催化学报

催化学报

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原子空位加速光化学太阳能燃料和增值化学生产: 从材料到机理

丁杨a*, 李志雪a, 张树增a, 杨国详b,*, 郑润田c, 王春花d,*   

  1. a杭州电子科技大学材料与环境工程学院, 浙江杭州 310018, 中国;
    b浙江工商大学环境科学与工程学院, 浙江杭州 310018, 中国;
    c比利时那慕尔大学无机材料化学实验室, 那慕尔, 比利时;
    d密歇根大学电气工程与计算机科学系, 密歇根, 美国
  • 收稿日期:2025-11-20 接受日期:2025-12-19
  • 通讯作者: *电子信箱: dingyang@hdu.edu.cn (丁杨), yangguoxiang@zjgsu.edu.cn (杨国详), chunhuaw@umich.edu (王春花).
  • 基金资助:
    国家自然科学基金(22402044, 22406169); 浙江省自然科学基金(LQ24E020011, LQ24B070001); 浙江省教育厅(Y202352478); 浙江工商大学基础研究经费(QRK23025).

Atomic vacancies accelerating photochemical solar fuel and value-added chemical production: From materials to mechanism

Yang Dinga,*, Zhixue Lia, Shuzeng Zhanga, Guoxiang Yangb,*, Runtian Zhengc, Chunhua Wangd,*   

  1. aCollege of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, Zhejiang, China;
    bSchool of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, Zhejiang, China;
    cLaboratory of Inorganic Materials Chemistry (CMI), University of Namur, Namur B-5000, Belgium;
    dDepartment of Electrical Engineering and Computer Science, University of Michigan, 1301 Beal Avenue, Ann Arbor, Michigan 48109, USA
  • Received:2025-11-20 Accepted:2025-12-19
  • Contact: *E-mail: dingyang@hdu.edu.cn (Y. Ding), yangguoxiang@zjgsu.edu.cn (G. Yang), chunhuaw@umich.edu (C. Wang).
  • Supported by:
    National Natural Science Foundation of China (22402044, 22406169). This work was financially supported by the Zhejiang Provincial Natural Science Foundation of China (LQ24E020011, LQ24B070001). The financial support from the Zhejiang Education Department of China (Y202352478) and Basic Research Expenses of Zhejiang Gongshang University (QRK23025) were also thanked.

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摘要： 光催化技术因其绿色、可持续和低成本的反应过程被认为是解决能源危机和环境污染的有效方法. 推进光催化技术的一个主要挑战在于高效光催化剂研制, 因此制备高效的光催化剂仍然是光催化研究的核心课题. 截至目前, 研究人员已经开发了不同类型的半导体光催化剂, 如金属氧化物、硫化物、氮化物和铋基材料. 这些材料通常具有独特的电子结构、稳定的性能、简便的制备路线和较低的制备成本. 然而, 未改性的半导体材料通常存在活性位点较少、可见光响应较弱和光生载流子复合率高等问题, 导致光催化活性低下, 从而阻碍了该技术的实际应用.
本文系统地讨论了原子空位缺陷在半导体光催化太阳能燃料制备和高价值化学品生产中的关键作用, 包括增强可见光响应能力、调节电子带隙结构、降低活化能、促进反应物分子的吸附和活化以及提高催化剂稳定性. 同时, 详细介绍了目前原子空位缺陷的相关先进表征, 包括电子显微镜、X射线衍射技术、X射线光电子能谱、电子顺磁共振技术、拉曼光谱、同步辐射吸收光谱等. 概括了一些常用的策略(化学合成、物理合成、机械方法、电化学合成法)用于制备原子空位缺陷型光催化剂. 分析对比了这些缺陷合成方法的优势和劣势. 随后, 列举了一系列先进的原子空位缺陷型半导体光催化剂用于水分解以产生绿色氢气和氧气, 以及将二氧化碳还原为增值燃料和化学品, 如一氧化碳、甲烷、甲醇和乙醇等. 这种光催化能源转化技术能够有效地将丰富的太阳能储存在液体燃料和化学品中, 减少二氧化碳排放, 为可再生能源存储技术提供了一种有前景的解决方案. 除了太阳能燃料制备外, 文章还讨论了缺陷光催化剂用于一些高附加值的化学品(如H2O2和NH3)的高效制备. 概述了利用含原子空位光催化剂进行光化学太阳能燃料和增值化学品生产的优势之处. 最后, 对原子空位缺陷型半导体光催化剂的大规模商业化应用前景和关键科学问题进行了展望.
综上, 本综述总结了原子空位缺陷型半导体光催化剂的优势、研究进展、合成策略、表征方法、能源转化应用以及大规模生产存在的挑战, 希望通过推动科研人员进一步思考和探索推动原子空位缺陷半导体光催化在太阳能燃料制备和高价值化学品生产中的实际应用, 为实现双碳目标提供一定的借鉴.

关键词: 半导体材料, 原子空位, 载流子分离, 太阳能燃料演化, 光化学反应

Abstract: Atomic vacancies in semiconductor materials are usually considered detrimental due to their role in trapping photogenerated carriers, leading to attenuated crystallinity and poor photoelectric conversion efficiency. However, the deliberate and controlled introduction of atomic vacancies within an optimal ratio range in semiconductor photocatalysts can significantly improve their catalytic efficiency. Specifically, vacancy sites can optimize the electronic configuration, promote charge carrier separation, activate reactant molecules, lower activation energies, and improve visible light harvesting, thereby enhancing photocatalytic performance. In this review, we systematically highlight the multiplicity of vacancies in semiconductor materials and examine their innovative role in driving photochemical solar fuel and high-value chemical production. An in-depth discussion of the underlying photoreaction mechanisms associated with the vacancy-mediated process is firstly elaborated, followed by introducing the advanced characterizations employed to uncover the merits of vacancies as well as currently developed strategies for vacancy-engineering in photocatalysts. Next, the current advances in utilizing vacancy contained photocatalysts for photochemical solar fuel and value-added chemical production are discussed and appraised, putting emphasis on their applications in water splitting, CO2 conversion, H2O2 generation, and N2 fixation. With the opportunities and challenges in this field, we concluded by presenting an outlook on the further prospects and key issues for the practical application of vacancy contained semiconductor materials. We sincerely hope that this review can spur new concepts to advance industrial-scale solar fuel and value-added chemical generation using vacancy-engineered semiconductor photocatalysts.

Key words: Semiconductor materials, Atom vacancies, Carriers separation, Solar fuel evolution, Photochemical reaction