The modulation of electronic behavior of metal-based catalysts is vital to optimize their catalytic performance. Herein, metal−organic frameworks (MOFs) are pyrolyzed to afford a series of different-structured Cu−carbon composites and Cu@Ndoped carbon composites. Then a series of CO-resistant catalysts, namely, Co or Ni nanoparticles supported by the Cu-based composites, are synthesized for the hydrogen generation from aqueous NH 3 BH 3 . Their catalytic activities are boosted under light irradiation and regulated by the compositions and the fine structures of doped N species with pyridine, pyrrole, and graphitic configurations in the composite supports. Particularly, the optimized Co-based catalyst with the highest graphitic N content exhibits a high activity, achieving a total turnover frequency (TOF) value of 210 min −1 , which is higher than all the reported unprecious catalysts. Further investigations verify that the light-driven synergistic electron effect of plasmonic Cu-based composites and Co nanoparticles accounts for the high-performance hydrogen generation.
To rationally design photocatalysts with high generation rate and selectivity of target product remains an ongoing challenge for CO2 conversion in pure H2O. Herein, from the viewpoint of enhancing the separation efficiency of photoinduced electron‐hole pairs and the adsorption ability of CO2 molecule, we have constructed a series of Z‐scheme defective heterojunctions of BiOBr nanosheets and hollow NH2‐functionalized metal‐organic framework (MOF) MIL‐125 with Ti ions as metal centers (noted as NH2‐MIL‐125(Ti)). Systematic characterization demonstrates that the BiOBr nanosheets are anchored on the surface of hollow NH2‐MIL‐125(Ti), which facilitates the efficient visible‐light‐driven catalytic reduction of CO2 to CO with nearly 100% selectivity by pure H2O. Especially, the CO generation rate of optimized catalyst with oxygen vacancies reaches 459.7 μmol g−1 h−1, which is higher than those of all the previously reported photocatalysts without sacrificial reagents. This approach provides a new insight for using inorganic semiconductors to fabricate semiconducting MOFs for high‐efficiency photocatalytic reduction CO2 into value‐added chemicals by pure H2O.
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