Multifunctional Super-Hydrophilic MXene/Biomass Composite Aerogel Evaporator for Efficient Solar-Driven Desalination and Wastewater Treatment.

Solar-driven interfacial evaporation is recognized as a sustainable and effective strategy for desalination to mitigate the freshwater scarcity issue. Nevertheless, the challenges of oil contamination, salt accumulation, and poor long-term stability of the solar desalination process limit its applications. Herein, a 3D biomass-based multifunctional solar aerogel evaporator is developed for water production with fabricated chitosan/lignin (CSL) aerogel as the skeleton, encapsulated with carbonized lignin (CL) particles and Ti3C2TiX (MXene) nanosheets as light-absorbing materials. Benefitting from its super-hydrophilic wettability, interconnected macropore structure, and high broadband light absorption (ca. 95.50%), the prepared CSL-C@MXene-20 mg evaporator exhibited a high and stable water evaporation flux of 2.351 kg m-2 h-1 with an energy conversion efficiency of 88.22% under 1 Sun (1 kW m-2) illumination. The CSL-C@MXene-20 mg evaporator performed excellent salt tolerance and long-term solar vapor generation in a 3.5 wt.% NaCl solution. Also, its super-hydrophilicity and oleophobicity resulted in superior salt resistance and anti-fouling performance in high salinity brine (20 wt.% NaCl) and oily wastewater. This work offers new insight into the manufacture of porous and eco-friendly biomass-based photothermal aerogels for advanced solar-powered seawater desalination and wastewater purification.

Tannin-Assisted Synthesis of Nanocomposites Loaded with Silver Nanoparticles and Their Multifunctional Applications.

Nanocomposites have been widely used in many important areas due to their particular physical/chemical properties; however, just though a simple technology, endowing multiple functions into a single nanomaterial for realizing their multifunctional applications is still a challenge. Here, we report a robust method for the facile synthesis of Ag-based multifunctional nanocomposites via using tannin-coated phenol-formaldehyde resin nanospheres (TA-PFRN) as silver nanoparticle (Ag NP) carriers. The thickness of the tannin coating is readily tuned from 50 to 320 nm by regulating the concentration of tannin added. Under the optimal conditions, the TA-PFRN has a 23.8 wt % of Ag NPs loading capacity with only 17.2 nm Ag NP layers. Consequently, the novel TA-PFRN@Ag nanocomposites possess multiple functions and integrated characteristics. As catalysts, the catalytic efficiency of TA-PFRN@Ag is nearly 6 times higher than that of the PFRN@Ag. As highly effective free radical initiators, TA-PFRN@Ag nanocomposites can trigger ultrafast acrylic acid (AA)/acrylamide (AM) polymerization at room temperature (in only a few minutes). As nano-reinforced fillers, the addition of 0.04 wt % nanocomposites can improve the tensile strength of PVA film from 60 to 153.2 MPa. In addition, the nanocomposites can also serve as antibacterial agents, efficiently inhibiting the growth of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus); as antiultraviolet agents, the presence of TA-PFRN@Ag nanocomposites endows the film/hydrogel materials excellent ultraviolet (UV) shielding. This work provides a novel strategy for the green synthesis of Ag-based multifunctional nanocomposites that show promising applications in catalysis, nanomaterials, and biomedicine.

Integration of renewable deep eutectic solvents with engineered biomass to achieve a closed-loop biorefinery.

Despite the enormous potential shown by recent biorefineries, the current bioeconomy still encounters multifaceted challenges. To develop a sustainable biorefinery in the future, multidisciplinary research will be essential to tackle technical difficulties. Herein, we leveraged a known plant genetic engineering approach that results in aldehyde-rich lignin via down-regulation of cinnamyl alcohol dehydrogenase (CAD) and disruption of monolignol biosynthesis. We also report on renewable deep eutectic solvents (DESs) synthesized from phenolic aldehydes that can be obtained from CAD mutant biomass. The transgenic Arabidopsis thaliana CAD mutant was pretreated with the DESs and showed a twofold increase in the yield of fermentable sugars compared with wild type (WT) upon enzymatic saccharification. Integrated use of low-recalcitrance engineered biomass, characterized by its aldehyde-type lignin subunits, in combination with a DES-based pretreatment, was found to be an effective approach for producing a high yield of sugars typically used for cellulosic biofuels and biobased chemicals. This study demonstrates that integration of renewable DES with plant genetic engineering is a promising strategy in developing a closed-loop process.

PdWND3A, a wood-associated NAC domain-containing protein, affects lignin biosynthesis and composition in Populus.

BACKGROUND: Plant secondary cell wall is a renewable feedstock for biofuels and biomaterials production. Arabidopsis VASCULAR-RELATED NAC DOMAIN (VND) has been demonstrated to be a key transcription factor regulating secondary cell wall biosynthesis. However, less is known about its role in the woody species. RESULTS: Here we report the functional characterization of Populus deltoides WOOD-ASSOCIATED NAC DOMAIN protein 3 (PdWND3A), a sequence homolog of Arabidopsis VND4 and VND5 that are members of transcription factor networks regulating secondary cell wall biosynthesis. PdWND3A was expressed at higher level in the xylem than in other tissues. The stem tissues of transgenic P. deltoides overexpressing PdWND3A (OXPdWND3A) contained more vessel cells than that of wild-type plants. Furthermore, lignin content and lignin monomer syringyl and guaiacyl (S/G) ratio were higher in OXPdWND3A transgenic plants than in wild-type plants. Consistent with these observations, the expression of FERULATE 5-HYDROXYLASE1 (F5H1), encoding an enzyme involved in the biosynthesis of sinapyl alcohol (S unit monolignol), was elevated in OXPdWND3A transgenic plants. Saccharification analysis indicated that the rate of sugar release was reduced in the transgenic plants. In addition, OXPdWND3A transgenic plants produced lower amounts of biomass than wild-type plants. CONCLUSIONS: PdWND3A affects lignin biosynthesis and composition and negatively impacts sugar release and biomass production.

Front-end recovery of protein from lignocellulosic biomass and its effects on chemical pretreatment and enzymatic saccharification.

Front-end protein recovery from biomass at different maturities, and its effects on chemical pretreatment and enzyme hydrolysis of partially deproteinized fiber were investigated. The protein recovery from alfalfa and switchgrass biomass using sodium dodecyl sulfate and potassium hydroxide treatments was ~50-65 % of initial biomass protein. When hot water was used as extraction media, the protein recovery was 52.9 and 43.7 % of total protein in switchgrass and alfalfa, respectively. For any treatment, relative protein recovery was higher from switchgrass than from alfalfa. Only approximately half the total protein was recovered from relatively mature (early fall) biomass compared with midsummer harvested biomass. When protein was recovered partially using sodium dodecyl sulfate or potassium hydroxide, and leftover fiber pretreated, aqueous ammonia pretreatment removed 58.5-60.1 % of lignin and retained more cellulose in the fiber compared with acid pretreatment (nearly no lignin removal). Protein removal was helpful in the enzyme digestibility of fibers. Delignification of ammonia pretreated partially deproteinized alfalfa fiber was in the range of 34.4-45 %, while dilute sulfuric acid did not remove lignin effectively. Overall, the higher delignification and enzyme digestibilities were observed in aqueous ammonia pretreated partially deproteinized alfalfa fibers regardless of biomass type.

Photoelectrochemical approaches for the conversion of lignin at room temperature.

The selective cleavage of C-C/C-O linkages represents a key step toward achieving the chemical conversion of biomass to targeted value-added chemical products under ambient conditions. Using photoelectrosynthetic solar cells is a promising method to address the energy intensive depolymerization of lignin for the production of biofuels and valuable chemicals. This feature article gives an in-depth overview of recent progress using dye-sensitized photoelectrosynthetic solar cells (DSPECs) to initiate the cleavage of C-C/C-O bonds in lignin and related model compounds. This approach takes advantage of N-oxyl mediated catalysis in organic electrolytes and presents a promising direction for the sustainable production of chemicals currently derived from fossil fuels.

"Rigid-Flexible" Anisotropic Biomass-Derived Aerogels with Superior Mechanical Properties for Oil Recovery and Thermal Insulation.

Aerogels with low density, high mechanical strength, and excellent elasticity have a wide potential for applications in wastewater treatment, thermal management, and sensors. However, the fabrication of such aerogels from biomass materials required complex preparation processes. Herein, a sustainable and facile strategy was reported to construct lignin/cellulose aerogels (LCMA) with three-dimensional interconnected structures by introducing homologous lignin with a polyphenyl propane structure as a structural enhancer through a top-down directional freezing approach, prompting a 2036% enhancement in compressive modulus and an 8-12-fold increase in oil absorption capacity. In addition, the hydrophobic aerogels with superelasticity were achieved by combining the aligned polygon-like structure and flexible silane chains, which exhibited remarkable compressional fatigue resistance and superhydrophobicity (WCA = 168°). Attributed to its unique pore design and surface morphology control, the prepared aerogel exhibited excellent performance in immiscible oil-water separation and water-in-oil emulsion separation. Due to the ultra-low density (8.3 mg·cm-3) as well as high porosity (98.87%), the obtained aerogel showed a low thermal conductivity (0.02565 ± 0.0024 W·m-1·K-1), demonstrating a potential in insulation applications. The synthetic strategy and sustainability concept presented in this work could provide guidance for the preparation of advanced biomass-based aerogels with unique properties for a wide range of applications.

Poly(3-hydroxybuyrate) production from industrial hemp waste pretreated with a chemical-free hydrothermal process.

In this study, a mild two-stage hydrothermal pretreatment was employed to optimally valorize industrial hemp (Cannabis sativa sp.) fibrous waste into sugars for Poly(3-hydroxybuyrate) (PHB) production using recombinant Escherichia coli LSBJ. Biomass was pretreated using hot water at 160, 180, and 200 °C for 5 and 10 min (15% solids), followed by disk refining. The sugar yields during enzymatic hydrolysis were found to improve with increasing temperature and the yields for hot water-disk refining pretreatment (HWDM) were higher compared to only hot water pretreatment at all conditions. The maximum glucose (56 g/L) and cellulose conversion (92%) were achieved for HWDM at 200 °C for 10 min. The hydrolysate obtained was fermented at a sugar concentration of 20 g/L. The PHB inclusion and concentration of 48% and 1.8 g/L, respectively, were similar to those from pure sugars. A pH-controlled fermentation resulted in a near bi-fold increase in PHB yield (3.46 g/L).

Review of chemical pretreatment of lignocellulosic biomass using low-liquid and low-chemical catalysts for effective bioconversion.

Chemical pretreatment of lignocellulosic biomass (LCB) is essential for effective biological conversion in subsequent steps to produce biofuels or biochemicals. For effective pretreatment, high lignin content and its recalcitrant nature of LCB are major factors influencing bioconversion, especially lignin is known to be effectively solubilized by alkaline, organic, and deep eutectic solvents, ionic liquids, while hemicellulose is effectively dissolved by various acid catalysts and organic solvents. Depending on the pretreatment method/catalyst used, different pretreatment process scheme should be applied with different amounts of catalyst and water inputs to achieve a satisfactory effect. In addition, the amount of processing water required in the following processes such as washing, catalyst recovery, and conditioning after pretreatment is critical factor for scale-up (commercialization). In this review, the amount of catalyst and/or water used, and the effect of pretreatment, properties of the products, and recovery of liquid are also discussed.

Applications of biomass-derived solvents in biomass pretreatment - Strategies, challenges, and prospects.

Biomass pretreatment is considered a key step in the 2nd generation biofuel production from lignocellulosic biomass. Research on conventional biomass pretreatment solvents has mainly been focused on carbohydrate conversion efficiency, while their hazardousness and/or carbon intensity were not comprehensively considered. Recent sustainability issues request further consideration for eco-friendly and sustainable alternatives like biomass-derived solvents. Carbohydrate and lignin-derived solvents have been proposed and investigated as green alternatives in many biomass processes. In this review, the applications of different types of biomass pretreatment solvents, including organic, ionic liquid, and deep eutectic solvents, are thoroughly discussed. The role of water as a co-solvent in these pretreatment processes is also reviewed. Finally, current research challenges and prospects of utilizing biomass-derived pretreatment solvents for pretreatment are discussed. Given bioethanol's market potential and increasing public awareness about environmental concerns, it will be a priority adopting sustainable and green biomass pretreatment solvents in biorefinery.

Novel candidate genes for lignin structure identified through genome-wide association study of naturally varying Populus trichocarpa.

Populus is a promising lignocellulosic feedstock for biofuels and bioproducts. However, the cell wall biopolymer lignin is a major barrier in conversion of biomass to biofuels. To investigate the variability and underlying genetic basis of the complex structure of lignin, a population of 409 three-year-old, naturally varying Populus trichocarpa genotypes were characterized by heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR). A subsequent genome-wide association study (GWAS) was conducted using approximately 8.3 million single nucleotide polymorphisms (SNPs), which identified 756 genes that were significantly associated (-log10(p-value)>6) with at least one lignin phenotype. Several promising candidate genes were identified, many of which have not previously been reported to be associated with lignin or cell wall biosynthesis. These results provide a resource for gaining insights into the molecular mechanisms of lignin biosynthesis and new targets for future genetic improvement in poplar.

Opportunities and challenges for flow-through hydrothermal pretreatment in advanced biorefineries.

Hydrothermal pretreatment (HTP) using only water offers great potential to reduce the overall cost of the bioconversion process. However, traditional HTP performed in a batch has limitations in removing lignin and often needs to be performed under severe conditions to achieve reasonable pretreatment effects. Lignin left in the pretreated residue at these conditions is also highly condensed, thus possessing an even more adverse impact on the hydrolysis process, which requires high enzyme loadings. To address these technical challenges, HTP performed in a flow-through configuration was developed to simultaneously achieve near-complete hemicellulose recovery, high lignin removal and high sugar release. Despite facing challenges such as potentially large water usage, flow-through HTP still represents one of the most cost-effective and eco-friendly pretreatment methods. This review mainly covers the latest cutting-edge innovations of flow-through HTP along with structural and compositional changes of cellulose, hemicellulose, and lignin before and after pretreatment.

A combination of deep eutectic solvent and ethanol pretreatment for synergistic delignification and enhanced enzymatic hydrolysis for biorefinary process.

A novel pretreatment system containing deep eutectic solvents and ethanol (DES-E) for synergistic carbohydrate conversion and delignification was reported in this study. The DES-E pretreatment resulted in an enhanced glucose yield compared to individual DES and ethanol pretreatment for the three tested biomass, including Broussonetia papyrifera, corn stover and pine. To further explore the delignification mechanism, the solubilized lignin and residual lignin from Broussonetia papyrifera was recovered and extracted, then thoroughly characterized. The highest total OH content was found in the DES-E solubilized lignin, which could be used as antioxidant. The presence of ethanol in pretreatment liquor could protect the ß-O-4 substructure from breakage and reduce lignin condensation, which favors the subsequent enzymatic hydrolysis. Comparable glucose yield and delignification performance was achieved by recycled DES. DES-E pretreatment offers a promising method for lignin isolation and cellulose digestibility improvement simultaneously.

A review on physico-chemical delignification as a pretreatment of lignocellulosic biomass for enhanced bioconversion.

Effective pretreatment of lignocellulosic biomass (LCB) is one of the most important steps in biorefinery, ensuring the quality and commercial viability of the overall bioprocess. Lignin recalcitrance in LCB is a major bottleneck in biological conversion as the polymerization of lignin with hemicellulose hinders enzyme accessibility and further bioconversion to fuels and chemicals. Therefore, there is a need to delignify LCB to ease further bioprocessing. The efficiency of delignification, quality and quantity of the desired products, and generation of inhibitors depend upon the type of pretreatment employed. This review summarizes different single and integrated physicochemical pretreatments for delignification. Additionally, conditions required for effective delignification and the advantages and drawbacks of each method were evaluated. Advances in overcoming the recalcitrance of residual lignin to saccharification and the methods to recover lignin after delignification are also discussed. Efficient lignin recovery and valorization strategies provide an avenue for the sustainable lignocellulose biorefinery.

Lignin-silver triggered multifunctional conductive hydrogels for skinlike sensor applications.

Conductive hydrogels have attracted tremendous attention as a novel generation of wearable devices and body monitoring due to their great stretchability and high flexibility. Here, a multifunctional cellulose nanocrystal @sodium lignosulfonate-silver-poly(acrylamide) nanocomposite hydrogel was prepared by radical polymerization within only a few minutes. This polymerization rapidly occurred by lignosulfonate-silver (Ls-Ag) dynamic catalysis that efficiently activated ammonium persulfate (APS) to initiate the free-radical polymerization. In particular, the hydrogel exhibited excellent tensile strength (406 kPa), ultrahigh stretchability (1880 %), self-recovery, and fatigue resistance. Furthermore, due to the inclusion of Ls-Ag metal ion nanocomposite in the hydrogels, the composite hydrogel presented repeated adhesion to various objects, excellent conductivity (σ âˆ¼ 9.5 mS cm-1), remarkable UV resistance (100 % shielding of the UV spectral region), and high antibacterial activity (above 98 %), which enabled the hydrogel to be applied to epidermal sensors. In addition, the high-sensitivity (gauge factor of 2.46) sensor constructed of the hydrogel monitored the large and subtle movements of the human body and was used as a biological electrode to collect human electromyography and electrocardiographic signals. This work provided a novel strategy for the high-value utilization of lignin, which had potential application prospects in many fields such as wearable bioelectrodes.

Enhanced Photocatalytic Alcohol Oxidation at the Interface of RuC-Coated TiO2 Nanorod Arrays.

Visible-light-driven organic oxidations carried out under mild conditions offer a sustainable approach to performing chemical transformations important to the chemical industry. This work reports an efficient photocatalytic benzyl alcohol oxidation process using one-dimensional (1D) TiO2 nanorod (NR)-based photoanodes with surface-adsorbed ruthenium polypyridyl photocatalysts at room temperature. The photocatalyst bis(2,2'-bipyridine)(4,4'-dicarboxy-2,2'-bipyridine)Ru(II) (RuC) was covalently anchored onto TiO2 nanorod arrays grown on fluorine-doped tin oxide (FTO) electrode surfaces (FTO|t-TiO2|RuC, t = the thickness of TiO2 NR). Under aerobic conditions, the photophysical and photocatalytic properties of FTO|t-TiO2|RuC (t = 1, 2, or 3.5 µm) photoanodes were investigated in a solution containing a hydrogen atom transfer mediator (4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl, ACT) as cocatalyst. Dye-sensitized photoelectrochemical cells (DSPECs) using the FTO|t-TiO2|RuC (t = 1, 2, or 3.5 µm) photoanodes and ACT-containing electrolyte were investigated for carrying out photocatalytic oxidation of a lignin model compound containing a benzylic alcohol functional group. The best-performing anode surface, FTO|1-TiO2|RuC (shortest NR length), oxidized the 2° alcohol of the lignin model compound to the Cα-ketone form with a > 99% yield over a 4 h photocatalytic experiment with a Faradaic efficiency of 88%. The length of TiO2 NR arrays (TiO2 NRAs) on the FTO substrate influenced the photocatalytic performance with longer NRAs underperforming compared to the shorter arrays. The influence of the NR length is hypothesized to affect the homogeneity of the RuC coating and accessibility of the ACT mediator to the RuC-coated TiO2 surface. The efficient photocatalytic alcohol oxidation with visible light at room temperature as demonstrated in this study is important to the development of sustainable approaches for lignin depolymerization and biomass conversion.

Catalytic conversion of waste corrugated cardboard into lactic acid using lanthanide triflates.

The efficient strategy for waste conversion and resource recovery is of great interest in the sustainable bioeconomy context. This work reports on the catalytic upcycling of waste corrugated cardboard (WCC) into lactic acid using lanthanide triflates catalysts. WCC, a primary contributor to municipal solid wastes, has been viewed as a feedstock for producing a wide range of renewable products. Hydrothermal conversion of WCC was carried out in the presence of several lanthanide triflates. The reaction with erbium(III) triflate (Er(OTf)3) and ytterbium(III) triflate (Yb(OTf)3) resulted in high lactic acid yields, 65.5 and 64.3 mol%, respectively. In addition, various monomeric phenols were readily obtained as a co-product stream, opening up opportunities in waste management and resource recovery. Finally, technoeconomic analysis was conducted based on the experimental results, which suggests a significant economic benefit of chemocatalytic upcycling of WCC into lactic acid.

Utilization of guaiacol-based deep eutectic solvent for achieving a sustainable biorefinery.

This study proposed a renewable deep eutectic solvent (DES) pretreatment using lignin-derived guaiacol as the hydrogen bond donor. The DES showed excellent biomass fractionation efficiency after the incorporation of trace AlCl3 as the reinforcer, which removed 79.1 % lignin while preserving more than 90 % glucan. The pretreated bamboo exhibited 96.2 % glucan enzymatic hydrolysis yield at only 110 °C. The physicochemical properties of the pretreated solids were comprehensively investigated to explain how the DES fractionation overcame the biomass recalcitrance. The regenerated lignin from the DES pretreatment was also analyzed, which revealed that lignin ß-O-4 bond was significantly cleaved. This guaiacol-based DES could greatly contribute to establish a closed-loop biorefinery sequence with high lignin fractionation efficiency and great solvent recyclability.

Innovative production of lignin nanoparticles using deep eutectic solvents for multifunctional nanocomposites.

A green and simple lignin nanoparticles (LNPs) production strategy was developed using deep eutectic solvents (DES). The LNPs were formed with corncob alkali lignin by sequential DES dissolution and self-assembling process. Uniform size and spherical shape of LNPs were observed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential analyzer and gel permeation chromatography (GPC). Less than 100 nm of LNPs were formed, and these particles were preserved without significant size-increase or precipitation within 30 days. The nanocomposite films prepared by incorporating the LNPs into biodegradable poly(vinyl alcohol) (PVA) matrix display good mechanical properties (tensile strength of 82.5 MPa and breaking strain of 103.3%), excellent UV-blocking (100% shielding of the UV spectrum region), strong hydrophobicity (static contact angle of 117.0°) and relatively high thermal stability (the maximum thermal weight loss temperature increased by 40 °C). Overall, this study not only facilitates the advancement of lignin-based nanotechnology by DES but also paves the way for the PVA polymer composites as potential food and medical packaging materials.

Engineered Sorghum Bagasse Enables a Sustainable Biorefinery with p-Hydroxybenzoic Acid-Based Deep Eutectic Solvent.

Integrating multidisciplinary research in plant genetic engineering and renewable deep eutectic solvents (DESs) can facilitate a sustainable and economic biorefinery. Herein, we leveraged a plant genetic engineering approach to specifically incorporate C6 C1 monomers into the lignin structure. By expressing the bacterial ubiC gene in sorghum, p-hydroxybenzoic acid (PB)-rich lignin was incorporated into the plant cell wall while this monomer was completely absent in the lignin of the wild-type (WT) biomass. A DES was synthesized with choline chloride (ChCl) and PB and applied to the pretreatment of the PB-rich mutant biomass for a sustainable biorefinery. The release of fermentable sugars was significantly enhanced (∼190 % increase) compared to untreated biomass by the DES pretreatment. In particular, the glucose released from the pretreated mutant biomass was up to 12 % higher than that from the pretreated WT biomass. Lignin was effectively removed from the biomass with the preservation of more than half of the ß-Ο-4 linkages without condensed aromatic structures. Hydrogenolysis of the fractionated lignin was conducted to demonstrate the potential of phenolic compound production. In addition, a simple hydrothermal treatment could selectively extract PB from the same engineered lignin, showing a possible circular biorefinery. These results suggest that the combination of PB-based DES and engineered PB-rich biomass is a promising strategy to achieve a sustainable closed-loop biorefinery.