Qiu Zhao-Feng, Wang Peng, Zhang Kai-Yang, Zhao Yue, Sun Wei-Yin
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, China.
Inorg Chem. 2024 Sep 30;63(39):18193-18199. doi: 10.1021/acs.inorgchem.4c03075. Epub 2024 Sep 18.
As heterogeneous photocatalysts that can effectively transform CO to CO, two MOFs with different metal centers, namely, M(tipe)(HO)·solvent (M = Ni named as and M = Co referred to as ), were synthesized by reactions of 1,1,2,2-tetrakis(4-(imidazole-1-yl)phenyl)ethene (tipe) with the corresponding metal perchlorate. Both and have 3D structures, in which the metal centers have the same coordination environment with the NO donor set. Driven by visible light, the CO production catalyzed by is 6734.1 μmol g with 45.3% selectivity, and in contrast, has 4601.3 μmol g CO production with 97.6% selectivity in 5 h. Through photoelectrochemical characterization, DFT calculations, and in situ FT-IR measurements, the photocatalytic CO reduction process catalyzed by and was investigated. The results show that the metal center of the MOF is crucial for photocatalytic CO reduction. This work offers an innovative approach for controlling the performance of photocatalytic CO reduction through tuning the metal centers of architectures.
作为能够有效将CO转化为CO₂的多相光催化剂，通过1,1,2,2-四（4-（咪唑-1-基）苯基）乙烯（tipe）与相应的金属高氯酸盐反应，合成了两种具有不同金属中心的金属有机框架材料，即[M(tipe)(H₂O)] (ClO₄)·溶剂（M = Ni命名为 ，M = Co称为 ）。 和 均具有三维结构，其中金属中心与NO供体组具有相同的配位环境。在可见光驱动下， 催化的CO₂生成量为6734.1 μmol g，选择性为45.3%，相比之下， 在5小时内的CO₂生成量为4601.3 μmol g，选择性为97.6%。通过光电化学表征、密度泛函理论计算和原位傅里叶变换红外光谱测量，研究了 和 催化的光催化CO₂还原过程。结果表明，金属有机框架材料的金属中心对光催化CO₂还原至关重要。这项工作为通过调整结构的金属中心来控制光催化CO₂还原性能提供了一种创新方法。
