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  • Title: Ligand-Functionalization-Controlled Activity of Metal-Organic Framework-Encapsulated Pt Nanocatalyst toward Activation of Water.
    Author: Ogiwara N, Kobayashi H, Inukai M, Nishiyama Y, Concepción P, Rey F, Kitagawa H.
    Journal: Nano Lett; 2020 Jan 08; 20(1):426-432. PubMed ID: 31833371.
    Abstract:
    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.
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