Dataset Information

Distribution of Pt single atom coordination environments on anatase TiO₂ supports controls reactivity.

ABSTRACT: Single-atom catalysts (SACs) offer efficient metal utilization and distinct reactivity compared to supported metal nanoparticles. Structure-function relationships for SACs often assume that active sites have uniform coordination environments at particular binding sites on support surfaces. Here, we investigate the distribution of coordination environments of Pt SAs dispersed on shape-controlled anatase TiO₂ supports specifically exposing (001) and (101) surfaces. Pt SAs on (101) are found on the surface, consistent with existing structural models, whereas those on (001) are beneath the surface after calcination. Pt SAs under (001) surfaces exhibit lower reactivity for CO oxidation than those on (101) surfaces due to their limited accessibility to gas phase species. Pt SAs deposited on commercial-TiO₂ are found both at the surface and in the bulk, posing challenges to structure-function relationship development. This study highlights heterogeneity in SA coordination environments on oxide supports, emphasizing a previously overlooked consideration in the design of SACs.

SUBMITTER: Zang W

PROVIDER: S-EPMC10837418 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Distribution of Pt single atom coordination environments on anatase TiO<sub>2</sub> supports controls reactivity.

Zang Wenjie W Lee Jaeha J Tieu Peter P Yan Xingxu X Graham George W GW Tran Ich C IC Wang Peikui P Christopher Phillip P Pan Xiaoqing X

Nature communications 20240202 1

Single-atom catalysts (SACs) offer efficient metal utilization and distinct reactivity compared to supported metal nanoparticles. Structure-function relationships for SACs often assume that active sites have uniform coordination environments at particular binding sites on support surfaces. Here, we investigate the distribution of coordination environments of Pt SAs dispersed on shape-controlled anatase TiO<sub>2</sub> supports specifically exposing (001) and (101) surfaces. Pt SAs on (101) are f ...[more]

PMID: 38307931

Similar Datasets

Project description:Anatase TiO2 nanoparticle aggregates were used as model systems for studying at different water activities the reactivity of electron centers at semiconductor surfaces. The investigated surface conditions evolve from a solid/vacuum interface to a solid/bulk electrolyte interface. Hydrogen-related electron centers were generated either chemically-upon sample exposure to atomic hydrogen at the semiconductor/gas interface-or electrochemically-upon bias-induced charge accumulation at the semiconductor/electrolyte interface. Based on their corresponding spectroscopic and electrochemical fingerprints, we investigated the reactivity of hydrogen-related electron centers as a function of the interfacial condition and at different levels of complexity, that is, (i) for dehydrated and (partially) dehydroxylated oxide surfaces, (ii) for oxide surfaces covered by a thin film of interfacial water, and (iii) for oxide surfaces in contact with a 0.1 M HClO4 aqueous solution. Visible (Vis) and infrared (IR) spectroscopy evidence a chemical equilibrium between hydrogen atoms in the gas phase and-following their dissociation-electron/proton centers in the oxide. The excess electrons are either localized forming (Vis-active) Ti3+ centers or delocalized as (IR-active) free conduction band electrons. The addition of molecular oxygen to chemically reduced anatase TiO2 nanoparticle aggregates leads to a quantitative quenching of Ti3+ centers, while a fraction of ∼10% of hydrogen-derived conduction band electrons remains in the oxide pointing to a persistent hydrogen doping of the semiconductor. Neither trapped electrons (i.e., Ti3+ centers) nor conduction band electrons react with water or its adsorption products at the oxide surface. However, the presence of an interfacial water layer does not impede the electron transfer to molecular oxygen. At the semiconductor/electrolyte interface, inactivity of trapped electrons with regard to water reduction and electron transfer to oxygen were evidenced by cyclic voltammetry.

Dataset Information

Distribution of Pt single atom coordination environments on anatase TiO₂ supports controls reactivity.

Publications

Distribution of Pt single atom coordination environments on anatase TiO<sub>2</sub> supports controls reactivity.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dataset Information

Distribution of Pt single atom coordination environments on anatase TiO2 supports controls reactivity.

Publications

Distribution of Pt single atom coordination environments on anatase TiO<sub>2</sub> supports controls reactivity.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Distribution of Pt single atom coordination environments on anatase TiO₂ supports controls reactivity.