Wang Chao, Liu Chao, Li Lei-Jiao, Sun Zhong-Ming
State Key Laboratory of Rare Earth Resource Utilization , Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street , Changchun , Jilin 130022 , China.
University of Chinese Academy of Sciences , Beijing 100049 , P. R. China.
Inorg Chem. 2019 May 6;58(9):6312-6319. doi: 10.1021/acs.inorgchem.9b00508. Epub 2019 Apr 24.
The incorporation of heterometallic atoms into the structure of titanium-oxygen nanomaterials is one of the known and effective strategies to develop new high-performance photovoltaic active materials. In this study, we have synthesized three benzoic acid-stabilized heterometallic titanium oxo clusters with the different transition metals Co, Cu, and Cd, formulated as [TiCo(μ-O)(μ-O)(CHCOO)(CHCN)]·2CHCN (1), [TiCu(μ-O)(CHCOO)] (2), and [TiCd(μ-O)(μ-O)(μ-O)(CHCOO)(CHCOOH)(CHCN)]·CHCN·CHCOOH (3), and then we characterized their structures. UV-vis spectroscopy analysis revealed an enhanced UV-vis-light absorption of those heterometallic clusters. The density functional theory calculations indicated that charge transfer occurs from the p orbital of O atoms to the d orbital of Ti atoms in the TiO core (O → Ti) as well as from the metal to the core in 1 and 2. We also measured the photocurrent response and photocatalytic H evolution, which shows enhancement in the photocurrent intensity and good H evolution ability because of the cooperative effect of heterometal doping in titanium oxo clusters.
将异金属原子引入钛-氧纳米材料结构是开发新型高性能光伏活性材料的已知有效策略之一。在本研究中，我们合成了三种由苯甲酸稳定的、含有不同过渡金属Co、Cu和Cd的异金属钛氧簇，其化学式分别为[TiCo(μ-O)(μ-O)(CHCOO)(CHCN)]·2CHCN (1)、[TiCu(μ-O)(CHCOO)] (2) 和 [TiCd(μ-O)(μ-O)(μ-O)(CHCOO)(CHCOOH)(CHCN)]·CHCN·CHCOOH (3)，然后对其结构进行了表征。紫外-可见光谱分析表明，这些异金属簇的紫外-可见光吸收增强。密度泛函理论计算表明，在TiO核中发生了从O原子的p轨道到Ti原子的d轨道的电荷转移（O→Ti），在1和2中还发生了从金属到核的电荷转移。我们还测量了光电流响应和光催化析氢，结果表明，由于异金属掺杂对钛氧簇的协同作用，光电流强度增强，析氢能力良好。
