Ogiwara, NaokiKobayashi, HirokazuInuka, MunehiroNishiyama, YusukeConcepción Heydorn, PatriciaRey Garcia, FernandoKitagawa, Hiroshi2021-11-052021-11-052020-011530-6984https://riunet.upv.es/handle/10251/176227[EN] 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.Reserva de todos los derechosMetal-organic frameworkMetal nanocrystalWater chemistryLigand designHeterogeneous catalysisArtículo10.1021/acs.nanolett.9b04124Cerrado31833371