SPR金属/金红石纳米棒复合体的构筑与改性及其可见光催化醇选择性氧化的性能研究

Utilizing sunlight to drive the photocatalytic selective alcohol oxidation is of great significance to develop the future green chemical techniques. How to enlarge the visible light adsorption, facilitate the photogenerated charge separation and improve the adsorption of reactants are the key scientific problems to develop the green chemical technique of highly effective selective alcohol oxidation driven by visible light. This project intends to first construct the plasmonic metal Bi, Au nanoparticle-rutile nanorod composite then introduce ionic liquid [C1tespim]Beti to modify the surface of rutile nanorod, aiming at realizing the highly effective visible-light photocatalytic selective benzyl alcohol oxidation. Plasmonic metals Bi and Au with surface plasmon resonace (SPR) effect could enlarge and modulate the visible-light adsorption; rutile nanorod with suitable conduction band (CB) position could serve as the thermodynamic election energy platform for the hot electrons of supported plasmonic metals hence is capable of significantly improving the photogenerated charge separation; [C1tespim]Beti would facilitate the adsorption of O2 and alcohol. Basing above, this project intends to construct and modify the plasmonic metal nanoparticle-rutile nanorod composite as the highly effective photocatalytic systems to realize the aerobic selective alcohol oxidation under visible light irradiation. The techniques including time-resolved surface photovoltage，in situ infrared spectroscopy and theoretical calculation are applied to deeply investigate the kinetics of charge transfer and separation of the photocatalyst as well as the mechanism of the surficial photochemical process, which assists to obtain the insight of strategies to improve the photocatalytic activity. This project will back up the development of the highly effective green photocatalytic organic transformations.

利用太阳能催化醇选择性氧化对发展未来绿色化工技术具有重要意义。如何增强可见光吸收、促进电荷分离及改善反应物的表面吸附,是发展高效可见光催化醇选择性氧化的关键科学问题。本项目拟构筑等离子共振（SPR）金属纳米粒子Bi、Au与金红石纳米棒的复合体光催化体系，并进一步以离子液体[C1tespim]Beti对复合体金红石纳米棒进行表面改性，以实现高效的可见光催化醇选择性氧化。利用Bi、Au的SPR效应扩展和调控可见光吸收；利用金红石纳米棒合适的导带位置为SPR热电子提供合适的热力学电子能量平台，促进光生电荷分离；利用离子液体表面改性促进光催化剂表面对O2和醇的吸附。结合气氛控制/时间分辨的表面光电压、原位红外等技术及理论计算深入研究光催化剂的电荷转移、分离、传输等动力学及电荷进一步引发表面化学反应过程机制，深入洞察改善性能的策略。该项目将为发展高效绿色的光催化转化有机物的化工技术提供支持。

本项目发展了基于钛基材料及氮化碳等新型复合光催化材料，实现了高效的光催化芳香醇有氧选择性氧化及CO2还原等重要光催化转化过程。具体针对影响光催化性能的可见光吸收不足，光生电荷分离较差及催化效率较低等关键科学问题，通过引入具有可见光响应组分（如具有等离子共振效应金纳米颗粒及宽可见光吸收半导体材料）拓展可见光吸收；通过引入具有合适能级位置的传统半导体或有机半导体作为合适能量电子平台构建异质结促进光生电荷分离；通过引入特定电子结构的金属纳米颗粒/位点捕获光生载流子同时提供催化功能促进反应物分子活化，从而实现系列高活性复合光催化材料构筑。此外，采用气氛控制的稳态及瞬态表面光伏技术，准原位电子顺磁共振谱及荧光光谱及原位红外光谱等技术，结合理论计算揭示了光生电荷分离过程机制及后续催化过程，从而对复合光催化材料的构效关系进行了深入探究。

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