Two Ti₁₃-oxo-clusters showing non-compact structures, film electrode preparation and photocurrent properties

Abstract

Two benzene dicarboxylate (BDC) and salicylate (SAL) substituted titanium-oxo-clusters, Ti13O10(o-BDC)4(SAL)4(O(i)Pr)16 (1) and Ti13O10(o-BDC)4(SAL-Cl)4(O(i)Pr)16 (2), are prepared by one step in situ solvothermal synthesis. Single crystal analysis shows that the two Ti13 clusters take a paddle arrangement with an S4 symmetry. The non-compact (non-sphere) structure is stabilized by the coordination of BDC and SAL. Film photoelectrodes are prepared by the wet coating process using the solution of the clusters and the photocurrent response properties of the electrodes are studied. It is found that the photocurrent density and photoresponsiveness of the electrodes are related to the number of coating layers and the annealing temperature. Using ligand coordinated titanium-oxo-clusters as the molecular precursors of TiO2 anatase films is found to be effective due to their high solubility, appropriate stability in solution and hence the easy controllability.

Synthesis, structural and physicochemical characterization of a new type Ti6-oxo cluster protected by a cyclic imide dioxime ligand

“…Crystalline polyoxo-titanium clusters (PTCs) have attracted considerable attention the last years [1][2][3][4][5][6][7][8][9][10][11][12] due to their potential applications in catalysis, medicine, electro-optics, and nanotechnology. [13][14][15][16][17][18][19] In particular, the precise structural information of PTCs can help the understanding of the binding modes of sensitizers to Ti-O 20 surfaces and potential applications in photoelectronic [21][22][23][24] and photocatalytic chemistry. 2,[25][26][27][28][29] Moreover, the development of more efficient TOC photocatalysts for waste water treatment and splitting of the water is a hot topic in renewable energy and environmental research.…”

Mo-doped TiO2photoanodes using [Ti4Mo2O8(OEt)10]2bimetallic oxo cages as a single source precursor

“…with M ¼ Co, Ni, and Mo), nuclearities, spatial arrangements, and functionalities via simple solvothermal methods and isolated by crystallization. [18][19][20][21][22][23] Some of these cages, also called clusters, have successfully been used as precursors for photocatalysts or electrocatalysts, for example using graphene oxide as a sacricial template or impregnating WO 3 photoanodes. 20,24 However, their wide adoption as single source precursors still requires nding facile and effective approaches that overcome their instability in water or humid environments.…”

Novel properties and potential applications of functional ligand-modified polyoxotitanate cages

“…23 Other than 10, such microspheres have also been observed in the deposited films of 7 and 13, 22,25 but not for other similar L-POT cages such as 5 and 8, which only show the formation of microplate morphology (Figure 8c) 25 or simply films without any special features (Figure 8d). 53 Although the detailed formation mechanism is not fully understood yet, there is no doubt that the morphology of deposited films is highly dependent on the L-POT precursor cage used, especially the presence of a functional ligand. This conclusion is further supported by the interesting behaviour of crystalline blocks of [Ti 6 O 3 (O i Pr) 14 (TTF) 2 ]ˑ0.5H 2 O (9), which self-exfoliate upon exposure to air or oxygen, giving rise to stacks of 'floorboardlike' plates (Figure 8e,f).…”