光催化产氢双助催化剂:类别、合成和设计策略  

Dual cocatalysts for photocatalytic hydrogen evolution:Categories,synthesis,and design considerations

作　　者：伍超 吕康乐[1] 李鑫[2] 李覃[1] Chao Wu;Kangle Lv;Xin Li;Qin Li(Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education&Hubei Key Laboratory of Catalysis and Materials Science&Key Laboratory of Analytical Chemistry of the State Ethnic Affairs Commission,South‐Central Minzu University,Wuhan 430074,Hubei,China;Institute of Biomass Engineering,Key Laboratory of Energy Plants Resource and Utilization,Ministry of Agriculture and Rural Affairs,South China Agricultural University,Guangzhou 510642,Guangdong,China)

机构地区：[1]中南民族大学,催化与能源材料化学教育部重点实验室,催化与材料科学湖北省重点实验室,国家民委分析化学重点实验室,湖北武汉430074 [2]华南农业大学,生物质工程研究所,农业农村部能源植物资源与利用重点实验室,广东广州510642

出　　处：《Chinese Journal of Catalysis》2023年第11期137-160,共24页催化学报（英文）

基　　金：国家自然科学基金(21972171);中南民族大学中央高校基本研究经费(CZQ23037);湖北省自然科学基金(2021CFA022).

摘　　要：在低碳经济背景下,开发以氢能为代表的清洁可再生能源至关重要.利用太阳能驱动半导体进行光催化分解水,是未来可持续制取氢气的有效方法之一.然而,光催化制氢技术产业化受限于半导体表面光生载流子复合效率高和量子效率低.解决上述问题的办法是在半导体中引入双元助催化剂,这不仅可以促使三相界面的形成,促进界面电荷的有效转移,而且不同种类的双助催化剂可以为半导体提供各自的积极作用,协同提高光催化产氢效率和稳定性.因此,需要密切关注双助催化剂的开发,以建立一个集优异的光活性和光稳定性于一体的光催化产氢体系.本文系统地介绍了光催化产氢双助催化剂的类别、优势、合成方法和设计策略.首先,双助催化剂被分为双还原型(Red-Red)和还原-氧化型(Red-Ox)两类,详细概述了在光催化产氢领域中还原型和氧化型助催化剂相互匹配后形成的双助催化剂的实例及其协同效应.总结了在制氢体系中双助催化剂相对于单一助催化剂的五大优势:促进载流子快速迁移、实现电子-空穴空间分离、提高产氢吸附/脱附动力学、提高催化剂光稳定性和阻断可逆反应.随后,概括了双助催化剂-半导体光催化剂的合成策略,基于通常报道的水/溶剂热处理、煅烧、光沉积、自组装和化学沉积等助催化剂的合成方法,可以采用一步法和两步法将两种助催化剂加载到半导体上,获得三元复合材料.探讨了双助催化剂-半导体光催化体系的设计策略,详细总结了如何设计具有优化电子传递路径的Red-Red助催化剂体系和具有空间分离电荷的Red-Ox助催化剂体系.其中,为了优化电子传递路径,两种还原型助催化剂的位置关系可分为三类:核壳包裹结构、分散分布结构和相邻结构;为了实现氧化/还原位点空间分离,氧化-还原型双助催化剂在半导体表面可设计为三种结构:内外To enable a low-carbon economy,it is vital to develop clean and renewable energy sources such as hydrogen energy.One promising strategy is to sustainably generate H2 by solar-driven photocatalytic water splitting using semiconductors.However,the bottleneck in the industrialization of photocatalysis technology lies in the high recombination rate of photogenerated charge carriers in the semiconductors.Fortunately,introducing dual cocatalysts into the semiconductor can promote the development of three-phase interfaces that enable the efficient transfer of interfacial charges,thereby enhancing the photocatalytic H2-evolution efficiency.In this review,we provide a detailed and systematic description of the development of ternary composite photocatalysts with high H2-evolution efficiencies by loading dual cocatalysts onto semiconductors.First,we categorize dual cocatalysts into two types:dual-reductive pairs and reductive-oxidative pairs,and then summarize four advantages of the dual-cocatalyst-based systems for H2 production.Subsequently,the synthesis strategies for dual cocatalyst-semiconductor photocatalysts and their design considerations are presented in detail.Finally,the current status,challenges,and future developmental directions of dual cocatalysts for photocatalytic H2 production are summarized.

关 键 词：双助催化剂 异质结 电荷载流子动力学 光催化 产氢 

分 类 号：O64[理学—物理化学]