Functionalized hierarchical porous polymeric monoliths as versatile platforms to support uniform and ultrafine metal nanoparticles for heterogeneous catalysis

Tan, Liangxiao; Tan, Bien

doi:10.1016/j.cej.2020.124485

Cited by 48 publications

(37 citation statements)

References 60 publications

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“…When metal acts as a catalyst, its preferred form are nanoparticles providing a high surface area. They can be introduced onto the polymer pore surface via immobilization [ 9 , 10 ]. However, their high tendency toward agglomeration can result in a decrease in their specific surface [ 11 ], non-uniform surface coverage, or even pore clogging.…”

Section: Introductionmentioning

confidence: 99%

Flow-Through PolyHIPE Silver-Based Catalytic Reactor

et al. 2021

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Catalytic reactors performing continuously are an important step towards more efficient and controllable processes compared to the batch operation mode. For this purpose, homogenous high internal phase emulsion polymer materials with an immobilized silver catalyst were prepared and used as a continuous plug flow reactor. Porous material with epoxide groups was functionalized to bear aldehyde groups which were used to reduce silver ions using Tollens reagent. Investigation of various parameters revealed that the mass of deposited silver depends on the aldehyde concentration as well as the composition of Tollens reagent. Nanoparticles formed on the pore surface showed high crystallinity with a cuboctahedra crystal shape and highly uniform surface coverage. The example of the 4-nitrophenol catalytic reduction in a continuous process was studied and demonstrated to be dependent on the mass of deposited silver. Furthermore, productivity increased with the volumetric silver density and flow rate, and it was preserved during prolonged usage and storage.

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Section: Introductionmentioning

confidence: 99%

Flow-Through PolyHIPE Silver-Based Catalytic Reactor

et al. 2021

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“…[2,20,21] For traditional porous polymeric monoliths, DVB is used as an important co-monomer to construct networks having macro-/mesopores, and the microporosity is obtained even by further crosslinking mesoporous/macorporous networks by various knitting methods. [11,[23][24][25][26][27] Herein, following the establishment of multiple Friedel-Crafts alkylation based strategies, we, for the first time, report the synthesis of HCPs monoliths with microporsity and high mechanical strength by employing DVB as a sole selfcrosslinking monomer in a two-step method. This is achieved by a slow, low-degree, and uniform crosslinking of monolith precursors at room temperature using a small amount of catalyst.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, the BET surface area of the HCPs monoliths produced by this simple method is much higher than those of the reported porous polymer monoliths. [11,[23][24][25][26][27] For practical applications, the mechanical strength of porous monoliths is very important and, therefore, the mechanical strength of HCPs monoliths was measured by a 2 kN intelligent strength tester at room temperature. The HCPs monoliths 2-6 showed different types of stress-strain curve and compressive strength, and the compressive strength was enhanced with an increase in DVB concentration (Figure 4a).…”

Section: Resultsmentioning

confidence: 99%

Unprecedented Processable Hypercrosslinked Polymers with Controlled Knitting

Wang

Zhang

Liu

et al. 2021

Macromol. Rapid Commun.

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Processable microporous organic polymers (MOPs) attract incomparable research interest because their vairous types, such as monoliths and membranes are for practical application. Most processable MOPs usually need harsh conditions such as the use of expensive metal catalysts, specialized stereospecific monomers, etc., which restrict the sustainable and real applications of processable MOPs. Therefore, the economical mass production of processable MOPs remains a formidable challenge. Herein, a novel strategy is reported for constructing processable hypercrosslinked polymers (HCPs) need two steps synthesis of pre-crosslinking and deep-crosslinking using divinylbenzene (DVB) as a self-crosslinking monomer under the catalysis of a small amount of FeCl 3 . The resulting HCPs monoliths possess high BET surface area of 1033-1056 m 2 g −1 with hierarchical porosity, and show excellent mechanical strength up to 65 MPa. It is, to the best of authors' knowledge, the first report of using aromatic vinyl monomers as self-crosslinking monomers to generate HCPs monoliths with high surface area, yielding no by-products, and high mechanical strength.

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“…Porosity is a property that offers a variety of benefits within polymer-based structures, including high surface area-to-volume ratio, flexibility, and selective permeability . Thus, porous materials have broad applications in adsorption, , separation, − sensing, , catalysis, , and biomedical engineering. − Combining porosity with advanced manufacturing methods such as 3D printing (3DP) is an attractive option for producing objects with complex geometries, such as custom shoe midsoles, , football helmet linings, battery electrodes, tissue scaffolds, ,, and biomimicking materials. − Despite these benefits, further developments are required for porous polymeric materials to realize their full potential within 3DP.…”

Section: Introductionmentioning

confidence: 99%

Structure–Processing–Property Relationships of 3D Printed Porous Polymeric Materials

Cipriani

Defilló

et al. 2021

ACS Mater. Au

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Imparting porosity to 3D printed polymeric materials is an attractive option for producing lightweight, flexible, customizable objects such as sensors and garments. Although methods currently exist to introduce pores into 3D printed objects, little work has explored the structure–processing–property relationships of these materials. In this study, photopolymer/sacrificial paraffin filler composite inks were produced and printed by a direct ink writing (DIW) technique that leveraged paraffin particles as sacrificial viscosity modifiers in a matrix of commercial elastomer photocurable resin. After printing, paraffin was dissolved by immersion of the cured part in an organic solvent at elevated temperature, leaving behind a porous matrix. Rheometry experiments demonstrated that composites with between 40 and 70 wt % paraffin particles were able to be successfully 3D printed; thus, the porosity of printed objects can be varied from 43 to 73 vol %. Scanning electron microscopy images demonstrated that closed-cell porous structures formed at low porosity values, whereas open-cell structures formed at and above approximately 53 vol % porosity. Tensile tests revealed a decrease in elastic modulus as the porosity of the material was increased. These tests were simulated using finite element analysis (FEA), and it was found that the Neo-Hookean model was appropriate to represent the 3D printed porous material at lower and higher void fractions within a 75% strain, and the Ogden model also gave good predictions of porous material performance. The transition between closed- and open-cell behaviors occurred at 52.4 vol % porosity in the cubic representative volume elements used for FEA, which agreed with experimental findings that this transition occurred at approximately 53 vol % porosity. This work demonstrates that the tandem use of rheometry, FEA, and DIW enables the design of complex, tailorable 3D printed porous structures with desired mechanical performance.

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Functionalized hierarchical porous polymeric monoliths as versatile platforms to support uniform and ultrafine metal nanoparticles for heterogeneous catalysis

Cited by 48 publications

References 60 publications

Flow-Through PolyHIPE Silver-Based Catalytic Reactor

Flow-Through PolyHIPE Silver-Based Catalytic Reactor

Unprecedented Processable Hypercrosslinked Polymers with Controlled Knitting

Structure–Processing–Property Relationships of 3D Printed Porous Polymeric Materials

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