College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211800, P. R. China.
Dalton Trans. 2023 Jul 11;52(27):9465-9471. doi: 10.1039/d3dt01296d.
Two polyoxometalate (POM)-based hybrid compounds have been successfully designed and constructed by the hydrothermal method with molecular formulas [K(HO)FeII0.33Co(HO)(DAPSC)]{[FeII0.33Co(HO)(DAPSC)][FeII0.33Co(HO)][NaFeIII4PWO]}·21.5HO (1), and [Na(HO)FeII0.33Mn(HO)(DAPSC)]{[FeII0.33Mn(HO)(DAPSC)][FeII0.33Mn(HO)][NaFeIII4PWO(HO)]}·24HO (2) (DAPSC = 2,6-diacetylpyridine bis-(semicarbazone)), respectively. Structural analysis revealed that 1 and 2 consisted of metal-organic complexes containing DAPSC ligands with dumbbell-type inorganic clusters, iron-cobalt (iron-manganese) and some other ions. By utilizing a combination of strongly reducing {PW} units and bimetal-doped centres the CO photoreduction catalytic capacity of 1 and 2 was improved. Notably, the photocatalytic performance of 1 was much better than that of 2. In CO photoreduction, 1 exhibited CO selectivity as high as 90.8%. Furthermore, for 1, the CO generation rate reached 6885.1 μmol g h at 8 h with 3 mg, and its better photocatalytic performance was presumably due to the introduction of cobalt and iron elements to give 1 a more appropriate energy band structure. Further recycling experiments indicated that 1 was a highly efficient CO photoreduction catalyst, which could still possess catalytic activity after several cycles.
两种基于多金属氧酸盐（POM）的杂化化合物已经通过水热法成功设计和构建，它们的分子式分别为[K(HO)FeII0.33Co(HO)(DAPSC)]{[FeII0.33Co(HO)(DAPSC)][FeII0.33Co(HO)][NaFeIII4PWO]}·21.5HO（1）和[Na(HO)FeII0.33Mn(HO)(DAPSC)]{[FeII0.33Mn(HO)(DAPSC)][FeII0.33Mn(HO)][NaFeIII4PWO(HO)]}·24HO（2）（DAPSC=2,6-二乙酰基吡啶双（缩氨基硫脲））。结构分析表明，1 和 2 由含有 DAPSC 配体的金属-有机配合物组成，具有哑铃型无机簇、铁-钴（铁-锰）和其他一些离子。通过结合强还原剂{PW}单元和双金属掺杂中心，提高了 1 和 2 的 CO 光还原催化能力。值得注意的是，1 的光催化性能明显优于 2。在 CO 光还原中，1 表现出高达 90.8%的 CO 选择性。此外，对于 1，在 8 小时内，3mg 的 CO 生成速率达到 6885.1 μmol g h，其更好的光催化性能可能归因于钴和铁元素的引入，使 1 具有更合适的能带结构。进一步的循环实验表明，1 是一种高效的 CO 光还原催化剂，经过多次循环后仍具有催化活性。
