Integration of Pd nanoparticles with engineered pore walls in MOFs for enhanced catalysis

DOI: 10.1016/j.chempr.2020.11.023

Source and publish data:

Chem p. 686 - 698 (2021)

Update date:2022-08-30

Topics:

Authors:

Li, Luyan

Li, Zhixin

Yang, Weijie

Huang, Yamin

Huang, Gang

Guan, Qiaoqiao

Dong, Yemin

Lu, Junling

Yu, Shu-Hong

Jiang, Hai-Long

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Article abstract of DOI:10.1016/j.chempr.2020.11.023

Achieving free-access metal sites with the ability to regulate interactions with substrates is highly desired yet remains a grand challenge in catalysis. Herein, naked Pd nanoparticles were encapsulated inside a metal-organic framework (MOF), giving Pd@MIL-101-NH₂. Its activity and selectivity toward de/hydrogenation reactions can be greatly promoted via the MOF pore wall engineering to regulate Pd surrounding microenvironment and substrate adsorption behavior. Creating free-access active sites and regulating their interaction with substrates are crucial for efficient catalysis, yet remain a grand challenge. Herein, naked Pd nanoparticles (NPs) have been encapsulated in a metal-organic framework (MOF), MIL-101-NH₂, to afford Pd@MIL-101-NH₂. The hydrophobic perfluoroalkyls were post-synthetically modified onto -NH₂ group to yield Pd@MIL-101-F_x (x = 3, 5, 7, 11, 15), which engineer the MOF pore walls to regulate Pd surrounding microenvironment and interaction with substrates. As a result, both the dehydrogenation coupling of organosilane and hydrogenation of halogenated nitrobenzenes show that their activity and selectivity can be greatly promoted upon hydrophobic modification due to the favorable substrate enrichment and regulated interactions between Pd and the modified MOF hosts, far surpassing the traditional supported or surfactant-protected Pd NPs. We envision metal NPs@MOF composites would be an ideal platform integrating the inherent activity of well-accessible metal sites with engineered microenvironment via readily tunable MOFs. Regulating the interaction between active sites and substrates is of great importance in catalysis. The common strategy is to modify the surface of active sites (mostly, metal nanoparticles/NPs in heterogeneous catalysts) with diverse molecules, which, unfortunately, is unfavorable to substrate accessibility and, thus, detrimental to activity. Therefore, it is highly desired to develop heterogeneous catalysts featuring naked metal NPs, which are simultaneously able to regulate interaction with substrates. This puts forward long-standing contradictory challenges on metal NP-based catalysts: (1) exposed active sites, requiring naked metal surface, for their good accessibility; (2) functional molecules around active sites, affording tunable interaction with substrates, for enhanced activity and selectivity. To meet the above challenges, we judiciously encapsulate surface-naked metal NPs into MOFs, achieving tunable interaction with substrates by engineering the MOF pore wall microenvironment.

Full text of DOI:10.1016/j.chempr.2020.11.023

Article

Integration of Pd nanoparticles with

engineered pore walls in MOFs for enhanced

catalysis

Luyan Li, Zhixin Li, Weijie

Yang, ..., Junling Lu, Shu-Hong

Yu, Hai-Long Jiang

jianglab@ustc.edu.cn

HIGHLIGHTS

Tunable interaction between

metal nanoparticles with

substrates is desired

Metal@MOF composites

integrate metal nanoparticles with

tunable interaction

Tunable microenvironment

achieved by metal@MOF via the

MOF wettability modiﬁcation

Enhanced activity/selectivity by

modulated microenvironment

and substrate enrichment

Achieving free-access metal sites with the ability to regulate interactions with

substrates is highly desired yet remains a grand challenge in catalysis. Herein,

naked Pd nanoparticles were encapsulated inside a metal-organic framework

(MOF), giving Pd@MIL-101-NH₂. Its activity and selectivity toward de/

hydrogenation reactions can be greatly promoted via the MOF pore wall

engineering to regulate Pd surrounding microenvironment and substrate

adsorption behavior.

Li et al., Chem 7, 1–13

March 11, 2021 ª 2020 Elsevier Inc.

https://doi.org/10.1016/j.chempr.2020.11.023

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CHEMPR, Corrected proof. doi:10.1016/j.chempr.2020.11.023

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