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Water-Mediated Proton Hopping Mechanisms at the SnO2(110)/H2O Interface from Ab Initio Deep Potential Molecular Dynamics
Shangqiu Normal Univ, Coll Chem & Chem Engn, Henan Key Lab Biomol Recognit & Sensing, Henan Joint Int Res Lab Chemo Biosensing & Early D, Shangqiu 476000, Peoples R China..
Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, IChEM, Xiamen 361005, Peoples R China.;EPFL, CSEA, Lausanne 1015, Chandigarh, India..ORCID iD: 0000-0001-5182-8084
Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, IChEM, Xiamen 361005, Peoples R China..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-7167-0840
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2024 (English)In: PRECISION CHEMISTRY, ISSN 2771-9316, Vol. 2, no 12, p. 644-654Article in journal (Refereed) Published
Abstract [en]

The interfacial proton transfer (PT) reaction on the metal oxide surface is an important step in many chemical processes including photoelectrocatalytic water splitting, dehydrogenation, and hydrogen storage. The investigation of the PT process, in terms of thermodynamics and kinetics, has received considerable attention, but the individual free energy barriers and solvent effects for different PT pathways on rutile oxide are still lacking. Here, by applying a combination of ab initio and deep potential molecular dynamics methods, we have studied interfacial PT mechanisms by selecting the rutile SnO2(110)/H2O interface as an example of an oxide with the characteristic of frequently interfacial PT processes. Three types of PT pathways among the interfacial groups are found, i.e., proton transfer from terminal adsorbed water to bridge oxygen directly (surface-PT) or via a solvent water (mediated-PT), and proton hopping between two terminal groups (adlayer PT). Our simulations reveal that the terminal water in mediated-PT prefers to point toward the solution and forms a shorter H-bond with the assisted solvent water, leading to the lowest energy barrier and the fastest relative PT rate. In particular, it is found that the full solvation environment plays a crucial role in water-mediated proton conduction, while having little effect on direct PT reactions. The PT mechanisms on aqueous rutile oxide interfaces are also discussed by comparing an oxide series composed of SnO2, TiO2, and IrO2. Consequently, this work provides valuable insights into the ability of a deep neural network to reproduce the ab initio potential energy surface, as well as the PT mechanisms at such oxide/liquid interfaces, which can help understand the important chemical processes in electrochemistry, photoelectrocatalysis, colloid science, and geochemistry.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024. Vol. 2, no 12, p. 644-654
Keywords [en]
Proton transfer mechanism, ab initio molecular dynamics, deep potential molecular dynamics, rutile oxide, machine learning, solvation effect, free energy
National Category
Physical Chemistry Theoretical Chemistry Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-555195DOI: 10.1021/prechem.4c00056ISI: 001315910300001PubMedID: 39734759Scopus ID: 2-s2.0-85205688329OAI: oai:DiVA.org:uu-555195DiVA, id: diva2:1954379
Available from: 2025-04-24 Created: 2025-04-24 Last updated: 2025-04-24Bibliographically approved

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