Hu Zhao, Li Xiaofang, Zhang Sushu, Li Qin, Fan Jiajie, Qu Xianlin, Lv Kangle
The State Key Laboratory of Refractories and Metallurgy, College of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan, 430081, China.
Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan, 430074, China.
Small. 2020 Nov;16(47):e2004583. doi: 10.1002/smll.202004583. Epub 2020 Oct 27.
Recently, single-atom catalysts have aroused extensive attention in fields of clean energy and environmental protection due to their unique activity and efficient utilization of the active atoms. It is of great importance but still remains a great challenge to unveil the effect of single atoms on precise catalysis. Herein, it is reported that doping TiO hollow microspheres (TiO -HMSs) with single atomic Fe can boost the photoreactivity of TiO -HMSs towards NO oxidation due to the synergistic effects of atomically dispersed Fe and bonded Ti atom which act as dual active sites. The atomically dispersed Fe atoms occupy the subsurface Ti vacancies, and the interaction between Ti 3d and Fe 3d orbitals result in the formation of FeTi bond. Single atomic Fe modulates the electronic structure of the bonded Ti atoms by electron transfer, which facilitates the adsorption and activation of NO and O at Fe and bonded Ti sites, respectively. In addition, the introduction of single atomic Fe sharply suppresses the production of toxic NO byproduct. The synergistic effects of the dual active sites then cause a drastic promotion in photocatalytic oxidation of NO.
近年来，单原子催化剂因其独特的活性和活性原子的高效利用，在清洁能源和环境保护领域引起了广泛关注。揭示单原子对精确催化的影响至关重要，但仍然是一个巨大的挑战。在此，据报道，由于原子分散的铁和键合的钛原子作为双活性位点的协同作用，用单原子铁掺杂TiO中空微球（TiO -HMSs）可以提高TiO -HMSs对NO氧化的光反应活性。原子分散的铁原子占据次表面钛空位，Ti 3d和Fe 3d轨道之间的相互作用导致FeTi键的形成。单原子铁通过电子转移调节键合钛原子的电子结构，这分别促进了NO和O在铁和键合钛位点的吸附和活化。此外，单原子铁的引入显著抑制了有毒NO副产物的产生。双活性位点的协同作用随后导致NO光催化氧化的急剧促进。
