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    氧化物半导体调控策略及光催化制氢研究进展

    Research progress on regulation strategies of oxide semiconductors and photocatalytic hydrogen production

    • 摘要: 光催化分解水制氢技术因其绿色、可再生和环境友好等优势,在清洁能源开发与“碳中和”目标实现中备受关注。光催化剂作为反应的核心,其物理化学性能直接决定了光催化制氢过程的效率与可行性。氧化物半导体因具有结构稳定性高、制备工艺简便、原料成本低廉以及化学性质可调等优点,已成为光催化制氢研究的重要材料体系。然而,该类材料普遍存在可见光响应范围有限、光生电子–空穴对易复合、表面反应动力学缓慢等固有缺陷,显著制约了其在实际应用中的性能发挥。因此,亟需通过有效的结构与性能调控手段,提升其光吸收能力、载流子分离效率及表面催化活性。系统综述了近年来氧化物半导体光催化剂在制氢领域的性能调控策略及最新研究进展,重点分析了3类典型方法的作用机制与优化效果。表面工程通过构筑特定缺陷、引入表面等离子体效应、沉积助催化剂等方式,有效增加光吸收与反应活性位点数量,并调控表面能级结构;界面工程利用异质结构设计实现界面能带匹配与内建电场调控,从而促进光生载流子的定向迁移与空间分离,同时保持较强的氧化还原能力。极化工程依托压电或铁电材料在外力或温度变化下产生的极化电场,构建稳定的内生电势梯度,实现对载流子分布与反应路径的有效调控。通过对不同调控机制的原理解析与代表性研究成果的对比,总结了各策略在提升可见光利用率、延长载流子寿命及提高产氢速率方面的优势与不足,并指出当前研究仍面临界面精细调控难、缺陷可控性不足及长期稳定性有限等挑战。在此基础上,提出未来可结合多策略协同设计、原位表征与理论计算及工程化应用探索等方向开展深入研究,以推动氧化物半导体光催化制氢技术向高效、稳定及可规模化的目标迈进。

       

      Abstract: Photocatalytic water splitting for hydrogen production has attracted significant attention in the field of clean energy due to its green, renewable, and environmentally friendly characteristics. As the core of the reaction, the physicochemical properties of photocatalysts directly determine the efficiency and feasibility of photocatalytic hydrogen evolution. Oxide semiconductors have emerged as an important class of materials for photocatalytic hydrogen production because of their high structural stability, simple preparation process, low cost, and tunable chemical properties. However, their limited visible-light response, rapid recombination of photogenerated electron-hole pairs, and sluggish surface reaction kinetics significantly restrict their practical performance. Therefore, effective structural and performance modulation strategies are urgently required to enhance their light-harvesting capacity, carrier separation efficiency, and surface catalytic activity. This review systematically summarizes recent advances in performance modulation strategies for oxide semiconductor photocatalysts in hydrogen production, with a focus on the mechanisms and optimization effects of three representative approaches. Surface engineering effectively increases the number of light absorption sites and reactive active sites, and regulates the surface energy level structure by means of constructing specific defects, introducing surface plasmon effects, depositing cocatalysts, and so on. Interface engineering uses heterostructure design to realize interface energy band matching and built-in electric field regulation, thereby promoting the directional migration and spatial separation of photogenerated carriers while maintaining strong redox capability. Polarization engineering utilizes the polarization fields generated by piezoelectric or ferroelectric materials under external stress or temperature variation to establish a stable intrinsic potential gradient, effectively controlling carrier distribution and reaction pathways. By analyzing the fundamental principles and representative studies of these modulation strategies, this work summarizes their respective advantages and limitations in enhancing visible-light utilization, extending carrier lifetimes, and improving hydrogen evolution rates. It also highlights current challenges, including the difficulty of precise interfacial control, insufficient defect tunability, and limited long-term stability. Finally, future research directions are proposed, such as synergistic multi-strategy design, in situ characterization combined with theoretical calculations, and pilot-scale and engineering application exploration, to accelerate the development of oxide semiconductor photocatalysts toward high-efficiency, stable, and scalable hydrogen production systems.

       

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