MOF-Directed Construction of Cu-Carbon and Cu@N-Doped Carbon as Superior Supports of Metal Nanoparticles toward Efficient Hydrogen Generation.

Abstract

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@N-doped 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 NH3BH3. 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.