A Purely Inorganic Quasi-Keggin Polyoxometalate for Photocatalytic Conversion of Carbon Dioxide to Carbon Monoxide,ChemPlusChem

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A Purely Inorganic Quasi-Keggin Polyoxometalate for Photocatalytic Conversion of Carbon Dioxide to Carbon Monoxide
ChemPlusChem ( IF 3.0 ) Pub Date : 2021-07-04 , DOI: 10.1002/cplu.202100260
Xiao-Mei Liu ₁ , Run-Kun Kang ₁ , Ji-Lei Wang ₁ , Jia-Nian Li ₁ , Qiao-Ling Chen ₁ , Yan Xu _{1,

2}

Affiliation

A pure inorganic cluster, H₄₇Na₂Co₄Mo₂₄(PO₄)₁₁O₇₂ ⋅ 15H₂O (denoted as {Co₄Mo₂₄}), has been successfully synthesized by hydrothermal method. Notably, the assembly of a central {Co₂PO₄} tetrahedron and four peripheral {Co[P₄Mo₆]} fragments gives rise to a rare “quasi-Keggin” structure of {Co₄Mo₂₄}, in which Co linkers continue to bridge adjacent substructures, resulting in the generation of 3D framework with large cavities. Benefitting from the combination of strong reductive {P₄Mo₆} units and Co active centers, the photocatalytic system with {Co₄Mo₂₄} as heterogeneous catalyst exhibits excellent activity for CO₂ conversion to CO, offering the CO formation rate of 1848.3 μmol g⁻¹ h⁻¹ with high selectivity of 97.0 %. Besides, thermogravimetric and X-ray diffraction analysis confirm that {Co₄Mo₂₄} can maintain stable during the photocatalytic reaction process.

中文翻译：

一种用于将二氧化碳光催化转化为一氧化碳的纯无机准 Keggin 多金属氧酸盐

通过水热法成功合成了纯无机簇H ₄₇ Na ₂ Co ₄ Mo ₂₄ (PO ₄ ) ₁₁ O ₇₂ ⋅ 15H ₂ O（记为{ Co ₄ Mo ₂₄ }）。值得注意的是，中央 {Co ₂ PO ₄ } 四面体和四个外围 {Co[P ₄ Mo ₆ ]} 碎片的组装产生了一种罕见的 { Co ₄ Mo _{24 的}“准凯金”结构，其中 Co 连接器继续桥接相邻的子结构，导致生成具有大腔的 3D 框架。受益于强还原性{P ₄ Mo ₆ }单元和Co活性中心的结合，以{ Co ₄ Mo ₂₄ }为多相催化剂的光催化体系表现出优异的CO ₂转化为CO的活性，CO生成率为1848.3 μ mol g ^-1 h ^-1具有 97.0 % 的高选择性。此外，热重分析和 X 射线衍射分析证实 { Co ₄ Mo ₂₄} 可以在光催化反应过程中保持稳定。

更新日期：2021-07-19

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