用于太阳光催化反应的空位工程

doi:10.1016/S1872-2067(17)62821-3

摘要/Abstract

摘要：

空位是一种点缺陷，广泛存在于非化学计量比的半导体光催化材料的晶格中.不同于其它研制复杂结构和组成的新型光催化剂的策略，空位工程设计方法可以基于传统的，由丰量元素组成的光催化剂进行表面或体相晶格的空位调控，以获得宽谱响应的高效光催化材料.该方法具有不引入杂质元素、成本低廉、方法简便等优点，且通过表面化学吸附作用可以耦合热催化和光催化过程，以实现增强的选择性光催化反应.
空位的表征技术包括元素分析，扫描隧道显微镜，催化发光，光致发光或顺磁共振等直接和间接观测技术.近期正电子湮没谱发展成为一种研究空位的重要手段.这种方法可以区分不同位置（如体相和表面）和不同形式（如单一空位或联合空位）的空位并确定其相对浓度，从而用于探索空位影响光催化活性的规律.
氧、氮、硫和卤素原子空位均属于阴离子空位.氢化处理法可以在光催化剂晶格中形成高浓度氧空位，并导致纳米材料表面层的晶格混乱.处理后光催化剂的光学吸收拓展到近红外区，电子给体浓度大大提高，促进了电子输运和界面电荷的迁移与分离；然而，可见光区的吸收对增强的光催化活性没有贡献.氧空位还可以作为活性位点吸附和解离反应物，促进电子从催化剂到吸附质间的转移，甚至直接参与到光催化和光化学反应中.富含氧空位的WO₃可以耦合热催化和光催化反应促进CO₂的选择性还原，或者利用近红外光活化分子氧并选择性氧化胺.氮空位是含氮的n型半导体光催化材料的本质属性.石墨氮化碳中的氮空位有助于促进电荷分离，同时可以作为化学吸附位用于选择性吸附，活化和还原氮气，因此富含氮空位的光催化剂在还原含氮化合物方面具有应用潜力.由于卤素原子在层状卤氧化铋的层间以较弱的范德华力存在，该类化合物容易形成卤原子空位.通过热处理碘氧化铋可以获得活性增强的含碘空位化合物.空位的出现导致带隙变宽和价带下移，光生空穴氧化能力提高，从而获得更好的光催化活性.
传统的n型半导体光催化剂中难以形成阳离子空位.理论研究表明，含阳离子空位的TiO₂具有一系列优点，包括电子传输性能提高，载流子复合受到抑制等.并且钛空位可以作为表面活性位促进水的吸附和离解，从而提高光解水效率.含钛空位的p型TiO₂可以通过焙烧甘油化的前驱体制备，钛空位的出现使得光解水和催化降解有机物活性均大幅提高.含碳空位的石墨氮化碳不仅表现出增强的光催化活性，同时能够提高氧吸附并促进两电子还原氧气产生H₂O₂的反应过程.铋空位能够有效提高铋基光催化剂BiPO₄和Bi₆S₂O₁₅的活性.二维纳米材料的晶面和厚度可以影响表面空位的组成和浓度.BiOCl纳米片的表面是以铋空位为主，而超薄的BiOCl纳米片则是以铋氧联合空位为主，从而表现更优异的光催化活性.最近研究者在含空位的高性能光催化剂制备以及性能调控规律方面取得了长足进展，今后还将继续发展先进的表征技术，进一步研究空位的调控和稳定化手段，并全面理解空位对光催化反应的影响基本规律.空位工程将在半导体光催化技术中发挥更加重要的作用.

关键词: 氧空位, 氢化处理, 光催化, 化学吸附, 钛空位

Abstract:

In contrast to the exploration of novel photocatalytic materials, vacancy engineering of traditional photocatalysts comprising earth-abundant elements represents an effective method for enhancing photocatalytic performance without introducing alien elements. This minireview analyzes the latest progress in engineering vacancies in photocatalysts, remarks on state-of-the-art characterization techniques for vacancies, and reviews the formation chemistry and fundamental benefits of anion and cation vacancies in typical photocatalysts. Although knowledge of these vacancies is increasing, challenges remain in this field, and possible further research is therefore also discussed.

Key words: Oxygen vacancy, Hydrogenated treatment, Photocatalysis, Chemisorption, Titanium vacancy

龙明策, 郑龙辉. 用于太阳光催化反应的空位工程[J]. 催化学报, 2017, 38(4): 617-624.

Mingce Long, Longhui Zheng. Engineering vacancies for solar photocatalytic applications[J]. Chinese Journal of Catalysis, 2017, 38(4): 617-624.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(17)62821-3

https://www.cjcatal.com/CN/Y2017/V38/I4/617

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