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Computational Study of Fluorinated Diglyoxime-Iron Complexes: Tuning the Electrocatalytic Pathways for Hydrogen Evolution by Aparna Karippara Harshan; Brian H. Solis; Jay R. Winkler; Harry B. Gray; Sharon Hammes-Schiffer is a Chemistry article available to read on EtoBox.

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The ability to tune the properties of hydrogen-evolving molecular electrocatalysts is important for developing alternative energy sources. Fluorinated diglyoxime-iron complexes have been shown to evolve hydrogen at moderate overpotentials. Herein two such complexes, [(dAr(F)gBF2)2Fe(py)2], denoted A, and [(dAr(F)g2H-BF2)Fe(py)2], denoted B [dAr(F)g = bis(pentafluorophenyl-glyoximato); py = pyridine], are investigated with density functional theory calculations. B differs from A in that one BF2 bridge is replaced by a proton bridge of the form O-H-O. According to the calculations, the catalytic pathway for A involves two consecutive reduction steps, followed by protonation of an Fe(0) species to generate the active Fe(II)-hydride species. B is found to proceed via two parallel pathways, where one pathway is similar to that for A, and the additional pathway arises from protonation of the O-H-O bridge, followed by spontaneous reduction to an Fe(0) intermediate and intramolecular proton transfer from the ligand to the metal center or protonation by external acid to form the same active Fe(II)-hydride species. Simulated cyclic voltammograms (CVs) based on these mechanisms are in qualita

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Author

Aparna Karippara Harshan; Brian H. Solis; Jay R. Winkler; Harry B. Gray; Sharon Hammes-Schiffer

Published

2016

Language

EN

Field

Chemistry (Physical Sciences)