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<p>Rare earth metal-organic frameworks (RE-MOFs) have drawn wide attention owing to diverse network structures and various application prospects. However, due to the unpredictable formation of the nodes, it is still challenging to design novel RE-MOFs. A novel versatile strategy was developed employing a RE-acetate complex (RE<sub>2</sub>(CH<sub>3</sub>COO)<sub>6</sub>·4H<sub>2</sub>O) as a precursor to construct RE-MOFs. 2D RE-MOFs (RE-DBP) and 3D RE-MOFs (RE-TCPP) could be obtained by using dicarboxylic porphyrin ligands H<sub>2</sub>DBP and tetracarboxylic porphyrin ligands H<sub>2</sub>TCPP, respectively. Ten RE-MOFs were further synthesized to verify the universality of the methodology. Highly crystalline RE-MOFs could also be prepared at room temperature via the developed strategy, which could significantly promote large-scale preparation and practical application of RE-MOFs. As proof of the concept, the performance of porphyrin-based RE-MOFs was investigated in the photocatalytic cycloaddition of CO<sub>2</sub> with epoxides. Among the RE-DBP(Co) MOFs, Tb-DBP(Co) exhibited the best photocatalytic performance, which was also greater than that of the corresponding 3D MOF Tb-TCPP(Co) due to the optimal 2D structure and thus the accelerated photogenerated charge separation and transfer process. This work not only provides a novel versatile strategy to design and develop RE-MOFs, but also proposes a promising approach for the potential bulk production of RE-MOFs at room temperature.</p>

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A versatile synthetic strategy towards rare earth based metal-organic frameworks

  • 期刊论文

  • 发表日期：

    2025年1月2日

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  • Quan Shi,
  • Yun-Hao Xu,
  • Ming-Hui Chen,
  • Peng Zhao,
  • Wen-Bo Deng,
  • Ji Xiong,
  • Kai Guo,
  • Ya-Qing Feng,
  • Bao Zhang

摘要

Rare earth metal-organic frameworks (RE-MOFs) have drawn wide attention owing to diverse network structures and various application prospects. However, due to the unpredictable formation of the nodes, it is still challenging to design novel RE-MOFs. A novel versatile strategy was developed employing a RE-acetate complex (RE2(CH3COO)6·4H2O) as a precursor to construct RE-MOFs. 2D RE-MOFs (RE-DBP) and 3D RE-MOFs (RE-TCPP) could be obtained by using dicarboxylic porphyrin ligands H2DBP and tetracarboxylic porphyrin ligands H2TCPP, respectively. Ten RE-MOFs were further synthesized to verify the universality of the methodology. Highly crystalline RE-MOFs could also be prepared at room temperature via the developed strategy, which could significantly promote large-scale preparation and practical application of RE-MOFs. As proof of the concept, the performance of porphyrin-based RE-MOFs was investigated in the photocatalytic cycloaddition of CO2 with epoxides. Among the RE-DBP(Co) MOFs, Tb-DBP(Co) exhibited the best photocatalytic performance, which was also greater than that of the corresponding 3D MOF Tb-TCPP(Co) due to the optimal 2D structure and thus the accelerated photogenerated charge separation and transfer process. This work not only provides a novel versatile strategy to design and develop RE-MOFs, but also proposes a promising approach for the potential bulk production of RE-MOFs at room temperature.