Modulating the Chemical Microenvironment of Pt Nanoparticles within Ultrathin Nanosheets of Isoreticular MOFs for Enhanced Catalytic Activity

The catalytic activity of metal nanoparticles (MNPs) embedded in metal-organic frameworks (MOFs) is affected by the electronic interactions between MNPs and MOFs. In this report, we fabricate a series of ultrathin nanosheets of isoreticular MOFs (NMOFs) with different metal nodes as supports and successfully encapsulate Pt NPs within these NMOFs, affording Pt@NMOF-Co, Pt@NMOF-Ni1Co1, Pt@NMOF-Ni3Co1, and Pt@NMOF-Ni nanocomposites. The microchemical environment on the surface of Pt NPs can be modulated by varying the metal nodes of NMOFs. The catalytic activity of the nanocomposites toward liquid-phase hydrogenation of 1-hexene shows obvious difference, in which Pt@NMOF-Ni possesses the highest activity followed by Pt@NMOF-Ni3Co1, Pt@NMOF-Ni1Co1, and Pt@NMOF-Co in a decreasing order of activity. Obviously, increasing gradually the amount of Ni2+ nodes in the carriers can improve the catalytic activity. The difference of catalytic activity of the nanocomposites might originate from the distinct electron interactions between Pt NPs and NMOFs, as ascertained by X-ray photoelectron spectroscopy spectrum and density functional theory calculations. This work provides a rare example that the catalytic activity of MNPs could be controlled by accurately regulating the microchemical environment using ultrathin NMOFs as supports.

Automated summary

This study demonstrates that the catalytic activity of Pt NPs in nanocomposites can be controlled by modulating the microchemical environment using ultrathin NMOFs as supports. The catalytic activity of the nanocomposites towards liquid-phase hydrogenation shows a significant difference, with Pt@NMOF-Ni exhibiting the highest activity. Increasing the amount of Ni2+ nodes in the carriers can improve the catalytic activity. X-ray photoelectron spectroscopy and density functional theory calculations confirm the distinct electron interactions between Pt NPs and NMOFs as the possible origin of the difference in catalytic activity.