4 years ago

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction
Junko Yano, Walter S. Drisdell, Nathan S. Lewis, Fadl H. Saadi, Jack H. Baricuatro, Sheraz Gul, Manuel P. Soriaga, Azhar I. Carim
Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogen-evolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η, of −η < 100 mV at a current density of −10 mA cm–2 in 0.500 M H2SO4(aq). To obtain a chemical description of the material as-prepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H2SO4(aq). Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b07606

DOI: 10.1021/jacs.7b07606

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