Ab Initio Molecular Dynamics with Explicit Solvation Reveals the Volmer–Heyrovsky Mechanism for Chlorine Evolution on Dimensionally Stable Anodes
- 1School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China
- 2Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
Abstract
The chlorine evolution reaction (CER) is the core anodic process in the chlor-alkali industry, where RuO2–TiO2 mixed oxides serve as the industrial standard material as dimensionally stable anodes (DSA). Understanding how the local chemical environment around the active metal sites governs CER kinetics is essential for rational catalyst design. Herein, we employ ab initio molecular dynamics (AIMD) with an explicit liquid–solid interface to investigate the Volmer–Heyrovsky mechanism on the Ru0.5Ti0.5O2(110) surface. The active surface is identified as a fully oxygen-covered configuration, exposing two chemically distinct active sites, i.e., terminal oxygen occupied Ti (Oc_Ti) and Ru (Oc_Ru). The calculated free energy profiles reveal that while the Volmer step proceeds with comparable barriers on both sites, the subsequent Heyrovsky step is significantly favored on the Oc_Ru site over the Oc_Ti site. The Oc_Ru site contributes predominantly to catalytic activity, with the Volmer step serving as the rate-determining step. These findings highlight the essential role of Ru in working as active sites on DSA-type electrodes and demonstrate the importance of explicit solvation in capturing the mechanistic picture of the CER process.
Related
- Dynamic Evolution and Stability of Ketenes in MAPO-18 (M = Si or Mg): Molecular Insights into the Reaction Mechanism for CO2-to-Hydrocarbons
- From Hydrogen Bonding to Hydrophobic Control: The Shifting Solvation Mechanism of Ibuprofen in Deep Eutectic Solvents
- Composition‐Dependent Solvation in Low‐Concentration Multi‐Salt DME Electrolytes: Correlations With Lithium Deposition and Interfacial Evolution
- ElectrolyteMD-Bench: How Well Do AI Agents Conduct Molecular Dynamics Studies across Electrolyte Solvation Regimes?
- Vicem: Automating Molecular Mechanics Modeling of Solvation Dynamics with Applications to Time-Resolved X-ray Scattering
BibTeX
@article{chen2026initio,
title = {{Ab Initio Molecular Dynamics with Explicit Solvation Reveals the Volmer–Heyrovsky Mechanism for Chlorine Evolution on Dimensionally Stable Anodes}},
author = {Zijin Chen and Jiejie Li and Ziqi Tian},
journal = {Catalysts},
year = {2026},
month = oct,
doi = {10.3390/catal16110939},
url = {https://www.mdpi.com/2073-4344/16/11/939},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Ab Initio Molecular Dynamics with Explicit Solvation Reveals the Volmer–Heyrovsky Mechanism for Chlorine Evolution on Dimensionally Stable Anodes
AU - Zijin Chen
AU - Jiejie Li
AU - Ziqi Tian
PY - 2026
DA - 2026/10/23
JO - Catalysts
DO - 10.3390/catal16110939
UR - https://www.mdpi.com/2073-4344/16/11/939
AB - The chlorine evolution reaction (CER) is the core anodic process in the chlor-alkali industry, where RuO2–TiO2 mixed oxides serve as the industrial standard material as dimensionally stable anodes (DSA). Understanding how the local chemical environment around the active metal sites governs CER kinetics is essential for rational catalyst design. Herein, we employ ab initio molecular dynamics (AIMD) with an explicit liquid–solid interface to investigate the Volmer–Heyrovsky mechanism on the Ru0.5Ti0.5O2(110) surface. The active surface is identified as a fully oxygen-covered configuration, exposing two chemically distinct active sites, i.e., terminal oxygen occupied Ti (Oc_Ti) and Ru (Oc_Ru). The calculated free energy profiles reveal that while the Volmer step proceeds with comparable barriers on both sites, the subsequent Heyrovsky step is significantly favored on the Oc_Ru site over the Oc_Ti site. The Oc_Ru site contributes predominantly to catalytic activity, with the Volmer step serving as the rate-determining step. These findings highlight the essential role of Ru in working as active sites on DSA-type electrodes and demonstrate the importance of explicit solvation in capturing the mechanistic picture of the CER process.
SN - 2073-4344
ER -