Theoretical design of molecular electrocatalysts with flexible pendant amines for hydrogen production and oxidation

Laura E. Fernandez, Samantha Horvath, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

Abstract

The design of hydrogen oxidation and production electrocatalysts is important for the development of alternative renewable energy sources. The overall objective is to maximize the turnover frequency and minimize the overpotential. We use computational methods to examine a variety of nickel-based molecular electrocatalysts with pendant amines. Our studies focus on the proton-coupled electron transfer (PCET) process involving electron transfer between the complex and the electrode and intramolecular proton transfer between the nickel center and the nitrogen of the pendant amine. The concerted PCET mechanism, which tends to require a lower overpotential, is favored by a smaller equilibrium Ni-N distance and a more flexible pendant amine ligand, thereby decreasing the energetic penalty for the nitrogen to approach the nickel center for proton transfer. Our calculations provide predictions about designing catalysts that incorporate these properties. These design principles will be useful for developing the next generation of hydrogen catalysts.

Original languageEnglish (US)
Pages (from-to)542-546
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume4
Issue number3
DOIs
StatePublished - Feb 7 2013

Keywords

  • electrochemistry
  • electron transfer
  • proton transfer
  • proton-coupled electron transfer

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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