Synergistic Pd Single Atoms, Clusters, and Oxygen Vacancies on TiO2 for Photocatalytic Hydrogen Evolution Coupled with Selective Organic Oxidation. Issue 2 (16th December 2020)

• Record Type: Journal Article
• Authors: Wang, Ting; Tao, Xueqin; Li, Xiaoli; Zhang, Kun; Liu, Shoujie; Li, Benxia
• Is Part Of: Small. Volume 17:Issue 2(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-12-16
• Subjects: hydrogen evolution -- Pd active sites -- photocatalysis -- selective oxidation -- surface engineering; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.202006255
• Languages: English
• ISSNs: 1613-6810

Abstract

Abstract: Developing efficient photocatalysts for synchronously producing H2 and high value‐added chemicals holds great promise to enhance solar energy conversion. Herein, a facile strategy of simultaneously engineering Pd cocatalyst and oxygen vacancies (VO s) on TiO2 to promote H2 production coupled with selective oxidation of benzylamine is demonstrated. The optimized PdSA+C /TiO2 ‐VO photocatalyst containing Pd single atoms (SAs), clusters (C), and VO s exhibits much superior performance to those of TiO2 ‐VO and PdSA /TiO2 ‐VO counterparts. The production rates of H2 and N‐benzylidenebenzylamine over PdSA+C /TiO2 ‐VO are 52.7 and 1.5 times those over TiO2 ‐VO, respectively. Both experimental and theoretical studies have elucidated the synergistic effect of Pd SAs, clusters, and VO s on TiO2 in boosting the photocatalytic reaction. The presence of Pd SAs facilitates the generation and stabilization of abundant VO s by the formation of PdOTi 3+ atomic interface, while Pd clusters promote the photogenerated charge separation and afford the optimum active sites for H2 evolution. Surface VO s of TiO2 guarantee the efficient adsorption and dissociation/activation of reactant molecules. This study reveals the effect of active‐site engineering on the photocatalysis and is expected to shed substantial light on future structure design and modulation of semiconductor photocatalysts. Abstract : A novel photocatalyst is optimally synthesized by engineering Pd single atoms (SAs), clusters, and oxygen vacancies (VO s) on porous TiO2, to promote the synchronous productions of H2 and high value‐added chemicals. The synergistic effect of Pd SAs, clusters, and VO s in the photocatalytic reaction is elucidated by both experimental and theoretical studies.