Electrocatalyst Design for Direct Borohydride Oxidation Guided by First Principles

Gholamreza Rostamikia, Romesh J. Patel, Irene Merino-Jimenez, Michael Hickner, Michael J. Janik

Research output: Contribution to journalArticlepeer-review

8 Scopus citations


Density functional theory (DFT) calculations are used to propose a Au-Cu binary metal catalyst for the electrochemical borohydride oxidation reaction (BOR), which is evaluated experimentally and observed to show enhanced oxidation activity relative to a pure Au electrode. Our previous work has applied DFT methods to determine the BOR mechanism and elucidate the key reaction steps that dictate catalyst activity and selectivity to complete oxidation. A balanced initial adsorption strength of the borohydride anion is essential for an active and selective catalyst. Adsorption must be strong enough to provide a reasonable coverage of surface species and promote B-H bond dissociation but not so strong as to promote easy dissociation and provide a high coverage of surface H atoms that result in H2 evolution. Borohydride adsorption energetics were evaluated for a series of close-packed pure metal surfaces. Copper catalysts appear encouraging but are not electrochemically stable under reaction conditions. Gold-copper alloys are predicted to show increased activity compared to a pure gold electrode while maintaining the selectivity to direct oxidation and increasing the stability compared to pure Cu. DFT results suggest an approximately 0.2 V decrease in the overpotential for borohydride oxidation on a Au2Cu(111) electrode compared to that on a Au(111) electrode. This DFT-predicted reduction in overpotential is realized experimentally. Electrodeposition was used to prepare AuCu electrodes, and their borohydride oxidation electrokinetics were examined by linear sweep voltammetry. An 88.5% gold and 11.5% copper sample demonstrated an overpotential reduction of 0.17 V compared to a pure Au electrode. The binding energy and adsorption free energy of BH4- over other surface alloys are also examined to further identify promising BOR electrodes. (Chemical Equation Presented).

Original languageEnglish (US)
Pages (from-to)2872-2881
Number of pages10
JournalJournal of Physical Chemistry C
Issue number5
StatePublished - Feb 9 2017

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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