CoP as an acid-stable active electrocatalyst for the hydrogen-evolution reaction: Electrochemical synthesis, interfacial characterization and performance evaluation

Fadl H. Saadi, Azhar I. Carim, Erik Verlage, John C. Hemminger, Nathan S. Lewis, Manuel P. Soriaga

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141 Citations (Scopus)


Films of CoP have been electrochemically synthesized, characterized, and evaluated for performance as a catalyst for the hydrogen-evolution reaction (HER). The film was synthesized by cathodic deposition from a boric acid solution of Co2+ and H2PO2 - on copper substrates followed by operando remediation of exogenous contaminants. The films were characterized structurally and compositionally by scanning-electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectrophotometry. The catalytic activity was evaluated by cyclic voltammetry and chronopotentiometry. Surface characterization prior to electrocatalysis indicated that the film consisted of micrometer-sized spherical clusters located randomly and loosely on a slightly roughened surface. The composition of both the clusters and surface consisted of cobalt in the metallic, phosphide, and amorphous-oxide forms (CoO·Co2O3) and of phosphorus as phosphide and orthophosphate. The orthophosphate species, produced by air-oxidation, were eliminated upon HER electrocatalysis in sulfuric acid. The operando film purification yielded a functional electrocatalyst with a Co:P stoichiometric ratio of 1:1. After the HER, the surface was densely packed with micrometer-sized, mesa-like particles whose tops were flat and smooth. The CoP eletrodeposit exhibited an 85 mV overvoltage (η) for the HER at a current density of 10 mA cm-2 and was stable under operation in highly acidic solution, with an increase in η of 18 mV after 24 h of continuous operation. The comparative HER catalytic performance of CoP, film or nanoparticles, is as follows: ηPt < ηCoP film = ηCoP NP, ηNi2P < ηCoSe2 < ηMoS2 < ηMoSe2.

Original languageEnglish
Pages (from-to)29294-29300
Number of pages7
JournalJournal of Physical Chemistry C
Issue number50
Publication statusPublished - Dec 18 2014


ASJC Scopus subject areas

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

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