Quantum chemical simulation of reactions of hydrogen and oxygen with a gold–nickel bimetallic nanocoating

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Abstract

Quantum chemical calculations are performed to determine the heats of hydrogenation for the simplest nanosized Au3–/Ni2+ bimetallic system via three possible reaction pathways. It is shown that the reaction pathway releasing maximum energy is Au3–/Ni2+ + H2 → (Au3H2)–/Ni2+ with a heat of reaction of 43.7 kcal/mol. Quantum chemical methods are also used to calculate the heats of reaction for several reaction pathways between Au3–/Ni2+ and oxygen. It is found that the pathway that releases maximum energy adds one O atom to Au3H2 while the other one combines with nickel, (Au3H2)–/Ni2+ + O₂ → (Au3H2–O)–/(Ni2O)+, with a heat of reaction of 39.0 kcal/mol. The reaction mechanism and energy budget are determined for the elementary steps involved in the production of gold Au3– and water from the oxide (Au3H2–O)–. Based on the calculated results, an explanation is proposed for experimental results on successive exposure of a gold–nickel bimetallic nanocoating to hydrogen and oxygen. Since contact between gold and nickel results in negatively charged gold and positively charged nickel particles, the calculations are performed for negatively and positively charged gold- and nickel-containing particles, respectively.

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About the authors

M. V. Grishin

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: slutsky@chph.ras.ru
Russian Federation, Moscow

A. K. Gatin

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: slutsky@chph.ras.ru
Russian Federation, Moscow

S. Yu. Sarvadii

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: slutsky@chph.ras.ru
Russian Federation, Moscow

V. G. Slutskii

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Author for correspondence.
Email: slutsky@chph.ras.ru
Russian Federation, Moscow

D. T. Tastaibek

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: slutsky@chph.ras.ru
Russian Federation, Moscow

V. A. Kharitonov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: slutsky@chph.ras.ru
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Structures of Au₃⁻, Ni₂⁺ clusters and their hydrides. Black marks – hydrogen. Distances in Å.

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3. Fig. 2. Structures of oxides of negatively charged clusters (Au₃H₂)– and positively charged clusters Ni₂⁺. Black marks – hydrogen, white marks – oxygen. Distances in Å.

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4. Fig. 3. Mechanism of transformation of (Au₃H₂–O)– into Au₃⁻ and H₂O. Gray marks – Au, white – oxygen, black – hydrogen. Distances in Å. Heat effects of elementary reactions in kcal/mol are given in square brackets.

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