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Updated: May 25, 2026

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics
Published on: April 12, 2019
First principles study of sulfuric acid anion adsorption on a Pt(111) electrode
Ryosuke Jinnouchi1, Tatsuya Hatanaka, Yu Morimoto
1Toyota Central Research & Development Laboratories, Inc., Nagakute, Aichi 480-1192, Japan. e1262@mosk.tytlabs.co.jp
Abstract:
A first principles theory combined with a continuum electrolyte theory is applied to adsorption of sulfuric acid anions on Pt(111) in 0.1 M H(2)SO(4) solution. The theoretical free energy diagram indicates that sulfuric acid anions adsorb as bisulfate in the potential range of 0.41 < U ≤ 0.48 V (RHE) and as sulfate in 0.48 V (RHE) < U. This diagram also indicates that sulfate inhibits formations of surface oxide and hydroxide. Charge analysis shows that the total charge transferred for the formation of the full coverage sulfate adlayer is 90 μC cm(-2), and that the electrosorption valency value is -0.45 to -0.95 in 0.41 < U ≤ 0.48 V (RHE) and -1.75 to -1.85 in U > 0.48 V (RHE) in good agreement with experiments reported in the literature. Vibration analysis indicates that the vibration frequencies observed experimentally at 1250 and 950 cm(-1) can be assigned, respectively, to the S-O (uncoordinated) and symmetric S-O stretching modes for sulfate, and that the higher frequency mode has a larger potential-dependence (58 cm(-1) V(-1)) than the lower one.
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