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] ({Ti₆Cu₂}), [Ti₈Cu₂O₉(Dmg)₂(OAc)₂(ⁱPrO)₁₂] ({Ti₈Cu₂}), and [Ti₁₀Co₂O₆(Dmg)₂(Pdc)₄(ⁱPrO)₁₈Cl₃] ({Ti₁₀Co₂}, DmgH₂ = dimethylglyoxime; PdcH₂ = pyridine-2,3-dicarboxylic acid) using dimethylglyoxime and different carboxylates as the synergistic ligands. By depositing the clusters {Ti₆Cu₂} and {Ti₁₀Co₂} 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 {Ti₁₀Co₂}@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 {Ti₁₀Co₂}@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.

中文翻译：

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异金属多氧钛簇作为双功能电催化剂用于整体水分解

将异质金属掺入钛-氧簇（TOCs）是提高其催化活性的有效方法。在此，我们合成了三种新型异金属TOCs，分子式为[Ti ₆ Cu ₂ O ₇ (Dmg) ₂ (OAc) ₄ ( ⁱ PrO) ₆ ][H ₂ Ti ₆ Cu ₂ O ₇ (Dmg) ₂ (OAc) ₄ ( ⁱ PrO) ₈ ] ( {Ti ₆ Cu ₂ } ), [Ti ₈ Cu ₂ O ₉ (Dmg) ₂(OAc) ₂ ( ⁱ PrO) ₁₂ ]( {Ti ₈ Cu ₂ } )、[Ti ₁₀ Co ₂ O ₆ (Dmg) ₂ (Pdc) ₄ ( ⁱ PrO) ₁₈ Cl ₃ ] ( {Ti ₁₀ Co ₂ } , DmgH ₂ = 二甲基乙二肟；PdcH ₂ = 吡啶-2,3-二羧酸)，使用二甲基乙二肟和不同的羧酸盐作为协同配体。通过沉积簇{Ti ₆ Cu ₂ }和{Ti ₁₀ Co ₂ }在碳布上作为电极，我们首次研究了TOCs对全水分解的电催化性能。为了在碱性溶液中达到 10 mA cm ^{–2的电流密度，} {Ti ₁₀ Co ₂ } @CC 电极的析氢反应 (HER) 和析氧反应 (OER) 需要低至 120 和 400 mV 的过电位）， 分别。此外，以{Ti ₁₀ Co ₂ } @CC 为阴极和阳极的全水分解设备仅需 1.67 V 即可提供 10 mA cm ^{–2的电流密度}. 我们的工作证实了无贵金属 TOC 作为双功能簇基电催化剂用于水分解的潜力，并且它们的活性可以通过掺杂不同的金属离子来调节。