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

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.

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

“…Finally, in selecting papers for highlighting we have necessarily omitted other clearly relevant papers, including papers by groups led by Rahul Banerjee, 425 Silvia Bordiga, 426 Avelino Corma, [427][428][429][430][431] Deanna M. D'Alessandro, 432 Zhengping Dong, 433 Mohamed Eddaoudi, 434 Roland A. Fischer, 277,435,436 Jorge Gascon, [437][438][439] Stefan Kaskel, 440,441 Hiroshi Kitagawa, 442,443 Susumu Kitagawa, 444 Jing Li, 445 Yangyang Liu, 446,447 Tian-fu Liu, 448 Jeffery Long, 449 Connie C. Lu, 450 Amanda J. Morris, 451 Ali Morsali, 254,452,453 Unni Olsbye, 454 W. L. Queen, 455 Matthew Rosseinsky, 456 Natalia B. Shustova, 457 Berend Smit, 458,459 Norbert Stock, [460][461][462][463] Shane G. Telfer, [464][465][466] Fernando Uribe-Romo, 467 Jenny G. Vitillo,…”

Recent Progresses in Metal–Organic Frameworks Based Core–shell Composites

“…[35,58,73,74] Moreover, the tailorable/ functionalizable porosity of MOF endows the designed composites with tunable sorption selectivity and stability, which are key factors for catalysis. [59,75,76] In the following section, we will discuss the advances of core-shell MOF-based composites in selective, efficient energy-related catalytic reactions.…”

“…This revealed that apart from the core-shell encapsulation, the direct MOF functionalization is a convenient strategy to improve the catalytic properties. [75] Figure 14. A) Pt@UiO-66-H. B) Pt@UiO-66-H(Hf).…”

The Surface Chemistry of Metal Oxide Clusters: From Metal–Organic Frameworks to Minerals

“…For example, NH 2 groups added to the BDC linkers of UiO-66 increase the catalytic activity of the MOF for the hydrolysis of warfare agent simulants. 51 , 52 …”