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Title

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

AuthorsOgiwara, N.; Kobayashi, H.; Inukai, M; Nishiyama, Y; Concepción, Patricia; Rey García, Fernando; Kitagawa, H.
KeywordsFunctionalization
Platinum
Ligands
Metal organic frameworks
Reactivity
Issue Date13-Dec-2019
PublisherACS Publications
CitationNano Letters 20(1): 426-432 (2019)
AbstractWe first report the systematic control of the reactivity of HO 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 Zr ions with Hf 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 -Me group triply enhanced the activity. The origin of the enhanced catalytic activity was found to be the change in HO activity in the UiO-66 pores by the ligand functionalization, which was investigated using HO 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 HO.
Publisher version (URL)http://dx.doi.org/10.1021/acs.nanolett.9b04124
URIhttp://hdl.handle.net/10261/220879
Identifiersdoi: 10.1021/acs.nanolett.9b04124
issn: 1530-6992
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