PDMS-coated hypercrosslinked porous organic polymers modified <i>via</i> double postsynthetic acidifications for ammonia capture

Kang, Dong Won; Kang, Min‐Jung; Moon, Minkyu; Kim, Hyojin; Eom, Sunhwi; Choe, Jong Hyeak; Lee, William R.; Hong, Chang Seop

doi:10.1039/c8sc02640h

Cited by 41 publications

(32 citation statements)

References 39 publications

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“…While most of the block polymer-based approaches have been limited in the synthesis of mesoporous polymers, our results suggest that the use of block polymers as desirable templates for smaller nanopores can be achieved; a wide range from meso-to micropore size control can be rationally addressed, and surface area is accessible to differently sized guests which can be regulated by pore size. Ample opportunities such as size-selective catalysis can be envisioned by taking advantages of hyper-cross-linked networks for surface functionalization 71 and hosting inorganic nanoparticles. 72 We also believe our findings on securing domain purity and in reinforcing the framework are applicable to other self-assembly based approaches targeting length scale control in the range of 1 nm.…”

Section: Discussionmentioning

confidence: 99%

Downsizing of Block Polymer-Templated Nanopores to One Nanometer via Hyper-Cross-Linking of High χ–Low N Precursors

Lee

Seo

2021

ACS Nano

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Synthesizing nanoporous polymer from the block polymer template by selective removal of the sacrificial domain offers straightforward pore size control as a function of the degree of polymerization (N). Downscaling pore size into the microporous regime (<2 nm) has been thermodynamically challenging, because the low N drives the system to disorder and the small-sized pore is prone to collapse. Herein, we report that maximizing cross-linking density of a block polymer precursor with an increased interaction parameter (χ) can help successfully stabilize the structure bearing pore sizes of 1.1 nm. We adopt polymerization-induced microphase separation (PIMS) combined with hyper-cross-linking as a strategy for the preparation of the bicontinuous block polymer precursors with a densely cross-linked framework by copolymerization of vinylbenzyl chloride with divinylbenzene and also Friedel–Crafts alkylation. Incorporating 4-vinylbiphenyl as a higher-χ comonomer to the sacrificial polylactide (PLA) block and optimizing the segregation strength versus cross-linking density allow for further downscaling. Control of pore size by N of PLA is demonstrated in the range of 9.9–1.1 nm. Accessible surface area to fluorescein-tagged dextrans is regulated by the relative size of the pore to the guest, and pore size is controlled. These findings will be useful for designing microporous polymers with tailored pore size for advanced catalytic and separation applications.

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Section: Discussionmentioning

confidence: 99%

Downsizing of Block Polymer-Templated Nanopores to One Nanometer via Hyper-Cross-Linking of High χ–Low N Precursors

Lee

Seo

2021

ACS Nano

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“…Hong and co‐workers enhanced the NH 3 uptake of hypercrosslinked porous organic polymers (HCP) through double postsynthetic acidification and coating with hydroxyl‐terminated poly(dimethylsiloxane) (PDMS). [ 108 ] The HCP (1T) was prepared by the solvothermal reaction of toluene, formaldehyde dimethyl acetal (FDA), 1,2‐dichloroethane (DCE), and the FeCl 3 catalyst. The reaction time was shortened from 18–24 h to 5 h with a microwave‐assisted reaction.…”

Section: Porous Composite Materialsmentioning

confidence: 99%

Emerging Porous Materials and Their Composites for NH₃ Gas Removal

Kang

Kim

et al. 2020

Advanced Science

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NH 3 , essential for producing artificial fertilizers and several military and commercial products, is being produced at a large scale to satisfy increasing demands. The inevitable leakage of NH 3 during its utilization, even in trace concentrations, poses significant environmental and health risks because of its highly toxic and reactive nature. Although numerous techniques have been developed for the removal of atmospheric NH 3 , conventional NH 3 abatement systems possess the disadvantages of high maintenance cost, low selectivity, and emission of secondary wastes. In this context, highly tunable porous materials such as metal-organic frameworks, covalent organic frameworks, hydrogen organic frameworks, porous organic polymers, and their composite materials have emerged as next-generation NH 3 adsorbents. Herein, recent progress in the development of porous NH 3 adsorbents is summarized; furthermore, factors affecting NH 3 capture are analyzed to provide a reasonable strategy for the design and synthesis of promising materials for NH 3 abatement.

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“…In bottom‐up approach, the building block need primarily undergoes modification or guest anchoring procedure, and this approach may hold some limitations such as the anchored hydrophilic groups could potentially react with other active sites during POPs synthesis [11b] . Meanwhile, in the PSM approach, the constructed POPs framework should further modification through corresponding coupling reaction between POPs skeleton and incoming hydrophilic constituent [11c] . More importantly, under postsynthetic modification, the introduced hydrophilic functional groups were usually random with uneven distribution POPs framework [12] .…”

Section: Introductionmentioning

confidence: 99%

Solvent‐Induced Flower‐ and Cudgel‐Shaped Porous Organic Polymers: Effective Supports of Palladium Nanoparticles for Dehalogenation in Net Water

Sui

et al. 2022

ChemNanoMat

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Dehalogenation of aromatic halides is one of the most important reactions for detoxification of water ecosystems; at the same time the ability is inevitably tied to the dispersibility of catalyst in aqueous medium. Herein, we present aporous organic polymers containing hydrophilic urea groups (UPOPs) for effective immobilization of palladium nanoparticles (NPs) through a facile urea‐forming condensation reaction. The urea groups not only serve as an intriguing linkage of organic framework, but also endows Pd@UPOPs outstanding dispersibility in H2O. The morphology of UPOPs have exerted important influence upon the size and dispersion of palladium NPs as well as their catalytic performances. The palladium NPs are well dispersed on the surface of UPOP‐1 with an average size of 2.1±0.3 nm. In contrast, palladium NPs on UPOP‐2 exhibit a dual size distribution with an average diameter of 2.0±0.4 and 4.2±0.4 nm. The dehalogenation reactions of chlorobenzene have demonstrated that Pd@UPOP‐1 with flower‐shaped morphology show higher catalytic activity, recyclability and stability than that of Pd@UPOP‐2 with cudgel‐shaped morphology. This work offers/supplies a new insight for the development of efficient catalytic systems based on porous organic polymers supported metal NPs in aqueous medium.

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PDMS-coated hypercrosslinked porous organic polymers modified via double postsynthetic acidifications for ammonia capture

Abstract: Double postsynthetic acidifications of a hypercrosslinked polymer afforded record high NH3 adsorption capacity per surface area. Its PDMS coating provided an 40-fold enhancement of low-pressure NH3 adsorption capacity and hydrophobicity.

Cited by 41 publications

References 39 publications

Downsizing of Block Polymer-Templated Nanopores to One Nanometer via Hyper-Cross-Linking of High χ–Low N Precursors

Downsizing of Block Polymer-Templated Nanopores to One Nanometer via Hyper-Cross-Linking of High χ–Low N Precursors

Emerging Porous Materials and Their Composites for NH₃ Gas Removal

Solvent‐Induced Flower‐ and Cudgel‐Shaped Porous Organic Polymers: Effective Supports of Palladium Nanoparticles for Dehalogenation in Net Water

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PDMS-coated hypercrosslinked porous organic polymers modified via double postsynthetic acidifications for ammonia capture

Abstract: Double postsynthetic acidifications of a hypercrosslinked polymer afforded record high NH3 adsorption capacity per surface area. Its PDMS coating provided an 40-fold enhancement of low-pressure NH3 adsorption capacity and hydrophobicity.

Cited by 41 publications

References 39 publications

Downsizing of Block Polymer-Templated Nanopores to One Nanometer via Hyper-Cross-Linking of High χ–Low N Precursors

Downsizing of Block Polymer-Templated Nanopores to One Nanometer via Hyper-Cross-Linking of High χ–Low N Precursors

Emerging Porous Materials and Their Composites for NH3 Gas Removal

Solvent‐Induced Flower‐ and Cudgel‐Shaped Porous Organic Polymers: Effective Supports of Palladium Nanoparticles for Dehalogenation in Net Water

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Product

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Emerging Porous Materials and Their Composites for NH₃ Gas Removal