Effect of the Defect Modulator and Ligand Length of Metal–Organic Frameworks on Carbon Dioxide Photoreduction

The nature of defects and organic ligands can fine-tune the absorption energy (Eabs) of metal-organic frameworks (MOFs), which is crucial for photocatalytic reactions; however, the relevant studies are in their infancy. Herein, a series of typical MOFs of the UiO family (UiO-6x-NH2, x = 8, 7, and 6) with ligands of varied lengths and amino-group-modified defects were synthesized and employed to explore their performance for photocatalytic CO2 reduction. Sample UiO-66-NH2-2ABA (2ABA = 3,5-diamino-benzoate) with the shortest dicarboxylate ligand and two amino-group-modified defects exhibits superior photocatalytic activity due to the lowest Eabs. The CO yield photocatalyzed by UiO-66-NH2-2ABA is 17.5 μmol g-1 h-1, which is 2.4 times that of UiO-68-NH2-BA (BA = benzoate) with the longest ligand and no amino group involved in the defects. Both the experiments and theoretical calculations show that shorter dicarboxylate ligands and more amino groups result in smaller Eabs, which is favorable for photocatalytic reactions. This study provides new insights into boosting the photocatalytic efficiency by modulating the defects and ligands in MOFs.