Hydrogen (H) atomic migration over a metal oxide is an important surface process in various catalytic reactions. Control of the interaction between H atoms and the oxide surfaces is therefore important for better catalytic performance. For this investigation, we evaluated the adsorption energies of the H atoms over perovskite-type oxides (Sr1-x Ba x ZrO3; 0.00 ≤ x ≤ 0.50) using DFT (Density Functional Theory) calculations, then clarified the effects of cation-substitution in the A-site of perovskite oxides on H atom adsorption, migration, and reaction. Results indicated local distortion at the oxide surface as a key factor governing H atom adsorption. Subtle Ba2+ substitution for Sr2+ sites provoked local distortion at the Sr1-x Ba x ZrO3 oxide surface, which led to a decrement in the H atom adsorption energy. Furthermore, the effect of Sr2+/Ba2+ ratio on the H atoms' reactivities was examined experimentally using a catalytic reaction, which was promoted by activated surface H atoms. Results show that the surface H atoms activated by the substitution of Sr2+ sites with a small amount of Ba2+ (x = 0.125) contributed to enhancement of ammonia synthesis rate in an electric field, which showed good agreement with predictions made using DFT calculations.
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