TY - JOUR
T1 - Ligand-Functionalization-Controlled Activity of Metal-Organic Framework-Encapsulated Pt Nanocatalyst toward Activation of Water
AU - Ogiwara, Naoki
AU - Kobayashi, Hirokazu
AU - Inukai, Munehiro
AU - Nishiyama, Yusuke
AU - Concepción, Patricia
AU - Rey, Fernando
AU - Kitagawa, Hiroshi
N1 - Funding Information:
This work was supported by JSPS Grants-in-Aid for Scientific Research (B) (No. 15H03784), JSPS Grant-in-Aid for Research Activity start-up (No. 19K23648), JSPS Research Fellow (No. 17J10099), JST PRESTO (No. JPMJPR1514), and Spanish Government-MINECO through “Severo Ochoa” Excellence Programme (SEV-2016-0683).
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2020/1/8
Y1 - 2020/1/8
N2 - 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.
AB - 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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U2 - 10.1021/acs.nanolett.9b04124
DO - 10.1021/acs.nanolett.9b04124
M3 - Article
C2 - 31833371
AN - SCOPUS:85076887015
SN - 1530-6984
VL - 20
SP - 426
EP - 432
JO - Nano Letters
JF - Nano Letters
IS - 1
ER -