Edge engineering of platinum nanoparticles via porphyrin-based ultrathin 2D metal–organic frameworks for enhanced photocatalytic hydrogen generation

Edge-doping engineering in metal nanoparticles (MNPs) is always hard to achieve due to the high surface energy of the hybrid MNPs, while porphyrin-based ultrathin two-dimensional (2D) metal–organic framework (MOF) is demonstrated the positive role in stabilize this structure. Herein, a bottom-up method was developed to prepare platinum nanoparticles (PtNPs)-decorated 2D MOF nanosheets, where a porphyrin ligand of Pd-metalized tetrakis(4-carboxyphenyl)porphyrin (PdTCPP) was applied to synthesize ultrathin MOF nanosheets as Zr-TCPP(Pd) in high yield. Attributing to the high superficial area of ultrathin Zr-TCPP(Pd) nanosheets, Pt NPs can well anchor uniformly with small nanoparticle size to obtain 2% Pt/Zr-TCPP(Pd) hybrid nanosheets, which showed a higher photocatalytic hydrogen production rate of 3348 μmol g-1h−1. This is attributed to the coordination between Zr4+ and C = O of PVP, which promotes the contact between PtNPs and Zr-TCPP(Pd) nanosheets. As a result, the long-life electrons of PdTCPP photosensitizers are rapidly transferred to the electron capture center PtNPs, and the photoelectron-hole recombination is effectively inhibited. The apparent quantum efficiency of 2% Pt/Zr-TCPP(Pd) reaches up to 1.56% at 420 nm. The density functional theory (DFT) calculations revealed the Pd-doped position in Pt79 nanoparticle is important that the Pt78Pdsurf. model (Pd atom was doped on the surface of Pt nanoparticle) showed the highest activity with abundant exposed active region.