Moutsiou, A., Olivati, A., Cipriano, L.A. et al. (10 more authors) (2025) Tracking Charge Dynamics in a Silver Single-Atom Catalyst During the Light-Driven Oxidation of Benzyl Alcohol to Benzaldehyde. ACS Catalysis, 15. pp. 5601-5613. ISSN 2155-5435
Abstract
Understanding charge transfer in light-driven processes is crucial for optimizing the efficiency and performance of a photocatalyst, as charge transfer directly influences the separation and migration of photogenerated charge carriers and determines the overall reaction rate and product formation. However, achieving this understanding remains challenging in the context of single-atom photocatalysis. This study addresses this gap and investigates an Ag-based single-atom catalyst (Ag1@CNx) in the photocatalytic oxidation of benzyl alcohol to benzaldehyde. Comprehensive characterization was conducted using a battery of diffractive, textural, spectroscopic, and microscopic methods, confirming the catalyst crystallinity, porosity, elemental composition, and atomic dispersion of silver atoms. This material displayed efficient performance in the selective oxidation of benzyl alcohol to benzaldehyde. Density functional theory calculations were used to rationalize the catalyst structure and elucidate the reaction mechanism, unveiling the role of the photogenerated holes in lowering the reaction energy barriers. Time-resolved transient spectroscopic studies were used to monitor the dynamics of photogenerated charges in the reaction, revealing the lifetimes and behaviors of excited states within the catalyst. Specifically, the introduction of silver atoms led to a significant enhancement in the excited state lifetime, which favors the hole-transfer in the presence of the benzyl alcohol. This indicated that the photoexcited carriers were effectively transferred to the reactant, thereby driving the oxidation process in the presence of oxygen. These mechanistic insights are pivotal in spectroscopically elucidating the reaction mechanism and can be practically applied to design single-atom photocatalysts more rationally, targeting materials that combine both rapid reductive quenching and efficient charge transfer to the metal.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2025 The Authors. This is an open access article under the terms of the Creative Commons Attribution License (CC-BY 4.0), which permits unrestricted use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | single-atom catalyst; benzyl alcohol oxidation; density functional theory; transient absorption spectroscopy; photocatalysis |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 24 Mar 2025 11:01 |
Last Modified: | 24 Mar 2025 11:01 |
Status: | Published online |
Publisher: | American Chemical Society (ACS) |
Identification Number: | 10.1021/acscatal.4c05208 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:224747 |