4.7 Article

Dual-site oxygen activation for enhanced photocatalytic aerobic oxidation by S-scheme Ni2P/Bi3O4Br-OVs heterojunction

Journal

CHEMICAL ENGINEERING JOURNAL
Volume 452, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2022.139425

Keywords

Photocatalysis; O-2 activation; Dual-site; Photocatalytic aerobic oxidation; Bi3O4Br

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This study proposes an efficient approach to activate O2 through defect and heterojunction engineering. By introducing oxygen vacancies and Ni2P on Bi3O4Br nanosheets, the photocatalyst optimizes light absorption, facilitates the separation and transfer of photogenerated charge carriers, and provides active sites for the adsorption and activation of oxygen molecules, leading to highly efficient photocatalytic reactions.
Solar-driven activation of molecular oxygen (O-2) offers an appealing strategy to realize aerobic oxidation catalysis at room temperature, while the efficiency of photocatalytic O-2 activation is severely limited by lacking O-2 adsorption sites and poor carrier utilization. Herein, an efficient Ni2P/Bi3O4Br-OVs heterojunction is firstly proposed to overcome the limitation by the dual-site design of oxygen vacancies (OVs) and on Ni2P cocatalyst. By the joint observations from spectroscopic measurements and theoretical simulations, the introduction of OVs and Ni2P on Bi3O4Br nanosheets can not only optimize the light absorption, facilitate the separation and transfer of photogenerated charge carrier through the S-scheme mechanism, but also provide active sites for effective adsorption and activation of oxygen molecules, thereby contributing to highly efficient generation of center dot O-2(-) radicals. Benefiting from the more oxidative active species of center dot O-2(-) and h(+), the Ni2P/Bi3O4Br-OVs photocatalyst achieves near-unity conversion rate and selectivity in aerobic oxidation of sulfide to sulfoxide, and it also exhibits outstanding photoactivity in the aerobic degradation of phenolic pollutants under visible light. This study showcases a feasible O-2 activation approach by defect and heterojunction engineering, and provides a new perspective for designing high-performance photocatalysts in the field of aerobic oxidation catalysis.

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