Effect of Ligand Modification on the Mechanism of Electrocatalytic Hydrogen Production by Ni(pyridinethiolate)3- Derivatives

The Journal of Physical Chemistry. a
Carolyn N VircaTheresa M McCormick

Abstract

The effects of ligand modification on the catalytic mechanism of hydrogen production by Ni(PyS)3-derivatives, made with electron-withdrawing and -donating substitutions to the pyridinethiolate (PyS)-ligands, are studied experimentally and computationally using density functional theory. Thermodynamic data, spin density maps, and frontier molecular orbital diagrams were generated for reaction intermediates. Comparison of computed values for E0and p Kawith experimental values supports the proposed mechanisms. The rate of electrochemical hydrogen production is correlated with the effect of ligand modification. Notably, the presence of an electron-donating substituent favors an alternative mechanism for hydrogen production. Computationally it was determined that the electron-donating substituent causes deviation from the original chemical-electrochemical-chemical-electrochemical (CECE) mechanism of Ni(PyS)3-to a CCEE mechanism, while the CECE mechanism is maintained for all catalysts substituted with electron-withdrawing groups.

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Citations

Mar 19, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Qian LiaoDaniel L DuBois

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