posted on 2021-11-24, 21:13authored byYi-Xin Wu, Xue-Ru Liu, Guo Chen, Yi-Qi Tian, Jun Yan, Xiao-Yi Yi, Chao Liu
Incorporating heterometal and chromogenic
groups into the titanium
oxo cluster (TOC) nanomaterials is one of the effective strategies
for the development of new high-performance photoelectrically active
materials. In this Article, we report the structures and photoelectrochemical
(PEC) performances of a family of TOCs, including pure [Ti12O8(OEt)16L8] ({Me-Ti12}) and six Cd-doped clusters
formulated as [H4Cd2Ti10O8(OEt)16(L)8(H2O)2] ({Cd2Ti10}; L = salicylic acid and their derivatives).
The six Cd-doped clusters are isostructural, containing the same {Cd2Ti10O8} core, but are protected by salicylic
ligands modified with different functional groups. The compositions,
structures, and solution stability of these clusters have been studied
in detail by single-crystal X-ray diffraction and electrospray ionization
mass spectrometry measurements. The embedding of heterometallic Cd(II)
and chemical modification of organic protective shells can effectively
regulate the PEC water oxidation activity of those clusters, with {F-Cd2Ti10} having the highest turnover number of 518.55
and the highest turnover frequency of 172.85 h–1. Our work highlights the potential of using TOCs that do not contain
noble metals as water oxidation catalysts, and their catalytic activity
can be regulated by structural modification.