Shape-persistent porous organic cage supported palladium nanoparticles as heterogeneous catalytic materials

Jiang, Shan; Cox, Harrison J.; Papaioannou, Evangelos I.; Tang, Chenyang; Liu, Huiyu; Murdoch, Billy J.; Gibson, Emma K.; Metcalfe, Ian S.; Evans, John S. O.; Beaumont, Simon K.

doi:10.1039/c9nr04553h

Cited by 31 publications

(26 citation statements)

References 34 publications

(45 reference statements)

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“…X-ray photoelectron spectroscopy confirmed the presence of metallic Pd and minor Pd 2+ species. With CC3, CC3-R, and their analogs as the templates, ultrasmall Pd nanoparticles and Ag nanoparticles were also obtained by some other research groups. − …”

Section: Strategies For Encapsulating Metal Nanoparticlesmentioning

confidence: 99%

Encapsulated Metal Nanoparticles for Catalysis

2020

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Metal nanoparticles have drawn great attention in heterogeneous catalysis. One challenge is that they are easily deactivated by migration-coalescence during the catalysis process because of their high surface energy. With the rapid development of nanoscience, encapsulating metal nanoparticles in nanoshells or nanopores becomes one of the most promising strategies to overcome the stability issue of the metal nanoparticles. Besides, the activity and selectivity could be simultaneously enhanced by taking advantage of the synergy between the metal nanoparticles and the encapsulating materials as well as the molecular sieving property of the encapsulating materials. In this review, we provide a comprehensive summary of the recent progress in the synthesis and catalytic properties of the encapsulated metal nanoparticles. This review begins with an introduction to the synthetic strategies for encapsulating metal nanoparticles with different architectures developed to date, including their encapsulation in nanoshells of inorganic oxides and carbon, porous materials (zeolites, metal–organic frameworks, and covalent organic frameworks), and organic capsules (dendrimers and organic cages). The advantages of the encapsulated metal nanoparticles are then discussed, such as enhanced stability and recyclability, improved selectivity, strong metal–support interactions, and the capability of enabling tandem catalysis, followed by the introduction of some representative applications of the encapsulated metal nanoparticles in thermo-, photo-, and electrocatalysis. At the end of this review, we discuss the remaining challenges associated with the encapsulated metal nanoparticles and provide our perspectives on the future development of the field.

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Section: Strategies For Encapsulating Metal Nanoparticlesmentioning

confidence: 99%

Encapsulated Metal Nanoparticles for Catalysis

2020

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“…In the absence of guest species, the thermodynamically most stable polymorph is formed when CC3 crystallized. Considering the similarity of the size of PdNPs with the cage size (max diameter = 2 nm), it could be postulated that a guest PdNP occupied the space of one CC3 molecule within the porous crystalline structure after the PdNPs were immobilized …”

Section: Resultsmentioning

confidence: 99%

Incorporation of Metals and Enzymes with Porous Imine Molecule Cages for Highly Efficient Semiheterogeneous Chemoenzymatic Catalysis

et al. 2021

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Combining the advantages of homogeneous and heterogeneous catalysis is highly desired but remains a challenging goal. Herein, we fabricated a semiheterogeneous metal−enzyme-integrated catalyst using soluble porous imine molecule cages (IMCs), which could partially dissolve in organic solvents under heating conditions for catalytic tasks while precipitate completely at room temperature for catalyst recovery. The IMCs play three vital roles: (1) acting as a support and stabilizer for metal nanoparticles and enzymes, (2) partially solubilizing the heterogeneous catalyst in organic medium, and (3) creating hydrophobic and basic microenvironments for improved catalytic efficiency. The covalent immobilization of the enzyme by utilizing imine bonds via the Ugi-type reaction was disclosed, in which the effect of different parameters on enzyme immobilization and the structure−activity relationship were investigated. The semiheterogeneous catalyst exhibited high activity, selectivity, and reusability in chemoenzymatic dynamic kinetic resolution of amines at low temperature (50−60 °C) with high yields and enantioselectivities (up to 94% yield and 98% ee).

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“…Furthermore, the encapsulated MCs usually possess remarkable durability during the whole catalytic process as the leaching behaviour can be suppressed effectively at high temperature on account of the spatial confinement. In 2019, the Beaumont's group embedded Pd‐MCs (average size: 1.6±0.3 nm) into the cavity of an OMC material (CC3) via gas‐phase reduction in hydrogen [77] . This composite catalyst exhibited broadly comparable catalytic activity toward CO oxidation reaction to other congeneric catalysts such as Pd/SiO 2 , Pd/Al 2 O 3 , etc over the temperature range 100–200 °C.…”

Section: Catalysis Applicationsmentioning

confidence: 99%

Encapsulation of Metal Clusters within Porous Organic Materials: From Synthesis to Catalysis Applications

Yang

Tan

Sun

2022

Chemistry An Asian Journal

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Metal clusters (MCs) with dimensions between a single metal atom and nanoparticles of >2 nm usually possess distinct geometric and electronic structures, and their outstanding performance in catalysis applications have underpinned a broad research interest. However, smaller‐sized MCs are easily deactivated by migration coalescence during the catalysis process because of their high surface energy. Therefore, the search of an appropriate stabilizer for MCs is urgently demanded. In recent years, porous organic polymers (POPs) and organic molecular cages (OMCs), as emerging functional materials, have attracted significant attention. Benefiting from the spatial confinement, encapsulating MCs into these porous organic materials is a promising approach to guarantee the uniform size distribution and stability. In this review, we aim to provide a comprehensive summary of the recent progress in the synthetic strategies and catalysis applications of the encapsulated MCs, and seek to uncover promising ideas that can stimulate future developments at both the fundamental and applied levels.

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Shape-persistent porous organic cage supported palladium nanoparticles as heterogeneous catalytic materials

Abstract: Porous organic cage templates for Pd nanoparticle catalysts – a new porous, solution processable and fully soluble, recrystallisable support for heterogeneous catalysts.

Cited by 31 publications

References 34 publications

Encapsulated Metal Nanoparticles for Catalysis

Encapsulated Metal Nanoparticles for Catalysis

Incorporation of Metals and Enzymes with Porous Imine Molecule Cages for Highly Efficient Semiheterogeneous Chemoenzymatic Catalysis

Encapsulation of Metal Clusters within Porous Organic Materials: From Synthesis to Catalysis Applications

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