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Tendencies of alloyed engineering in BiOX-based photocatalysts: a state-of-the-art review

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Abstract

Energy-saving and environmentally friendly photocatalysis has emerged as a popular research area in response to issues with energy scarcity and environmental degradation. Due to the unique layer-like structure, BiOX (Cl, Br, I) is frequently used in photocatalysis. However, inherent flaws in BiOX, such as an inappropriate band gap and low carrier separation efficiency, restrict its capacity for photocatalysis. Owing to the tunable grouping layer, alloying engineering is employed to optimize the intrinsic properties of BiOX and alloyed BiOX becomes a promising photocatalytic material. This review describes the structure of BiOX, where tunable halogen layers provide favorable conditions for the implementation of alloying engineering to improve intrinsic properties. The article compares the effects and mechanisms of alloying engineering on the optimization of the energy band structure and carrier behavior of BiOX, and lists various modification methods used to improve the optimization of the intrinsic properties by alloying engineering, including defect engineering, morphology control as well as the synergy between alloying and other modification methods (bismuth-rich strategies, cation doping, construction of heterojunctions and plasma resonance effects). Subsequently, applications of alloyed BiOX in energy and environmental fields are summarized, including contaminant degradation, antibacterial, CO2 reduction, nitrogen fixation and organic synthesis. Finally, we summarize the current challenges and future directions of alloyed BiOX. It is expected that this work will provide guidance and assistance for an in-depth study and understanding of the mechanisms of alloying engineering to optimize intrinsic properties and design alloyed BiOX with higher photocatalytic activity.

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摘要

节能环保的光催化技术已成为应对能源短缺和环境恶化问题的热门研究领域。由于具有独特的层状结构, BiOX(Cl、Br、I) 经常被用于光催化领域。然而, BiOX 的固有缺陷 (如带隙不合适和载流子分离效率低) 限制了其光催化能力。由于BiOX具有可调的卤素层, 合金化工程被用来优化BiOX的本征特性, 合金化的BiOX成为一种很有前途的光催化材料。本综述介绍了 BiOX 的结构, 其中可调卤素层为实施合金工程以改善本征特性提供了有利条件。文章比较了合金化工程对优化 BiOX 能带结构和载流子行为的影响和机制, 并列举了通过合金化工程改善优化其本征特性的各种改性方法, 包括缺陷工程、形貌控制以及合金化与其他改性方法 (富铋策略、阳离子掺杂、异质结构建和等离子体共振效应) 的协同作用。随后, 总结了合金化BiOX在能源和环境领域的应用, 包括污染物降解、抗菌、CO2还原、固氮和有机合成。最后, 我们总结了合金化BiOX目前面临的挑战和未来的发展方向。希望这项工作能为深入研究和理解合金化工程的机理提供指导和帮助, 从而优化其内在特性, 设计出具有更高光催化活性的合金化 BiOX。

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Fig. 1

Reproduced with permission from Ref. [20]. Copyright 2017, Elsevier. b Mechanism of preparation of BiOBrxI1−x using Azadirachta indica leaf extract as solvent. Reproduced with permission from Ref. [28]. Copyright 2019, Elsevier

Fig. 2
Fig. 3

Reproduced with permission from Ref. [37]. Copyright 2020, Chemistry Europe. c Partial density of states of BiOCl, BiOI and I0.25-BiOCl obtained from theoretical calculations. Reproduced with permission from Ref. [29]. Copyright 2011, American Chemical Society. d, f Band gaps and e, g UV–Vis diffuse reflectance spectra of BiOClxBr1−x (Reproduced with permission from Ref. [38]. Copyright 2017, Springer Link) and BiOBrxI1−x. Reproduced with permission from Ref. [39]. Copyright 2019, Springer Link

Fig. 4
Fig. 5

Reproduced with permission from Ref. [44]. Copyright 2018, Elsevier. c Integrated area ratio of different O species in XPS peak of O 1s. Reproduced with permission from Ref. [54]. Copyright 2022, MDPI. d Raman spectra; e PL spectra of BiOBrxI1−x with fluorine substitution. Reproduced with permission from Ref. [46]. Copyright 2019, Elsevier. f EPR spectra of pristine BiOCl and BiOCl1−3xI3x. Reproduced with permission from Ref. [55]. Copyright 2022, Elsevier. High-resolution spectra of Bi g 4f BOCI-F and h Bi 4f BOCI-U. Reproduced with permission from Ref. [57]. Copyright 2019, Elsevier

Fig. 6

Reproduced with permission from Ref. [20]. Copyright 2017, Elsevier. TEM images of photooxidation deposition of i BOC and j BOC-3 under monochromatic UV light; TEM images of photoreduction deposition of e BOC and f BOC-3 under monochromatic UV light. Reproduced with permission from Ref. [59]. Copyright 2017, Royal society of chemistry. k Photocurrent responses of BiOBrxI1−x (water) and BiOBrxI1−x (EG). Reproduced with permission from Ref. [18]. Copyright 2018, Elsevier. l XRD patterns and m PL spectra of BiOCl/Br-x. Reproduced with permission from Ref. [23] Copyright 2019, WILEY

Fig. 7

Reproduced with permission from Ref. [60]. Copyright 2019, Elsevier. c Band energy structures; d photocurrent responses of Bi3O4Cl1−xBrx. Reproduced with permission from Ref. [62]. Copyright 2018, Elsevier. e PL spectra of as-prepared photocatalysts; f schematic diagram of electron transfer of Fe–O–Bi. Reproduced with permission from Ref. [65]. Copyright 2023, Springer Link

Fig. 8

Reproduced with permission from Ref. [67]. Copyright 2022, Elsevier. d Heterogeneous structural type; e PL spectra of g-C3N4 and g-C3N4/BiOCl0.2Br0.8. Reproduced with permission from Ref. [71]. Copyright 2014, Elsevier. f Heterogeneous structural type; g photocurrent responses of BCI-CN-P nanosheets. Reproduced with permission from Ref. [72]. Copyright 2019, Elsevier. h Heterogeneous structural type; i PL spectra of g-C3N4/BiOCl0.8I0.2. Reproduced with permission from Ref. [73]. Copyright 2020, Elsevier

Fig. 9
Fig. 10

Reproduced with permission from Ref. [35]. Copyright 2017, Elsevier. b Diagram of carrier photocatalytic process for 0.5BiOBr/0.5BiOI; c exciton photocatalytic process for BiOBr0.5I0.5. Reproduced with permission from Ref.[91]. Copyright 2017, American Chemical Society. d Mechanism of photooxidizing IPA over BiO(ClBr)(1−x)/2Ix. Reproduced with permission from Ref. [21]. Copyright 2015, Royal society of chemistry. e, f Antibacterial activities of BiOBrxI1−x under dark and g, h LED light illumination against E. coli and B. subtilis. Reproduced with permission from Ref. [94]. Copyright 2021, Elsevier. i Compared to BiOCl-OV, Br-BiOCl-OV extending N–N bond of adsorbed N2. Reproduced with permission from Ref. [31]. Copyright 2019, Elsevier. j Selective oxidation of benzylamine to N-benzylidenebenzylamine under visible light; k diagram of band energy for BiOIxCl1−x. Reproduced with permission from Ref. [96]. Copyright 2021, Elsevier

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 22376051), the Key Projects of Natural Science Research in Universities of Anhui Province (No. 2022AH050378), the University Synergy Innovation Program of Anhui Province (No. GXXT-2022-086).

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  1. Tianjin Key Laboratory of Clean Energy and Pollutant Control, School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin, 300401, China

    Yan-Dong Sun, Xue Zhang, Zi-Qi Zhang & Sheng-Qi Guo

  2. Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, School of Physics and Electronic Information, Anhui Province Industrial Generic Technology Research Center for Alumics Materials, Huaibei Normal University, Huaibei, 235000, China

    Bo Yang

  3. State-Province Joint Engineering Laboratory of Zeolite Membrane Materials, Institute of Advanced Materials, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, China

    Chao Zeng

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  1. Yan-Dong Sun
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Sun, YD., Zeng, C., Zhang, X. et al. Tendencies of alloyed engineering in BiOX-based photocatalysts: a state-of-the-art review. Rare Met. 43, 1488–1512 (2024). https://doi.org/10.1007/s12598-023-02569-6

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