytic Tafel plots relating TOF and the driving force of CO 2 -to-CO conversion, and benchmarking of the performance of 1 p (this work, black dashed line and solid line were obtained by Foot-of-the-wave analysis and catalytic plateau current analysis, respectively) with that of previously reported electrocatalysts: FeTPPÀ Ur, [6] Mn(tpy-phenol)CO 2 Br, [10] Mn(tpyamide)CO 2 Br, [11] Mn(bpy-t Bu)(CO) 3 Br, [8c] Scan rate 100 mV/s, 0.1 M n Bu 4 NPF 6 in CH 3 CN. Glassy carbon working electrode, Ag + /Ag reference electrode, and Pt wire counter electrode.…”

“…Furthermore, we performed a comparative investigation on the Mn terpyridine derivates to the analogue with a proximal phenol [10] (or amide [11] ) studied in our previous work. The latter features a single-point hydrogen-bonding patter, while the former bears two-points.…”

“…200 mV. [11] Much improvement is still needed, however, to optimize the rate of catalysis at a cost of slight increase in overpotential.…”

“…Design of catalytic active sites for CO 2 reduction with different 2 nd coordination environment. (a) Proximal phenol, [10] (b) amide [11] and (c) urea functionalized Mn terpyridine di-carbonyls complexes. R represents the substituents.…”