Publication | Closed Access
Synthesis, Crystal Structures, and Photochemical Properties of a Family of Heterometallic Titanium Oxo Clusters
54
Citations
65
References
2019
Year
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 [Ti<sub>4</sub>Co<sub>2</sub>(μ<sub>2</sub>-O)<sub>2</sub>(μ<sub>3</sub>-O)<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>COO)<sub>12</sub>(CH<sub>3</sub>CN)<sub>2</sub>]·2CH<sub>3</sub>CN (1), [Ti<sub>5</sub>Cu<sub>4</sub>(μ<sub>3</sub>-O)<sub>6</sub>(C<sub>6</sub>H<sub>5</sub>COO)<sub>16</sub>] (2), and [Ti<sub>12</sub>Cd<sub>5</sub>(μ<sub>2</sub>-O)(μ<sub>3</sub>-O)<sub>15</sub>(μ<sub>4</sub>-O)<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>COO)<sub>22</sub>(C<sub>6</sub>H<sub>5</sub>COOH)(CH<sub>3</sub>CN)]·CH<sub>3</sub>CN·C<sub>6</sub>H<sub>5</sub>COOH (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<sub>2</sub> evolution, which shows enhancement in the photocurrent intensity and good H<sub>2</sub> evolution ability because of the cooperative effect of heterometal doping in titanium oxo clusters.
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