Metal-organic frameworks with mixed-anion secondary building units as efficient photocatalysts for hydrogen generation

作者：Bu, Donglei^*; Bu, Duocheng; Chen, Wei; Huang, Changgeng; Li, Libo; Lei, Hao^*; Huang, Shaoming^*

来源：Journal of Catalysis, 2022, 407: 10-18.

DOI：10.1016/j.jcat.2022.01.008

• Photocatalysis
• Hydrogen productivity
• Mixed-anion SBUs
• Tunable activity

Three new CPs (Cu-X-bpy, X = Cl/Br, Cl/I or Br/I; bpy = 4,4'-bipyridine) with mixed-anion secondary build-ing units (SBUs) were successfully synthesized and their structures were confirmed by X-ray crystallog-raphy, PXRD, far-IR and Raman spectroscopy, EXAFS, EDX, element analysis and ICP-MS. Their photocatalytic H2 productivities were systematically investigated and compared with corresponding single-anion Cu-X-bpy (X = Cl, Br, I). It was found that the CPs possess excellent H2 productivity even without additional photosensitizer and cocatalyst, and their activities can be significantly enhanced from 2.79 (Cu-I-bpy) to 10.04 mmol/gh (Cu-Cl/I-bpy) by simply varying the anions, mu-X-, in SBUs. Mechanistic investigations indicate that the water dissociation and hydrogen adsorption energies during water split-ting can be regulated by just varying mu-X- in SBUs, which majorly accounts for their great discrepancy in H2 productivity rather than the light harvesting, charge separation and transfer efficiency of Cu-X-bpy. This finding enlightens a new approach for designing water splitting and related catalytic materials.

• 单位
  广东工业大学