Hydrogen Evolution Reaction Electrocatalysts Based on Electrolytic and Chemical-Catalytic Alloys of Rhenium and Nickel
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ogen Evolution Reaction Electrocatalysts Based on Electrolytic and Chemical-Catalytic Alloys of Rhenium and Nickel1 V. V. Kuznetsova, c, Yu. D. Gamburgb, *, V. M. Krutskikhb, V. V. Zhulikovb, E. A. Filatovaa, A. L. Trigubd, and O. A. Belyakovae aMendeleev
University of Chemical Technology, Moscow, 125047 Russia Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, 119071 Russia c National Research Nuclear University—Moscow Physical Engineering Institute, Moscow, 115409 Russia d Kurchatov University—National Research Center, Moscow, 123098 Russia e Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia *e-mail: [email protected]
b
Received September 24, 2019; revised February 7, 2020; accepted February 20, 2020
Abstract—The composition, structure, and electrocatalytic properties in HER are compared for Re–Ni electrodeposits and Ni–Re–P alloys synthesized by chemical-catalytic deposition with the use of sodium hypophosphite as the reducer. The coordination numbers of nickel and rhenium and the interatomic distances of synthesized materials are determined by EXAFS and XANES methods. It is shown that the structure of Re‒Ni catalysts with the highest catalytic activity lacks the far order as regards the position of rhenium and nickel atoms, which allows assuming that these electrode materials are in the amorphous state. For chemicalcatalytic Ni–Re–P coatings, it is shown that the introduction of rhenium into their composition lowers down the phosphorus content in the alloy formed. The chemical-catalytic Ni–Re–P coatings show promise as the HER catalysts in acid solutions. Keywords: electrocatalysis, alloys, rhenium, nickel, phosphorus, hydrogen evolution reaction DOI: 10.1134/S1023193520100079
INTRODUCTION The active development of hydrogen energetics requires the elaboration of new electrocatalytic materials for the hydrogen reaction. Both the cathodic catalysts of the hydrogen evolution reaction (HER) and the anodic catalysts for oxidation of H2 molecules are of interest for practice. The nonplatinum catalysts of hydrogen oxidation tolerant with respect to CO oxidation are promising for the use in low-temperature fuel cells. Although the hydrogen reaction was already studied for several decades [1–4], no unambiguous criteria exist so far of choosing the efficient electrocatalytic materials for it. In the majority of cases, the potentially advantageous systems were selected based on the volcano-shaped dependences of the HER rate on the enthalpy of the metal-hydrogen bond [5, 6], although no sufficiently rigorous substantiation was given to the this dependence [7, 8]. To obtain systems with the optimal enthalpy of the M–H bond, it is reasonable to synthesize alloys in which one of the components is located on the ascending branch of the “volcano” and 1 In
memory of the famous electrochemist Vladimir Sergeevich Bagotzky whose centenary is celebrated in 2020.
the other lies on its descending branch. In [9], the synergistic cata
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