Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment

Wen, Bo; Yin, Wen-Jin; Selloni, Annabella; Liu, Li-Min

doi:10.1039/C9CP05097C

Title: Site dependent reactivity of Pt single atoms on anatase TiO₂(101) in an aqueous environment

Journal Article · 14 October 2019 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/C9CP05097C · OSTI ID:1594492

^[1]; Yin, Wen-Jin ^[2];

^[3]; Liu, Li-Min ^[4]

Beijing Computational Science Research Center, Beijing (China); Princeton Univ., NJ (United States); Princeton University
Hunan Univ. of Science and Technology, Xiangtan (China)
Princeton Univ., NJ (United States)
Beihang Univ., Beijing (China)

The TiO₂–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for The TiO₂–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for enhancing hydrogen evolution in aqueous TiO₂. Using ab initio molecular dynamics, we investigated this interface focusing on Pt single atoms supported on anatase TiO₂(101) in a water environment. Based on recent experiments showing a broad distribution of Pt coordination sites in TiO₂, we examined six distinct single-Pt supported species with different nominal Pt oxidation states, namely: Pt, PtOH, and PtO₂ species adsorbed on the stoichiometric surface; Pt adsorbed at a surface oxygen vacancy (O_v); and Pt substituting a surface Ti cation (PtTi), both without and with an accompanying O_v (Pt_Ti+ O_v). As found for the pristine anatase surface, interfacial water remained intact in the presence of a nearly neutral Pt adatom within the time duration of our simulations (~15 ps). Similarly, no (or only temporary) water dissociation was observed at the Pt_Ti + O_v and PtO₂ interfaces, due to the formation of very stable planar Pt coordination structures that interact only weakly with water. In contrast, water dissociated with OH^– (H⁺) on the Pt atom when this substituted a surface Ti (oxygen) ion as well as on PtOH. Lastly, the significant proton affinity of Pt atoms at surface oxygen vacancies suggests that negatively charged Pt species are particularly efficient at catalyzing hydrogen evolution in aqueous TiO₂.hydrogen evolution in aqueous TiO₂.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China; Tianhe-2JK

Grant/Contract Number:: SC0007347

OSTI ID:: 1594492

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 19 Vol. 22; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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