Oxygen Vacancy‐Mediated Photocatalysis of BiOCl: Reactivity, Selectivity, and Perspectives

Abstract

Semiconductor photocatalysis is a trustworthy approach to harvest clean solar light for energy conversions, while state-of-the-art catalytic efficiencies are unsatisfactory because of the finite light response and/or recombination of robust charge carriers. Along with the development of modern material characterization techniques and electronic-structure computations, oxygen vacancies (OVs) on the surface of real photocatalysts, even in infinitesimal concentration, are found to play a more decisive role in determining the kinetics, energetics, and mechanisms of photocatalytic reactions. This Review endeavors to clarify the inherent functionality of OVs in photocatalysis at the surface molecular level using 2D BiOCl as the platform. Structure sensitivity of OVs on reactivity and selectivity of photocatalytic reactions is intensely discussed via confining OVs onto prototypical BiOCl surfaces of different structures. The critical understanding of OVs chemistry can help consolidate and advance the fundamental theories of photocatalysis, and also offer new perspectives and guidelines for the rational design of catalysts with satisfactory performance.

Efficient Degradation of Phenol and 4‐Nitrophenol by Surface Oxygen Vacancies and Plasmonic Silver Co‐Modified Bi2MoO6 Photocatalysts

“…[45] Figure 5c shows the EPR spectra of BMO, BMO-SOVs-375, and 2%A/ BMO-SOVs-375. [48] This result further corroborates the successfulf ormation of oxygen vacancieso nt he BMO surface by af acile impregnation-calcination method. [40] Compared to BMO, a strong symmetric peak centered at a g value of around2 .004 was observed for BMO-SOVs-375 and 2%A/BMO-SOVs-375, which is at ypical peak of surfaceo xygen vacancies.…”

Pyrene-Based Conjugated Polymer/Bi2MoO6 Z-Scheme Hybrids: Facile Construction and Sustainable Enhanced Photocatalytic Performance in Ciprofloxacin and Cr(VI) Removal under Visible Light Irradiation

“…To acquire suitable photocatalysts with broad photo absorption, fast charge transportation, and efficient surface reactions, several commonly used techniques have been explored, such as sensitization, doping, fabrication of heterojunction, surface engineering, and so on [5][6][7][8][9]. Among them, the fabrication of Z-scheme hybrids, especially the direct Z-scheme photocatalysts, is recognized to be extraordinarily attractive, since it can enormously extend the light absorption region and accelerate the separation of e − /h + pairs [10][11][12].…”

Unprecedented Eighteen‐Faceted BiOCl with a Ternary Facet Junction Boosting Cascade Charge Flow and Photo‐redox

“…BiOCl as ar epresentative layered bismuth-based photocatalysts with SillØn-structure has attracted widespread attentions for its various catalytic applications,l ike pollutant purification, [11] water splitting for H 2 and O 2 production, [12] CO 2 reduction, [13] ammonia synthesis, [14] selective benzyl alcohol oxidation, [15] aerobic oxidation of secondary amines, [16] photofuel cell. [17] It has the typical layered crystal configuration composed of (Bi 2 O 2 ) 2+ layers and double Cl À slice,w hich favors the formation of thin-layer structure with exposure of {001} top facets and {110} lateral facets.…”