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DFT and Empirical Considerations on Electrocatalytic Water/Carbon Dioxide Reduction by CoTMPyP in Neutral Aqueous Solutions **
Author(s) -
Bochlin Yair,
BenEliyahu Yeshayahu,
Kadosh Yanir,
Kozuch Sebastian,
Zilbermann Israel,
Korin Eli,
Bettelheim Armand
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000715
Subject(s) - porphyrin , cobalt , chemistry , formate , catalysis , aqueous solution , hydride , inorganic chemistry , electrochemistry , density functional theory , electrochemical reduction of carbon dioxide , metal , photochemistry , electrolyte , computational chemistry , electrode , organic chemistry , carbon monoxide
A combined experimental and density functional theory (DFT) investigation was employed in order to examine the mechanism of electrochemical CO 2 reduction and H 2 formation from water reduction in neutral aqueous solutions. A water soluble cobalt porphyrin, cobalt [5,10,15,20‐(tetra‐N‐methyl‐4‐pyridyl)porphyrin], (CoTMPyP), was used as catalyst. The possible attachment of different axial ligands as well as their effect on the electrocatalytic cycles were examined. A cobalt porphyrin hydride is a key intermediate which is generated after the initial reduction of the catalyst. The hydride is involved in the formation of H 2 and formate and acts as an indirect proton source for the formation of CO in these H + ‐starving conditions. The experimental results are in agreement with the computations and give new insights into electrocatalytic mechanisms involving water soluble metalloporphyrins. We conclude that in addition to the porphyrin's structure and metal ion center, the electrolyte surroundings play a key role in dictating the products of CO 2 /H 2 O reduction.