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 E0 and pKa with 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.
Article
Effect of Ligand Modification on the Mechanism of Electrocatalytic Hydrogen Production by Ni(pyridinethiolate)(3)(-) Derivatives
Journal of Physical Chemistry A
Sponsor
This work was funded by Portland State University.
Document Type
Citation
Publication Date
2-28-2018
Disciplines
Abstract
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DOI
10.1021/acs.jpca.7b11912
Persistent Identifier
https://archives.pdx.edu/ds/psu/25206
Citation Information
Virca, C.N. et al. Effect of Ligand Modification on the Mechanism of Electrocatalytic Hydrogen Production by Ni(pyridinethiolate)3– Derivatives. Journal of Physical Chemistry, 122(11):3057-3065.
© 2018 American Chemical Society