Electrochemical Hydrogen Evolution at Ordered Mo7Ni7

Peter M. Csernica, James R. McKone*, Catherine R. Mulzer, William R. Dichtel, Héctor D. Abruña, Francis J. DiSalvo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

Ni-Mo alloys containing up to ∼15 mol % Mo are excellent non-noble electrocatalysts for the hydrogen evolution reaction (HER) in alkaline aqueous electrolytes. To date, studies have not addressed the details of HER activity of ordered Ni-Mo intermetallic compounds, which can contain a significantly larger fraction of Mo (up to 50 mol %) than can be accessed through high-temperature alloying. Here, we present a straightforward and facile synthesis of three phase-pure electrocatalyst powders using a precipitation-reduction approach: ordered Mo7Ni7, disordered Ni0.92Mo0.08, and pure Ni. The Ni0.92Mo0.08 alloy exhibited a nearly 10-fold higher mass-specific HER activity than either pure Ni or Mo7Ni7, where much of the difference could be attributed to relative surface area. Therefore, we attempted to quantify and account for differences in surface areas using electron microscopy, impedance spectroscopy, and gas adsorption measurements. These data suggest that Ni-Mo alloys and intermetallic compounds exhibit substantial pseudocapacitance at potentials near the onset of hydrogen evolution, which can cause impedance spectroscopy to overestimate the interfacial capacitance, and thus the electrochemically active surface area, of these materials. From these observations, we postulate Mo redox activity as the chemical basis for the observed pseudocapacitance of Ni-Mo composites. Furthermore, using gas adsorption measurements, rather than capacitance, to estimate active surface area, we find that ordered Mo7Ni7 is more intrinsically active than the Ni0.92Mo0.08 alloy, implying that Mo7Ni7 intermetallics with high surface area will also give higher mass-specific activities than alloys with comparable roughness. (Graph Presented).

Original languageEnglish (US)
Pages (from-to)3375-3383
Number of pages9
JournalACS Catalysis
Volume7
Issue number5
DOIs
StatePublished - May 5 2017

Keywords

  • BET
  • HER
  • Ni-Mo
  • alkaline hydrogen evolution
  • electrolysis
  • intermetallic
  • pseudocapacitance

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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