基于Bi_xO_yBr_z的光催化剂的改性策略，以增强其在环境中的应用效果：综述

《Journal of Environmental Chemical Engineering》：Modification strategies of Bi xO yBr z-based photocatalysts for enhanced environmental applications: A review

　　摘要
富含铋的氧溴化物（BixOyBrz）光催化剂具有独特的层状结构、可调的电子性质和有效的可见光响应能力，使其成为环境修复和太阳能转换领域中具有前景的候选材料。然而，实际应用仍受到载流子快速复合、光吸收不足以及导带位置不利等因素的限制。本综述系统总结了基于BixOyBrz的光催化剂的最新进展，重点介绍了合成方法（包括水热/溶剂热法、煅烧法、原位合成法、前驱体法以及化学气相沉积法）及其对材料形态、缺陷形成和催化性能的影响。文章讨论了关键的改进策略，如元素掺杂、缺陷工程、形态控制以及异质结（II型、Z-结构型和S-结构型）的构建，并强调了这些策略在提高光吸收、电荷分离和氧化还原能力方面的作用。此外，还重点介绍了基于BixOyBrz的光催化剂在有机污染物去除、重金属去除和光催化CO2还原等环境中的应用及其背后的反应机制。通过综合现有研究结果，本文对解决现有的稳定性挑战、扩大实验室合成规模以及利用先进的表征技术和理论模拟来设计下一代高效BixOyBrz光催化系统提出了前瞻性观点。

引言
过去几十年快速的工业化和人口增长加剧了能源短缺和环境污染问题。随着石化、煤炭和制药等行业的发展，大量含有有害污染物的废水和废气排放到环境中，对全球生态系统和人类健康构成了严重威胁。因此，减少工业污染对于培育一个环保社会至关重要[1]，[2]，[3]，[4]。开发可持续和环保技术是应对能源危机和环境退化的全球优先事项。自1972年Fujishima和Honda发现半导体TiO2可通过光电化学过程分解水生成氢气以来，光催化技术受到了广泛关注[5]。在众多绿色技术中，半导体光催化技术因其同时利用太阳能和修复环境的双重优势而备受重视。该技术能够利用可见光驱动氧化还原反应，有效去除重金属并降解有机污染物，同时将CO2、N2和H2O等丰富资源转化为燃料和高附加值化学品，同时净化空气和水，且不会造成二次污染[6]，[7]，[8]，[9]，[10]。由于其温和的反应条件、可再生性和优良的环境适应性，光催化技术被认为是实现碳中和和可持续环境管理的有效途径。因此，在过去几十年里，开发具有耐用性和可持续性的光能收集及储能能力的光催化剂对于技术进步至关重要。
为了推进光催化技术的工业应用，研究人员研究了基于半导体的光催化剂，并充分利用了不同光催化剂在其各自领域中的优异催化性能。在众多光催化剂中，基于铋的光催化剂因其优异的光学、电学和光催化性能、独特的层状结构以及合适的带隙而受到广泛关注[11]，[12]。其中，通过富铋卤化物氧化法合成的BixOyBrz因其窄带隙、可调结构及优异的化学稳定性而脱颖而出，已在重金属去除[13]、污染物降解[15]、水分解[17]、[18]、[19]、N2固定[20]、[21]和CO2还原[22]等光催化应用中得到广泛应用。为了更全面地了解基于BixOyBrz的光催化剂的发展情况，进行了文献计量分析，以探讨出版物数量的增长和主要研究主题的演变。如图1a所示，从2016年到2025年，该材料的年度出版物数量显著增加，反映了持续的研究兴趣。图1b中的关键词共现叠加可视化进一步展示了研究主题的演变，近期研究聚焦于电荷分离、界面载流子转移和反应路径。特别是，近期研究越来越多地关注氧空位、Z-结构型和S-结构型以及内部电场。此外，污染物降解仍然是一个重要的应用方向，四环素去除和CO2还原等主题也受到了越来越多的关注。如图2所示，通过形态控制、元素掺杂、缺陷工程和异质结构建，可以调节代表性BixOyBrz材料的电子和界面性质，从而影响其在多种环境应用中的光催化性能。相关研究表明，富铋法可以缩小带隙并形成更负的导带最小值[24]，从而扩展可见光吸收范围。使用富铋法制备的光催化剂独特的层状结构有助于形成内在电场（IEF），促进光生电子和空穴的分离，从而提高可见光响应性[25]。然而，基于BixOyBrz的光催化剂仍然面临光生载流子高复合率、光吸收有限以及导带（CB）呈正值的挑战，这些因素限制了其催化效率的提升。研究人员通过多种改性策略（包括形态控制、元素掺杂、缺陷控制、异质结构制备和表面修饰）优化了这些材料的结构和带结构，显著提高了其催化性能。例如，Shi等人通过控制水热反应系统的pH值制备了主要暴露（001）和（010）晶面的BiOBr纳米片。通过利用形态控制改变晶面选择性，他们首次明确区分了不同BiOBr晶面的内在光反应性[26]；AgBr/BiOBr S-结构型异质结光催化剂通过水浴法原位制备，所得异质结光催化剂富含氧空位（OVs），显著提升了其CO2还原性能，CO2转化速率是纯BiOBr的9.2倍[27]；Dong等人通过缺陷工程制备了含有溴空位（BrV）的超薄Bi4O5Br2纳米片，展示了光依赖的表面氢化机制和光独立的表面保护机制，从而促进了可持续的光催化氨生产[28]；Xiao等人通过CTAB诱导的溶剂热法制备了碘掺杂的Bi4O5Br2光催化剂，这种非金属阴离子改性的BiOBr光催化剂表现出优异的性能和良好的光催化稳定性。新合成的碘掺杂Bi4O5Br2对四种对羟基苯甲酸酯（MeP、EtP、PrP和BuP）及其混合物的催化降解效率分别是纯Bi4O5Br2的9.5倍、10.4倍、15.7倍、24.2倍和27倍[29]。这些改性方法突显了基于BixOyBrz的光催化剂的应用潜力和未来前景，为设计新型、高效和稳定的光催化材料提供了坚实的理论基础和实践方法。

several reviews have addressed related aspects of Bi-based photocatalysts. Guan et al. [30] and Liu et al. [31] focused on Bi-based photocatalysts for the removal of elemental mercury, with emphasis on photocatalytic mechanisms, synthesis, and modification strategies. Chawla et al. [32] provided a comprehensive overview of BixOyBrz-based photocatalysts, covering their synthesis, modification strategies, and applications in environmental remediation and energy conversion. However, the relationships between structure and performance remain dispersed across studies. This review systematically examines recent advances in BixOyBrz-based photocatalysts from a structure-performance perspective. The effects of synthesis and modification strategies on morphology, defect states, band structure, interfacial electric field, and charge transfer pathway are discussed, followed by an analysis of how these properties influence photocatalytic performance in organic pollutant degradation, heavy metal removal, CO2 reduction, and other environmental applications. Finally, this review will explore the future directions and challenges for BixOyBrz-based photocatalysts, aiming to guide the design and application of highly efficient and sustainable photocatalytic systems.

Section Snippets
**Synthesis methods for BixOyBrz**
Previous reports have provided ample research demonstrating the excellent performance of BixOyBrz-based photocatalysts in photocatalytic reactions. Several synthesis strategies have been employed for the preparation of BixOyBrz-based photocatalysts. This section primarily focuses on hydrothermal/solvothermal methods, calcination methods, in-situ construction methods, precursor methods, and chemical vapor deposition (CVD).
**Modification strategies for BixOyBrz**
Researchers have been actively exploring ways to broaden its light absorption spectrum and improve the efficient separation of photo-generated carriers in recent years. Although BixOyBrz-based photocatalysts exhibit outstanding absorption capabilities in the visible light region, their charge carriers still suffer from rapid recombination, which limits the practical application of these materials in demanding reactions. Furthermore, even when bismuth-enrichment strategies are employed, some...
**Environmental applications of BixOyBrz**
Through various modification strategies described above, including morphology control, defect engineering, element doping, and the construction of heterostructures, the light absorption capacity, carrier separation efficiency, and surface reactivity of BixOyBrz-based photocatalysts have been significantly enhanced, demonstrating excellent application potential in a variety of environmental remediation scenarios. Currently, BixOyBrz-based photocatalytic systems have been widely applied in...
**Core progress summary**
This review systematically summarizes the latest research progress on BixOyBrz-based photocatalysts, focusing on their synthesis strategies, structural tuning, and environmental applications. Due to their unique layered structure and tunable band structure, BixOyBrz materials exhibit strong visible-light responsiveness and structural flexibility, making them highly promising for photocatalytic environmental purification. Significant progress has been achieved through various enhancement...

Peng Chen: Writing – original draft, Methodology, Formal analysis. Wenquan Zhou: Visualization, Investigation. Weiqi Kong: Formal analysis, Conceptualization. Lei Lin: Supervision, Investigation. Kaixuan Yang: Visualization, Supervision. Feng Yang: Writing – review & editing, Methodology. Jiang Wu: Writing – review & editing, Supervision, Methodology, Conceptualization, Funding acquisition. Le Chen: Visualization, Formal analysis. Huanan Wang: Supervision, Project administration. Lei Zhu: Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements
This work was partially sponsored by National Natural Science Foundation of China (52576128), the scientific and technological innovation project of carbon emission peak and carbon neutrality of Jiangsu province (BT2025010), Zhejiang Provincial Department of Science and Technology Funding (2025C01155), funding support from Baiyulan Project in Pujiang (25PJA046) of Shanghai, and Key Laboratory of Clean Power Generation and Environmental Protection Technology in Mechanical Industry.

Peng Chen | Wenquan Zhou | Weiqi Kong | Lei Lin | Kaixuan Yang | Feng Yang | Jiang Wu | Le Chen | Huanan Wang | Lei Zhu | Mengyuan Hu | Chaoen Li