A superelastic aerogel with fast shape recovery performance from large compressive strain is highly desired for numerous applications such as thermal insulation in clothing, high-sensitive sensors, and oil contaminant removal. Fabrication of superelastic cellulose nanofibrils (CNF) aerogels is challenging as the CNF can assemble into non-elastic sheet-like cell walls. Here, a dual ice-templating assembly (DITA) strategy is proposed that can control the assembly of CNF into sub-micrometer fibers by extremely low temperature freezing (-196 °C), which can further assemble into an elastic aerogel with interconnected sub-micron fibers by freezer freezing (−20 °C) and freeze drying. The CNF aerogel from the DITA process demonstrates isotropic superelastic behavior that can recover from over 80% compressive strain along both longitudinal and cross-sectional directions, even in an extremely cold liquid nitrogen environment. The elastic CNF aerogel can be easily modified by chemical vapor deposition of organosilane, demonstrating superhydrophobicity (164° water contact angle), high liquid absorption (489 g g −1 of chloroform absorption capacity), self-cleaning, thermal insulating (0.023 W (mK) −1 ), and infrared shielding properties. This new DITA strategy provides a facile design of superelastic aerogels from bio-based nanomaterials, and the derived high performance multifunctional elastic aerogel is expected to be useful for a wide-range of applications.

BackgroundThermochemical pretreatment of lignocellulose is crucial to bioconversion in the fields of biorefinery and biofuels. However, the enzyme inhibitors in pretreatment hydrolysate make solid substrate washing and hydrolysate detoxification indispensable prior to enzymatic hydrolysis. Sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL) is a relatively new process, but has demonstrated robust performance for sugar and biofuel production from woody biomass in terms of yield and energy efficiency. This study demonstrated the advantage of SPORL pretreatment whereby the presentation of lignosulfonate (LS) renders the hydrolysate non-inhibitory to cellulase (Cel) due to the formation of lignosulfonate-cellulase complexes (LCCs) which can mediate the Cel adsorption between lignin and cellulose, contrary to the conventional belief that pretreatment hydrolysate inhibits the enzymatic hydrolysis unless detoxified.ResultsParticular emphasis was made on the formation mechanisms and stability phase of LCCs, the electrostatic interaction between LCCs and lignin, and the redistributed Cel adsorption between lignin and cellulose. The study found that LS, the byproduct of SPORL pretreatment, behaves as a polyelectrolyte to form LCCs with Cel by associating to the oppositely charged groups of protein. Compared to Cel, the zeta potential of LCCs is more negative and adjustable by altering the molar ratio of LS to Cel, and thereby LCCs have the ability to mitigate the nonproductive binding of Cel to lignin because of the enlarged electrostatic repulsion. Experimental results showed that the benefit from the reduced nonproductive binding outweighed the detrimental effects from the inhibitors in pretreatment hydrolysate. Specifically, the glucan conversions of solid substrate from poplar and lodgepole pine were greatly elevated by 25.9% and 31.8%, respectively, with the complete addition of the corresponding hydrolysate. This contradicts the well-acknowledged concept in the fields of biofuels and biorefinery that the pretreatment hydrolysate is inhibitory to enzymes.ConclusionsThe results reported in this study also suggest significant advantages of SPORL pretreatment in terms of water consumption and process integration, that is, it should abolish the steps of solid substrate washing and pretreatment hydrolysate detoxification for direct simultaneous saccharification and combined fermentation (SSCombF) of enzymatic and pretreatment hydrolysate, thereby facilitating bioprocess consolidation. Furthermore, this study not only has practical significance to biorefinery and bioenergy, but it also provides scientific importance to the molecular design of composite enzyme-polyelectrolyte systems, such as immobilized enzymes and enzyme activators, as well as to the design of enzyme separation processes using water-soluble polyelectrolytes.

Because of the prevailing environment and energy challenges, there has been a growing interest in biobased materials for thermal insulation application. Although cellulose aerogel has been considered as an excellent thermal insulating material, its thermal conductivity is generally negatively affected by the interconnected internal pores. Herein, it is demonstrated that a cellulose nanofibril (CNF)/emulsion composite aerogel with quasiclosed internal pores can be facilely fabricated by Pickering emulsion templating and solvent exchange methods. The CNFstabilized oil-in-water Pickering emulsion (with an average diameter of 1.3 μm) can be converted into quasi-closed pores by sequential solvent exchange to acetone and tert-butanol (TBA), followed by freeze-drying from TBA to suppress the formation of large ice crystals. The presence of quasi-closed pores from emulsion templating is verified by both confocal microscopy and scanning electron microscopy images and is confirmed to reduce thermal conductivity to as low as 15.5 mW/(m K). Compared to the CNF aerogel, increasing emulsion content can lead to better volume retention with significantly reduced density (11.4 mg/cm 3 ), increased mesoporosity, and enhanced specific modulus (18.2 kPa/(mg/cm 3 )) and specific yield strength (1.6 kPa/(mg/cm 3 )). In addition, the CNF/emulsion composite aerogel also demonstrates superb flexibility and infrared shielding performance.

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