Efficient Benzylic C–H Bond Activation over Single-Atom Yttrium Supported on TiO<sub>2</sub> <i>via</i> Facilitated Molecular Oxygen and Surface Lattice Oxygen Activation
Zhen Xue, Jiangrong Yang, Lina Ma, H B Li, Lan Luo, Kaiyue Ji, Zhenhua Li, Xianggui Kong, Mingfei Shao, Lirong Zheng, Ming Xu, Haohong Duan
Abstract
Selective activation of C(sp 3 )–H bonds is important for value-added chemical production, but it remains challenging to proceed under moderate conditions. Herein, we report single-atom yttrium supported on TiO 2 (Y 1 /TiO 2 ) as a catalyst for photocatalytic benzylic C–H bond activation at room temperature. In toluene oxidation, it exhibits a toluene conversion rate of 850 μmol g –1 h –1 with a high benzaldehyde selectivity of 94.1%. Experimental data show that abundant Y 1 δ+ –O–Ti 3+ (δ > 3) sites are formed at the interface with strong electronic metal–support interactions, inducing highly spin-polarized electrons that facilitate charge separation. Furthermore, the single-atom Y species promote the formation of oxygen vacancies and lead to lattice distortion on TiO 2, which facilitates molecular oxygen and surface lattice oxygen activation. These reactive oxygen species can directly react with benzyl radical under light irradiation to produce benzaldehyde and hence increase the photocatalytic performance. This work shows the great potential of rare-earth single-atom catalysts in C(sp 3 )–H bond activation under mild conditions driven by renewable solar energy.