基于红外光高效利用的光子晶体复合光电极构建及其分解水制氢性能研究

Photoelectrochemistry (PEC) is an effective technology way to convert solar energy into green clean energy-hydrogen energy. However, the energy source of PEC hydrogen production which people recently concern is mainly limited to the ultraviolet and visible light, while the infrared light that accounts for about 50% proportion of the solar spectrum is difficult to apply in the PEC hydrogen production due to its low energy, which significantly limits the solar energy utilization of PEC hydrogen production. Therefore, the development of photoelectrode with responding ability to infrared light has become a hot research topic in the field of PEC hydrogen production. This project intends to design and fabricate the upconversion luminescent (Ln-UC) rare earth nanoparticles modifying VB-Group multi-metal oxide composited photoelectrode system with photonic crystal structure. The research objective of infrared light driving PEC hydrogen production from water splitting can be realized by the synergistic action between "Ln-UC spectrum" and "photonic crystal slow-photon effect". The systematic comprehension for the scientific problems in preparation process of composited photoelectrode with responding ability to infrared light can be obtained through controlling the unit characteristics of composited photoelectrode, photonic crystal structure and surface properties of composited materials. Reveal the effect rules of hydrogen production by PEC water splitting based on the photoelectrode with high responding ability to infrared light. Finally establish the new structure system and technology for PEC hydrogen production with efficient utilization of infrared light.

光电化学（PEC）制氢是将太阳能转换为绿色清洁能源--氢能的一个有效技术途径。然而，目前人们所关注PEC制氢的能量来源主要限于紫外及可见光，而在太阳光谱中占50%以上比例的红外光因其能量较低难以应用于PEC制氢，这极大限制了PEC制氢技术对太阳能的利用率。因此，开发红外光响应型光电极已成为PEC分解水制氢领域的一个热门研究课题。本课题拟设计并构建稀土上转换发光（Ln-UC）纳米粒子修饰的VB族多元金属氧化物光子晶体结构光电极体系，通过“Ln-UC光谱”和“光子晶体慢光子效应”协同作用以实现红外光高效响应PEC分解水制氢的研究目标。通过对复合光电极体系组成单元特性、光子晶体结构及复合材料表面性质等要素的调控，获得红外光高效响应型复合光电极制备过程中科学问题的系统认识。揭示基于红外光高效响应型复合光电极PEC分解水产氢性能的影响规律。最终实现红外光高效利用型PEC制氢新结构体系和新技术的建立。

如何拓展半导体光电极的光谱响应范围，并获得高效“太阳能–氢能”转换的光电化学体系，是目前新能源领域的研究热点之一。申请人主要围绕复合结构光电极构筑的关键问题，开展了系列富有成效的研究工作。成功构建了一类具有宽光谱响应范围和优异催化效率的新型光电极，实现了温和条件下光电化学反应性能的显著提升。申请人侧重研究了Ti基和Bi基复合光电极的调控制备及其光电化学分解水制氢性能，并进一步将该类型光电极拓展至光电化学氮气还原和光电化学传感方面研究。借助水分解、氮气还原、有机物催化反应模型，深入理解了金属氧化物（包括过渡金属氧化物和稀土氧化物）复合结构表面活位点的动力学作用机制。申请人在该结题项目资助下，发表国外内高水平论文26篇，授权或受理国家发明专利6项，荣获江苏省科学技术二等奖（排名6）和中国石油与化学工业联合会科技进步一等奖（排名3）各1项。