First principles study of sulfuric acid anion adsorption on a Pt(111) electrode
Literature Information
Ryosuke Jinnouchi, Tatsuya Hatanaka, Yu Morimoto, Masatoshi Osawa
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 H2SO4 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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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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