The utilization of sustainable resources provides a path to relieving the problem of dependence on fossil resources. In this context, biomass materials have become a feasible substitute for petroleum-based materials. The development of biomass materials is booming and advanced biomass materials with various functional properties are used in many fields including medicine, electrochemistry, and environmental science. In recent years, ionic liquids have been widely used in biomass pretreatments and processing owing to their “green” characteristics and adjustable physicochemical properties. Thus, the effects of ionic liquids in biomass materials generation require further study. This review summarizes the multiple roles of ionic liquids in promoting the synthesis and application of advanced biomass materials as solvents, structural components, and modifiers. Finally, a prospective approach is proposed for producing additional higher-quality possibilities between ionic liquids and advanced biomass materials.
Amino acids are important nitrogen-containing chemicals that have a variety of applications. Currently, fermentation is the widely employed method to produce amino acids; however, the products are mostly limited to natural amino acids in the L-configuration. Catalytic synthesis is an alternative approach for the synthesis of amino acids with different types and configurations, where the use of renewable biomass-based feedstocks is highly attractive. To date, several lignocellulose and triacylglycerol-derived intermediates, typically α-keto acids and α-hydroxyl acids, have been transformed into amino acids via the amination reaction in the presence of additional nitrogen sources (i.e., NH3·H2O). Making full use of inherent nitrogen in biomass (i.e., chitin and protein) to produce amino acids avoids the use of extra nitrogen sources and meets the requirements of green chemistry, which is attracting increasing attention. In this review, we summarize different chemical-catalytic systems for the transformation of biomass to amino acids. An outlook on the challenges and opportunities for more effective production of amino acids from biomass by catalytic methods is provided.
A multi-functional porous paper-based material was prepared from grass pulp by simple pore-forming and green cross-linking method. As a pore-forming agent, calcium citrate increased the porosity of the paper-based material from 30% to 69% while retaining the mechanical strength. The covalent cross-linking of citric acid between cellulose fibers improved both the wet strength and adsorption capacity. In addition, owing to the introduction of high-content carboxyl groups as well as the construction of hierarchical micro-nano structure, the underwater oil contact angle was up to 165°. The separation efficiency of the emulsified oil was 99.3%, and the water flux was up to 2020 L·m–2·h–1. The theoretical maximum adsorption capacities of cadmium ion, lead ion and methylene blue reached 136, 229 and 128.9 mg·g–1, respectively. The continuous purification of complex wastewater can be achieved by using paper-based materials combined with filtration technology. This work provides a simple, low cost and environmental approach for the treatment of complex wastewater containing insoluble oil, organic dyes, and heavy metal ions.
Herein, a Fe3+-loaded aminated polypropylene fiber has been reported as an efficient phosphate adsorbent. The remarkable phosphate removal ability of the fiber is due to Fe3+ immobilization, and it demonstrates a maximum adsorption capacity of 33.94 mg·P·g–1. Adsorption experiments showed that the fiber is applicable over a wide pH range from 2 to 9. Furthermore, the adsorption kinetics and isotherm data were consistent with the pseudo-second-order and Langmuir adsorption models, respectively. The adsorption equilibrium of the fiber for phosphate was reached within 60 min, indicating an efficient monolayer chemisorption process. Moreover, the adsorbent maintained prominent phosphate removal in the presence of competitive ions such as NO3– and Cl–, exhibiting high selectivity. More importantly, the fiber demonstrated excellent reusability (5 times) and low adsorption limit below 0.02 mg·P·g–1. In addition, the phosphate removal efficiency of the fiber can exceed 99% under continuous flow conditions. The adsorption mechanism was studied by X-ray photoelectron spectroscopy, showing that the adsorption of phosphate on the fiber mainly depended on the chemical adsorption of the modified Fe3+. Overall, this study proves that the fiber possesses many advantages for phosphate removal, including high adsorption efficiency, lower treatment limit, good recyclability, and environmental friendliness.
The discharge of large amounts of dye-containing wastewater seriously threats the environment. Adsorbents have been adopted to remove these dyes present in the wastewater. However, the high adsorption capacity, predominant pH-responsibility, and excellent recyclability are three challenges to the development of efficient adsorbents. The poly(acryloxyethyl trimethylammonium chloride)-graft-dialdehyde cellulose nanocrystals were synthesized in our work. Subsequently, the cationic dialdehyde cellulose nanocrystal cross-linked chitosan nanocomposite foam was fabricated via freeze-drying of the hydrogel. Under the optimal ratio of the cationic dialdehyde cellulose nanocrystal/chitosan (w/w) of 12/100, the resultant foam (Foam-12) possesses excellent absorption properties, such as high porosity, high content of active sites, strong acid resistance, and high amorphous region. Then, Foam-12 was applied as an eco-friendly adsorbent to remove acid red 134 (a representative of anionic dyes) from aqueous solutions. The maximum dye adsorption capacity of 1238.1 mg∙g‒1 is achieved under the conditions of 20 mg∙L‒1 adsorbents, 100 mg∙L‒1 dye, pH 3.5, 24 h, and 25 °C. The dominant adsorption mechanism for the anionic dye adsorption is electrostatic attraction, and Foam-12 can effectively adsorb acid red 134 at pH 2.5–5.5 and be desorbed at pH 8. Its easy recovery and good reusability are verified by the repeated acid adsorption–alkaline desorption experiments.
Polydopamine-functionalized nanosilica was synthesized using an inexpensive and easily obtainable raw material, mild reaction conditions, and simple operation. Subsequently, a flexible spacer arm was introduced by using dialdehyde starch as a cross-linking agent to bind with laccase. A high loading amount (77.8 mg∙g‒1) and activity retention (75.5%) could be achieved under the optimum immobilization conditions. Thermodynamic parameters showed that the immobilized laccase had a lower thermal deactivation rate constant and longer half-life. The enhancement of thermodynamic parameters indicated that the immobilized laccase had better thermal stability than free laccase. The residual activity of immobilized laccase remained at about 50.0% after 30 days, which was 4.0 times that of free laccase. Immobilized laccase demonstrated excellent removal of phenolic pollutants (2,4-dichlorophenol, bisphenol A, phenol, and 4-chlorophenol) and perfect reusability with 70% removal efficiency retention for 2,4-dichlorophenol after seven cycles. These results suggested that immobilized laccase possessed great reusability, improved thermal stability, and excellent storage stability. Organic–inorganic nanomaterials have a good application prospect for laccase immobilization, and the immobilized laccase of this work may provide a practical application for the removal of phenolic pollutants.
The zero-valent iron modified biochar materials are widely employed for heavy metals immobilization. However, these materials would be inevitably aged by natural forces after entering into the environment, while there are seldom studies reported the aging effects of zero-valent iron modified biochar. In this work, the hydrogen peroxide and hydrochloric acid solution were applied to simulate aging conditions of zero-valent iron modified biochar. According to the results, the adsorption capacity of copper(II) contaminants on biochar, zero-valent iron modified biochar-1, and zero-valent iron modified biochar-2 after aging was decreased by 15.36%, 22.65% and 23.26%, respectively. The surface interactions were assigned with chemisorption occurred on multi-molecular layers, which were proved by the pseudo-second-order and Langmuir models. After aging, the decreasing of capacity could be mainly attributed to the inhibition of ion-exchange and zero-valent iron oxidation. Moreover, the plant growth and soil leaching experiments also proved the effects of aging treatment, the zero-valent iron modified biochar reduced the inhibition of copper(II) bioavailability and increased the mobility of copper(II) after aging. All these results bridged the gaps between bio-adsorbents customization and their environmental behaviors during practical agro-industrial application.
A novel alginate/poly(acrylic acid/acrylamide) double-network hydrogel composite with silver nanoparticles was successfully fabricated using the sol–gel method. The presence of carboxyl and amide groups in the network structure provided abundant active sites for complexing silver ions, facilitating the in situ reduction and confinement of silver nanoparticles. In batch experiments, the optimal silver loading was 20%, and 5 mmol·L–1 of p-nitrophenol was completely degraded in 113 s with a rate constant value of 4.057 × 10−2 s–1. In the tap water system and simulated seawater system, the degradation time of p-nitrophenol at the same concentration was 261 and 276 s, respectively, with a conversion rate above 99%. In the fixed-bed experiment, the conversion rate remained above 74% after 3 h at a flowing rate of 7 mL·min–1. After 8 cycling tests, the conversion rate remained at 98.7%. Moreover, the catalyst exhibited outstanding performance in the degradation experiment of four typical organic dyes.
The industrial application of nano-photocatalysts in wastewater treatment has been severely restricted for a long time due to their difficult separation, poor reusability, and low efficiency. In this work, a facile strategy was proposed to enhance the photocatalytic activity and recovery performance of Ag@AgCl nanocatalysts. Biological veins (Bio-veins) with a unique 3D porous construction were used as carriers for the in-situ growth of Ag@AgCl nanoparticles. Scanning electron microscopy results showed that the Ag@AgCl nanoparticles were uniformly loaded on the surface and interior of the Bio-veins, and the size of the Ag@AgCl nanoparticles immobilized on the Bio-veins (50–300 nm) was significantly smaller than Ag@AgCl obtained by the co-precipitation method (1–3 μm). The Bio-veins played a vital role in the photocatalysis reaction system. The degradation efficiency of the Ag@AgCl/Bio-veins(CI4) was up to 3.50 times as high as pure Ag@AgCl. Furthermore, the composites also exhibited excellent recyclability and stability under both visible and solar light. This work provided a suitable strategy for nano-photocatalysts for practical application and may also offer new possibilities for the high-value utilization of biomass materials.
The casual discharge of dyes from industrial settings has seriously polluted global water systems. Owing to the abundance of biomass resources, preparing photocatalysts for photocatalytic degradation of dyes is significant; however, it still remains challenging. In this work, a cuprous oxide/copper oxide composite was interpenetrated onto carbon nanosheets of cellulose-based flexible carbon aerogels (Cu2O/CuO@CAx) via a simple freeze-drying-calcination method. The introduction of the carbon aerogel effectively prevents the aggregation of the cuprous oxide/copper oxide composite. In addition, Cu2O/CuO@CA0.2 has a larger specific surface area, stronger charge transfer capacity, and lower recombination rate of photogenerated carriers than copper oxide. Moreover, Cu2O/CuO@CA0.2 exhibited high photocatalytic activity in decomposing methylene blue, with a degradation rate reaching up to 99.09% in 60 min. The active oxidation species in the photocatalytic degradation process were systematically investigated by electron spin resonance characterization and poisoning experiments, among which singlet oxygen played a major role. In conclusion, this work provides an effective method for preparing photocatalysts using biomass resources in combination with different metal oxides. It also promotes the development of photocatalytic degradation of dyes.
Membrane technology for wastewater remediation has aroused wide interest owing to its unique properties and potential applications. However, it remains challenging to explore green, efficient and robust membrane material and technique for complex wastewater treatment. Herein, we proposed using a simple electrospinning and in situ seeding method to fabricate a lignin-based electrospun nanofiber membrane (LENM) decorated with photo-Fenton Ag@MIL-100(Fe) heterojunctions for efficient separation of oil/water emulsions and degradation of organic dye. Thanks to the embedded lignin in LENM, an ultrahigh MIL-100(Fe) loading (53 wt %) with good wettability and high porosity was obtained. As a result, the hybrid Ag@MIL-100(Fe)/LENM exhibited excellent oil/water emulsions separation efficiency (more than 97%) without a compromise of water flux. Moreover, the hybrid membrane showed an excellent dye removal with degradation of 99% methylene blue within 30 min under illumination, which is attributed to a synergy of dye adsorption/enrichment and photo-Fenton catalytic degradation from Ag@MIL-100(Fe). Therefore, the lignin-based photo-Fenton hybrid membrane can lay the foundation for the preparation and application of green, sustainable and versatile membrane materials and technologies for efficient complex wastewater remediation.
Volatile organic compounds have posed a serious threat to the environment and human health, which require urgent and effective removal. In recent years, the preparation of porous carbon from biomass waste for volatile organic compounds adsorption has attracted increasing attention as a very cost-effective and promising technology. In this study, porous carbon was synthesized from orange peel by urea-assisted hydrothermal carbonization and KOH activation. The role of typical components (cellulose, hemicellulose, and lignin) in pore development and volatile organic compounds adsorption was investigated. Among the three components, hemicellulose was the major contributor to high porosity and abundant micropores in porous carbon. Higher hemicellulose content led to more abundant –COOR, amine-N, and pyrrolic/pyridonic-N in the derived hydrochar, which were favorable for porosity formation during activation. In this case, the toluene adsorption capacity of the porous carbon improved from 382.8 to 485.3 mg·g–1. Unlike hemicellulose, cellulose reduced the >C=O, amine-N, and pyrrolic/pyridonic-N content of the hydrochar, which caused porosity deterioration and worse toluene adsorption performance. Lignin bestowed the hydrochar with slightly increased –COOR, pyrrolic/pyridonic-N, and graphitic-N, and reduced >C=O, resulting in comparatively poor porosity and more abundant micropores. In general, the obtained porous carbon possessed abundant micropores and high specific surface area, with the highest up to 2882 m2·g–1. This study can provide guidance for selecting suitable biomass waste to synthesize porous carbon with better porosity for efficient volatile organic compounds adsorption.
The shortage of freshwater has become a global challenge, and solar-driven interfacial evaporation for desalination is a promising way to alleviate the crisis. To develop highly efficient and environmentally friendly photothermal evaporator, the hydroxyethyl cellulose (HEC)/alkaline lignin (AL)/graphene oxide (GO) hydrogels (CLGs) with remarkable evaporative performance were successfully fabricated by a facile sol–gel method using biomass residues. The influence of AL content on the physicochemical properties of the evaporator was investigated. The increasing content of AL improves the mechanical properties, saturated water content and crosslink density of the hydrogels. The designed materials exhibit outstanding thermal insulation capacity (the thermal conductivity of less than 0.05 W·m–1·K–1) and high light absorption capacity of more than 97%. The solar evaporation efficiency and water evaporation rate of the HEC/64 wt % of AL/GO hydrogels (CLG4) achieve 92.1% and 2.55 kg·m–2·h–1 under 1 sun, respectively. The salt resistance test results reveal that the evaporation rate of the CLG4 can still reach 2.44 kg·m–2·h–1 in 3.5 wt % NaCl solution. The solar evaporation rate of the CLG4 can maintain in the range of 2.45–2.59 kg·m–2·h–1 in five cycles. This low-cost lignin-based photothermal evaporator offers a sustainable strategy for desalination.
The efficient utilization of natural lignin, which is the main by-product of the cellulose industry, is crucial for enhancing its economic value, alleviating the environmental burden, and improving ecological security. By taking advantage of the large sp2 hybrid domain of lignin and introducing amino functional groups, new lignin-derived carbon dots (SPN-CDs) with red fluorescence were successfully synthesized. Compared with green and blue fluorescent materials, red SPN-CDs have desirable anti-interference properties of short-wave background and exhibit superior luminescence stability. The SPN-CDs obtained exhibited sensitive and distinctive visible color with fluorescence-dual responses toward hypochlorite. Considering this feature, a portable, low-cost, and sensitive fluorescence sensing paper with a low limit of detection of 0.249 μmol∙L–1 was fabricated using the SPN-CDs for hypochlorite detection. Furthermore, a new type of visible-light and fluorescence dual-channel information encryption platform was constructed. Low-concentration hypochlorite can be employed as an accessible and efficient information encryption/decryption stimulus, as well as an information “eraser”, facilitating a safe and diversified transmission and convenient decryption of information. This work opens new avenues for high-value-added applications of lignin-based fluorescent materials.
Lignin exhibits antioxidative and various other biological properties. However, its neuroprotection capability has rarely been studied. In this study, three types of lignin with different structures were prepared from grape seeds by using different isolation techniques. The antioxidative and neuroprotective effects of the lignin fractions were evaluated with the apoptosis model of murine neuroectodermal (NE-4C) neural stem cells stimulated with bisphenol AF. The results demonstrated that the half maximal inhibitory concentration for scavenging 2,2-diphenyl-1-picrylhydrazyl with water-soluble lignin (L-W, 58.19 μg·mL–1) was lower than those of lignin in the autohydrolyzed residue of grape seeds (84.27 μg·mL–1) and original lignin in grape seeds (99.44 μg·mL–1). BPAF exposure had negative effects on the reactive oxygen species, malondialdehyde content, and superoxide dismutase and glutathione peroxidase activities in NE-4C cells, which can be reversed by using the prepared lignin to reduce oxidative stress. An immunofluorescence assay demonstrated that grape seed lignin induced protective effects on BPAF-injured NE-4C cells via the nuclear factor erythroid 2-related Factor 2 pathway. In addition, correlational analyses showed that lignin (L-W) with lower molecular weights and noncondensed phenolic hydroxyl group content and higher contents of COOH groups effectively prevented cell apoptosis, scavenged reactive oxygen species, and ensured protection from nerve injury. This study demonstrated that grape seed lignin can be used as a neuroprotective agent and serves as a demonstration of active lignin production from grape seed waste.
