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Heterometallic Polyoxotitanium Clusters as Bifunctional Electrocatalysts for Overall Water Splitting
Yi-Qi Tian1, Er-Meng Han1, Bo Wan1
1College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, P. R. China.
Abstract:
Incorporating heterometal into titanium-oxygen clusters (TOCs) is an effective way to improve its catalytic activity. Herein, we synthesize three novel heterometallic TOCs with the formula of [Ti6Cu2O7(Dmg)2(OAc)4(iPrO)6][H2Ti6Cu2O7(Dmg)2(OAc)4(iPrO)8] ({TiCu}), [Ti8Cu2O9(Dmg)2(OAc)2(iPrO)12] ({TiCu}), and [Ti10Co2O6(Dmg)2(Pdc)4(iPrO)18Cl3] ({TiCo}, DmgH2 = dimethylglyoxime; PdcH2 = pyridine-2,3-dicarboxylic acid) using dimethylglyoxime and different carboxylates as the synergistic ligands. By depositing the clusters {TiCu} and {TiCo} on carbon cloth as electrodes, we investigated the electrocatalytic performance of TOCs for full water splitting for the first time. To reach a 10 mA cm-2 current density in an alkaline solution, the {TiCo}@CC electrode needs an overpotential as low as 120 and 400 mV for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), respectively. In addition, full water-splitting equipment with {TiCo}@CC as a cathode and an anode need only 1.67 V to deliver a current density of 10 mA cm-2. Our work confirmed the potential of noble metal-free TOCs as bifunctional cluster-based electrocatalysts for water splitting, and their activities can be tuned by doping with different metal ions.
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