Zhu Kainan, Zhu Qian, Jiang Mengpei, Zhang Yaowen, Shao Zhiyu, Geng Zhibin, Wang Xiyang, Zeng Hui, Wu Xiaofeng, Zhang Wei, Huang Keke, Feng Shouhua
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
Shenyang National Laboratory for Materials Science Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua RD, Shenyang, 110016, China.
Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202207600. doi: 10.1002/anie.202207600. Epub 2022 Jul 14.
The electronic structure of composites plays a critical role in photocatalytic conversion, whereas it is challenging to modulate the orbital for an efficient catalyst. Herein, we regulated the t orbital occupancy state of Ti to realize efficient CO conversion by adjusting the amount of photo-deposited Cu in the Cu/TiO composite. For the optimal sample, considerable electrons transfer from the Cu d orbital to the Ti t orbital, as proven by X-ray absorption spectroscopy. The Raman spectra results also corroborate the electron enrichment on the Ti t orbital. Further theoretical calculations suggested that the orbital energy of the Ti 3d orbital in TiO is declined, contributing to accepting Cu 3d electrons. As a result, the Cu/TiO composite exhibited an extremely high selectivity of 95.9 % for CO, and the productivity was 15.27 μmol g h , which is almost 6 times that of the original TiO . Our work provides a strategy for designing efficient photocatalysis as a function of orbital regulation.
复合材料的电子结构在光催化转化中起着关键作用，然而，对于高效催化剂而言，调节轨道具有挑战性。在此，我们通过调节Cu/TiO复合材料中光沉积Cu的量来调控Ti的t轨道占据状态，以实现高效的CO转化。对于最佳样品，大量电子从Cu d轨道转移到Ti t轨道，这已通过X射线吸收光谱得到证实。拉曼光谱结果也证实了Ti t轨道上的电子富集。进一步的理论计算表明，TiO中Ti 3d轨道的轨道能量降低，有利于接受Cu 3d电子。结果，Cu/TiO复合材料对CO表现出95.9%的极高选择性，产率为15.27 μmol g h，几乎是原始TiO的6倍。我们的工作提供了一种基于轨道调控设计高效光催化的策略。
