Boosting Reactive Oxygen Species Generation Using Inter‐Facet Edge Rich WO3 Arrays for Photoelectrochemical Conversion. (1st December 2022)

• Record Type: Journal Article
• Authors: Li, He; Lin, Cheng; Yang, Yilong; Dong, Chaoran; Min, Yulin; Shi, Xiaoqin; Wang, Luyang; Lu, Siyu; Zhang, Kan
• Is Part Of: Angewandte Chemie. Volume 135:Number 1(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-01
• Subjects: Charge Transfer -- Oxygenation -- Photocatalysis -- Radicals -- Water Splitting; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202210804
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Water oxidation reaction leaves room to be improved in the development of various solar fuel productions, because of the kinetically sluggish 4‐electron transfer process of oxygen evolution reaction. In this work, we realize reactive oxygen species (ROS), H2 O2 and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter‐facet edge (IFE) rich WO3 arrays in an electrolyte containing CO3 2− . Our results demonstrate that the IFE favors the adsorption of CO3 2− while reducing the adsorption energy of OH⋅, as well as suppresses surface hole accumulation by direct 1‐electron and indirect 2‐electron transfer pathways. Finally, we present selective oxidation of benzyl alcohol by in situ using the formed OH⋅, which delivers a benzaldehyde production rate of ≈768 μmol h −1 with near 100 % selectivity. This work offers a promising approach to tune or control the oxidation reaction in an aqueous solar fuel system towards high efficiency and value‐added product. Abstract : Direct 1 e − electron and indirect 2 e − electron transfer pathways for photoelectrochemical water oxidation are achieved using an inter‐facet edge (IEF) rich WO3 photoanode in the presence of CO3 2− . The total Faraday efficiencies of H2 O2 and OH⋅ products exceed 90 %. Then, selective oxidation of benzyl alcohol by in situ using the formed OH⋅ delivers a benzaldehyde production rate of ≈768 μmol h −1 with near 100 % selectivity.