Ligand-Functionalization-Controlled Activity of Metal-Organic Framework-Encapsulated Pt Nanocatalyst toward...

We first report the systematic control of the reactivity of H₂O vapor in metal-organic frameworks (MOFs) with Pt nanocrystals (NCs) through ligand functionalization. We successfully synthesized Pt NCs covered with a water-stable MOF, UiO-66 (Pt@UiO-66), having different metal ions or functionalized ligands. The ligand functionalization of UiO-66 significantly affected the catalytic performance of the water-gas shift reaction, and the replacement of Zr⁴⁺ ions with Hf⁴⁺ ions in UiO-66 had no impact on the catalytic activity. The introduction of a -Br group lowered the reactivity of Pt@UiO-66 by nearly half, whereas the substitution of -Br with a -Me₂ group triply enhanced the activity. The origin of the enhanced catalytic activity was found to be the change in H₂O activity in the UiO-66 pores by the ligand functionalization, which was investigated using H₂O sorption, solid-state NMR, X-ray photoelectron spectroscopy, and in situ IR measurements. This work opens a new prospect to develop MOFs as a platform to activate H₂O.