Semiconductor photocatalysts: A critical review highlighting the various strategies to boost the photocatalytic performances for diverse applications.

Recent years have witnessed an upsurge of interest in exploiting advanced photo‐/electrocatalysts for efficient energy conversion and environmental remediation. Constructing internal electric fields has been highlighted as a rising star to help facilitate various catalytic processes, with the merits of promoting charge transfer/separation, optimizing redox potential and creating effective active/adsorption sites. Internal electric fields are usually formed by the polarization of uneven charge distributions between different constituent layers, which widely exist in piezoelectrics, polar surface terminations, and heterostructure materials. Herein, a groundbreaking and interdisciplinary overview of the latest advances in the construction of internal electric fields to improve photo(electro)catalytic and electrocatalytic activity is provided. This critical review begins with an encyclopedic summary of the classification, advantages, and synthesis strategies of internal electric fields. Subsequently, the identification methods are thoroughly discussed based on the characterization techniques, experiments, and theoretical calculations, which can provide profound guidance for the in‐depth study of internal electric fields. To elaborate the theory–structure–activity relationships for internal electric fields, the corresponding reaction mechanisms, modification strategies, and catalytic performance are jointly discussed, along with a discussion of their practical energy and environmental applications. Finally, an insightful analysis of the challenges and future prospects for internal electric field‐based catalysts are discussed.

Enabling Internal Electric Fields to Enhance Energy and Environmental Catalysis

Assembling different 2D nanomaterials into heterostructures with strong interfacial interactions presents a promising approach for novel artificial photocatalytic materials. Chemically implementing the 2D nanomaterials' construction/stacking modes to regulate different interfaces can extend their functionalities and achieve good performance. Herein, based on different fundamental principles and photochemical processes, multiple construction modes (e.g., face-to-face, edge-to-face, interface-to-face, edge-to-edge) are overviewed systematically with emphasis on the relationships between their interfacial characteristics (e.g., point, linear, planar), synthetic strategies (e.g., in situ growth, ex situ assembly), and enhanced applications to achieve precise regulation. Meanwhile, recent efforts for enhancing photocatalytic performances of 2D/2D heterostructures are summarized from the critical factors of enhancing visible light absorption, accelerating charge transfer/separation, and introducing novel active sites. Notably, the crucial roles of surface defects, cocatalysts, and surface modification for photocatalytic performance optimization of 2D/2D heterostructures are also discussed based on the synergistic effect of optimization engineering and heterogeneous interfaces. Finally, perspectives and challenges are proposed to emphasize future opportunities for expanding 2D/2D heterostructures for photocatalysis.

Interface Engineering in 2D/2D Heterogeneous Photocatalysts.

Construction of BiOBr/Ti3C2/exfoliated montmorillonite Schottky junction: New insights into exfoliated montmorillonite for inducing MXene oxygen functionalization and enhancing photocatalytic activity

The insufficient generation of oxidative active species severely limits the activity of photocatalytic aerobic oxidation for organic pollutants degradation in wastewater. Herein, transition metal phosphides (TMPs) cocatalysts, including Ni2P, Co2P, and NiCoP, were loaded on Bi4O5Br2 nanosheets by a simple liquid assembly method. Among which, 15% NiCoP/Bi4O5Br2 heterojunction exhibits the optimal photocatalytic activity for degrading phenolic pollutants owing to the high concentration of h+ and •O2− active species, and it displays excellent tolerance for the inorganic ions, pH value, water matrix, and outdoor sunlight. The S-scheme charge transfer mechanism was revealed for NiCoP/Bi4O5Br2 heterojunction, which significantly improves the separation efficiency of photogenerated charge carriers and facilitates the accumulation of active h+. Furthermore, NiCoP with high reduction potential and outstanding O2 activation ability is served as the active site for producing •O2−. This work can inspire the further design of bifunctional photocatalysts for efficient photocatalytic aerobic oxidation applications. 

Boosting holes generation and O2 activation by bifunctional NiCoP modified Bi4O5Br2 for efficient photocatalytic aerobic oxidation

Bi4O5Br2 anchored on Ti3C2 MXene with ohmic heterojunction in photocatalytic NH3 production: Insights from combined experimental and theoretical calculations

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Bi4O5Br2 anchored on Ti3C2 MXene with ohmic heterojunction in photocatalytic NH3 production: Insights from combined experimental and theoretical calculations