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Covalent organic framework (COF) aerogels arehierarchically porous polymeric materials with ultrahigh specific surface area, making them attractive for wide applications such as molecular capture, adsorption, and catalysis. Previous COF aerogel studies have focused on varying their chemical structures and linkage chemistries to fine-tune material properties and functionality, most of which have reported relatively unsatisfying performance (e.g., poor mechanical strength and strain tolerance). This study describes the synthesis and characterization of COF nanocomposite aerogels, whose material properties and functionality are effectively engineered through the incorporation of reinforcing fillers/binders or functional additives. Boron nitride (BN) fillers, cross-linked poly(acrylic acid) (XPAA) binders, and gold nanoparticles (AuNps) are incorporated into 1,3,5-tris(aminophenyl)benzene-terephthaldehyde (TAPB-PDA) COF aerogel matrices to form homogeneous nanocomposite aerogels with enhanced mechanical properties and unique photothermal conversion capabilities. Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy results confirm the successful filler/additive inclusion into the final COF nanocomposite aerogels. Specifically, BN filler loading at ∼17 wt % relative to final COF mass doubles COF aerogel’s Young’s modulus from 11 to 22 kPa according to mechanical compression tests, with only ∼10% reduction in COF’s accessible mesopores’ surface area according to nitrogen porosimeter analyses. Meanwhile, incorporating ∼7 wt % XPAA relative to final COF mass improves the Young’s modulus to 21 kPa, while increasing the aerogel’s yield strain from 10 to 65% strain, although this leads to a ∼35% reduction in COF’s accessible mesopores’ surface area. Furthermore, photothermal AuNps are incorporated to form functional COF nanocomposite aerogels, whose overall temperature increases by 5.5 °C after 1 sun (AM1.5G, 1000 W m−2) irradiation. Overall, this study demonstrates potential routes to fabricate hierarchically porous COF nanocomposite aerogels with high specific surface area, robust mechanical stability, and unique photothermal functionality, which hold promises for applications in adsorption separation, gas storage, and photocatalysis. 

Microporous two-dimensional covalent organic framework (2D COF) membranes offer promise for gas separation applications, but their gas transport mechanism remains unclear. In this study, a TpHz 2D COF membrane supported on a macroporous nylon substrate is prepared by substrate-assisted interfacial polymerization under mild conditions. The formation of a continuous and dense thin (∼300 nm thick) TpHz layer is confirmed by scanning electron microscopy and Fourier transform infrared spectroscopy. Characterization by X-ray diffraction, grazing incidence wide-angle X-ray scattering, and N2 porosimetry qualitatively reveals the microstructures of the supported TpHz membranes, i.e., they comprise partially oriented 2D COF lamellar crystallites with moderate crystallinity in an eclipsed (AA) stacking geometry, centering the effective membrane pore size distribution at ∼1.1 nm. Single gas permeation data show that the transport of common molecular gases, including H2, He, CH4, N2, and CO2, through the synthesized TpHz membranes follows the Knudsen transport mechanism, where single gas permeance decreases with an increasing molecular weight and permeation temperature. Binary gas separation results show that in the equimolar CO2/N2 mixture, the presence of the CO2 surface flow slightly hinders the N2 flow at room temperature due to the reduced membrane channel size by the adsorbed CO2 gas layer on TpHz’s pore wall. In contrast, permeation of the equimolar CH4/N2 binary mixture does not exhibit a discernible surface flow of both gases due to their much lower gas uptake on TpHz, and their transport mechanism follows Knudsen-like behavior. 

Abstract Graphene-based electrodes have been extensively investigated for supercapacitor applications. However, their ion diffusion efficiency is often hindered by the graphene restacking phenomenon. Even though holey graphene is fabricated to address this issue by providing ion transport channels, those channels could still be blocked by densely stacked graphene nanosheets. To tackle this challenge, this research aims at improving the ion diffusion efficiency of microwave-synthesized holey graphene films by tuning the water interlayer spacer towards the improved supercapacitor performance. By controlling the vacuum filtration during graphene-based electrode fabrication, we obtain dry films with dense packing and wet films with sparse packing. The SEM images reveal that 20 times larger interlayer distance is constructed in the wet film compared to that in the dry counterpart. The holey graphene wet film delivers a specific capacitance of 239 F/g, ~82% enhancement over the dry film (131 F/g). By an integrated experimental and computational study, we quantitatively show that the interlayer spacing in combination with the nanoholes in the basal plane dominates the ion diffusion rate in holey graphene-based electrodes. Our study concludes that novel hierarchical structures should be further considered even in holey graphene thin films to fully exploit the superior advantages of graphene-based supercapacitors. 

Thiol-acrylate photoresin containing dynamic disulfide bonds undergoes wavelength-selective photopolymerization under greenvs.UV light to produce a degradable step-growth networkvs.permanent chain-growth network. 

Chain orientation, a natural consequence of polymer film processing, often leads to enhanced mechanical properties parallel to the machine extrusion direction (MD), while leaving the properties in the transverse direction (TD) unaffected or diminished, as compared to the unoriented material. Here, we report that mixing poly(ethylene oxide)-block-poly(butylene oxide) (PEO-PBO) diblock copolymer that forms dispersed particles in an amorphous polylactide (PLA) matrix produces uniaxially stretched blend films with enhanced toughness in both the MD and TD. Small-angle X-ray scattering experiments and visual observations revealed that the dominant deformation mechanism for blend films transitions from crazing to shear yielding in the MD as the stretching ratio increases, while crazing is the primary deformation mechanism in the TD at all stretching ratios investigated. As the films age at room temperature, crazing becomes more prevalent in the MD without compromising the improved toughness. The stretched blend films were susceptible to some degree of mechanical aging in the TD but remained fivefold tougher than stretched neat PLA films for up to 150 days. This work presents a feasible route to produce uniaxially stretched PEO–PBO/PLA films that are mechanically tough, which provides a more sustainable plastic alternative.