Fabrication of lignosulfonate-derived porous carbon via pH-tunable self-assembly strategy for efficient atrazine removal.

Herein, a straightforward protocol was developed for the one-pot synthesis of N-doped lignosulfonate-derived carbons (NLDCs) with a tunable porous structure using natural amino acids-templated self-assembly strategy. Specifically, histidine was employed as a template reagent, leading to the preparation of 10-NLDC-21 with remarkable characteristics, including the large specific surface area (SBET = 1844.5 m2/g), pore volume (Vmes = 1.22 cm3/g) and efficient adsorption for atrazine (ATZ) removal. The adsorption behavior of ATZ by NLDCs followed the Langmuir and pseudo-second-order models, suggesting a monolayer chemisorption nature of ATZ adsorption with the maximum adsorption capacity reached up to 265.77 mg/g. Furthermore, NLDCs exhibited excellent environmental adaptability and recycling performance. The robust affinity could be attributed to multi-interactions including pore filling, electrostatic attraction, hydrogen bonding and π-π stacking between the adsorbents and ATZ molecules. This approach offers a practical method for exploring innovative bio-carbon materials for sewage treatment.

Preparation, characterization, and application of waterborne lignin-based epoxy resin as eco-friendly wood adhesive.

A series of novel waterborne lignin-based epoxy resin emulsions (WLEPs) were successfully synthesized, and then the WLEPs were cured with polyamide (PA) to give formaldehyde-free wood adhesives with high-performance. The chemical structures and properties of WLEP emulsions were determined. The effects of the emulsifiers on thermal and mechanical properties of the adhesives were investigated, and the potential application of WLEPs in the formulation of plywood were also evaluated. The results demonstrated that the WLEP dispersions presented excellent storage stability (>180 days) with their viscosities range from 110 mPa·s to 470 mPa·s and particle sizes in the range of 321-696 nm, which were beneficial for the fluidity and permeability of the wood adhesives. Furthermore, the thermal and mechanical properties of adhesives could be tuned effectively by controlling the length of PEG chains. The adhesive bearing PEG 6000 exhibited the highest tensile strength of 24.0 MPa and Young's modulus of 1439 MPa. Notably, the plywood prepared with the resulting adhesives displayed good bonding performance, especially water resistance, which were much higher than the national standard requirement for exterior-grade plywood type I. These results indicated that the WLEPs could be used as sustainable alternatives for traditional formaldehyde-based wood adhesives in practical applications.

Natural phenol-inspired porous polymers for efficient removal of tetracycline: Experimental and engineering analysis.

Efficient and feasible removal of trace antibiotics from wastewater is extremely important due to its environmental persistence, bioaccumulation, and toxicity, but still remains a huge challenge. Herein, three natural phenol-inspired porous organic polymers were fabricated from natural phenolic-derived monomers (p-hydroxy benzaldehyde, 2,4-dihydroxy benzaldehyde and 2,4,6-trihydroxy benzaldehyde) and melamine via polycondensation reaction. Characterization highlighted that the increasing contents of hydroxyl groups in monomers induced an increase of the polymer total porosity and promoted the formation of a highly microporous structure. With mesopore-dominated pore (average pore diameter 9.6 nm) and large pore volume (1.78 cm3/g), p-hydroxy benzaldehyde-based porous polymer (1-HBPP) exhibited ultra-high maximum adsorption capacity (qmax) of 697.6 mg/g for tetracycline (TC) antibiotic. Meanwhile, the porous networks and plentiful active sites of 1-HBPP enabled fast adsorption kinetics (within 10 min) for TC removal, which could be well described by the pseudo-second-order model. Dynamic adsorption studies showed that 1-HBPP could be used in fixed-bed adsorption column (FBAC) with high removal efficiency (breakthrough volume per unit mass, 13.2 L/g) and dynamic adsorption capacity (201.6 mg/g), which were much higher than other reported adsorbents. The breakthrough curves both well matched with Thomas and Yoon-Nelson models in FBAC treatment. Moreover, removal mechanism analysis affirmed that pore-filling, hydrogen bonding, electrostatic interactions and π-π stacking interactions were main driving forces for TC adsorption. The prepared natural phenol-inspired porous adsorbents show great potential in antibiotics removal from wastewater, and this strategy would promote the sustainable and high-value utilization of natural phenolic compounds.

Superhydrophobic film from silicone-modified nanocellulose and waterborne polyurethane through simple sanding process.

How to improve the water and pollution resistance of films has been a major stumbling block in applications of waterborne coatings. To solve this problem, a new strategy was developed to construct waterborne superhydrophobic polyurethane composite films by modifying cellulose nanocrystal (CNC) with polysiloxane and doping the modified CNC into waterborne polyurethane (WPU). The super-hydrophobic functionalization with a water contact angle >150° was achieved by simple sanding. The effects of CNC on the morphology, thermal, mechanical, and hydrophobic properties of the obtained superhydrophobic composite films were investigated. The simple sanding process formed a large number of rough porous structures on the surface of the film, which improved the superhydrophobic properties of the film. And after 30 sanding cycles, the film still had excellent hydrophobicity (water contact angle >150°). This easy and effective method for the preparation of superhydrophobic films has great practical application value in the area of waterborne coatings.

Preparation and properties of novel bio-based epoxy resin thermosets from lignin oligomers and cardanol.

A series of lignin-based epoxy resins (LEPs) were prepared by the reaction of epichlorohydrin with lignin oligomers derived from partial reductive depolymerization of lignin. To overcome the high viscosity and brittleness defects in practical applications, the LEPs were blended with renewable epoxied cardanol glycidyl ether (ECGE) and then cured with methyltetrahydrophthalic anhydride (MeTHPA) to form high-performance epoxy thermosets. The effects of degree of lignin depolymerization, chemical composition of lignin oligomers and dosage of ECGE on thermal and mechanical properties of the cured products were investigated. The LEP/MeTHPA thermosets exhibited good thermal and mechanical properties. Especially, by separating monomer-rich fractions from lignin oligomers, the thermal and mechanical properties of the cured product were improved obviously. Notably, the incorporation of ECGE also possessed a positive effect on reinforcing and toughening the cured products. With 20 wt% ECGE loadings, the tensile, flexural and impact strength of the cured product reached the maximum value of 77 MPa, 115 MPa and 14 kJ/m2, respectively, which were equivalent to the commercial bisphenol A epoxy resins thermosets. These findings indicated that the novel bio-based epoxy resins from lignin oligomers and cardanol could be utilized as renewable alternatives for BPA epoxy resins.

Recent advances in lignin-based porous materials for pollutants removal from wastewater.

Water pollution is one of the most serious threats facing mankind today and has obtained widespread attention. Significant advances have been made in the past decades to apply porous materials in wastewater treatment, due to their large specific surface areas (SBET) for interaction with the aimed ions or molecules. However, the majority of porous materials are prepared from fossil-based resources and still possess some drawbacks, such as high cost and non-degradability, which inevitably cause secondary pollution to the environment from their production to disposal. Lignin is the most abundant and the only scalable renewable aromatic resource on earth. Due to its unique physicochemical properties including high carbon content, plentiful functional groups and environmental friendliness, the lignin-based porous materials (LPMs) have shown promising prospects in efficient removal of soluble pollutants from wastewater. In this review, we firstly described the structural and chemical basis of LPMs, following presented the recent progress in the decontamination of heavy metal ions, organic dyes, antibiotics, anions and radionuclides from aqueous systems. Additionally, the outlook was provided to promote more practical implementation of LPMs in the near future.

Efficient and selective removal of Pb(ii) from aqueous solution by a thioether-functionalized lignin-based magnetic adsorbent.

The effective and selective removal of heavy metal ions from sewage is a major challenge and is of great significance to the treatment and recovery of metal waste. Herein, a novel magnetic lignin-based adsorbent L@MNP was synthesized by a thiol-ene click reaction under ultraviolet (UV) light irradiation. Multiple characterization techniques, including Fourier transform infrared (FT-IR) spectrometry, X-ray diffraction (XRD), elemental analysis, vibrating sample magnetometry (VSM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), confirmed the formed nano-morphology and structure of L@MNP. The effects of pH, contact time, initial metal concentration and temperature on the batch adsorption of Pb(ii) by L@MNP were investigated. Due to the existence of sulfur and oxygen-containing sites, the maximum adsorption capacity of L@MNP for Pb(ii) could reach 97.38 mg g-1, while the adsorption equilibrium was achieved within 30 min. The adsorption kinetics and isotherms were well described by the pseudo-second-order model and Langmuir model, respectively, suggesting a chemical and monolayer adsorption process. In addition, L@MNP showed a high adsorption selectivity (k Pb = 0.903) toward Pb(ii) in the presence of other co-existing metal ions. The experimental results also revealed that L@MNP displayed structural stability, ease of recovery under an external magnetic field, and acceptable recyclability after the fifth cycle. Considering its facile preparation, low cost and high adsorption efficiency, the developed L@MNP adsorbent demonstrated great potential in removing heavy metal ions from wastewater.

Synthesis and Properties of Organosilicon-Grafted Cardanol Novolac Epoxy Resin as a Novel Biobased Reactive Diluent and Toughening Agent.

The aim of this work is to develop a biobased functional reactive diluent for thermosetting epoxy resins suitable for high-performance applications. An advanced organosilicon-grafted cardanol novolac epoxy resin (SCNER) was synthesized from cardanol novolac epoxy resin and heptamethyltrisiloxane. After the chemical structure of SCNER was identified by Fourier transform infrared, 1H NMR, and 13C NMR, it was used to modify the diglycidyl ether of the bisphenol A (DGEBA)/methylhexahydrophthalic anhydride system. The SCNER showed unique advantages, reducing the viscosity of DGEBA and improving the properties of the cured resin. With 10 wt % SCNER, the cured resin exhibited a higher tensile strength (78.84 MPa) and impact strength (32.36 kJ·m-2). The single glass transition temperature (T g) step proved the homogeneous phase structure of the cured resin. Inevitably, the T g of the cured resin decreased for the addition of SCNER. The dynamic mechanical analysis results indicated that the storage modulus of the cured resin decreased with the increasing content of SCNER. The morphology showing the ductile fracture of the cured resin was testified by scanning electron microscopy. The dilution and toughening properties of SCNER paves the way to a wide range of possible "eco-friendly" applications, especially in the fields of coatings, paintings, and adhesives.

Thermoset nanocomposites from waterborne bio-based epoxy resin and cellulose nanowhiskers.

Thermoset nanocomposites were prepared from a waterborne terpene-maleic ester type epoxy resin (WTME) and cellulose nanowhiskers (CNWs). The curing behaviors of WTME/CNWs nanocomposites were measured with rotational rheometer. The results show that the storage modulus (G') of WTME/CNWs nanocomposites increased with the increase of CNWs content. Observations by scanning electron microscopy (SEM) demonstrate that the incorporation of CNWs in WTME matrix caused microphase separation and destroyed the compactness of the matrix. This effect leads to the glass transition temperatures (Tg) of WTME/CNWs nanocomposites slightly decrease with the increase of CNWs content, which were confirmed by both DSC and DMA tests. The mechanical properties of WTME/CNWs nanocomposites were investigated by tensile testing. The Yong's modulus (E) and tensile strength (σb) of the nanocomposites were significantly reinforced by the addition of CNWs. These results indicate that CNWs exhibit excellent reinforcement effect on WTME matrix, due to the formation and increase of interfacial interaction by hydrogen bonds between CNWs nano-filler and the WTME matrix.

Thermoset nanocomposites from two-component waterborne polyurethanes and cellulose whiskers.

We prepared thermoset nancomposites from biomass-based two-component waterborne polyurethane (2K-WPU) and cellulose namowhiskers (CNWs). Due to the formation of hydrogen bonds, the viscosity of 2K-WPU dispersion was found to be increased with the addition of CNWs. SEM images showed "sea-island structure" corresponding to the microphase separation between CNWs nano-filler and the 2K-WPU matrix. The α-relaxation temperature (Tα) and glass transition temperature (Tg) increased with the increase of CNWs content, which was due to the formation of a rigid CNWs nano-phase acting as crosslinking points in the 2K-WPU matrix. Mechanical properties from tensile test showed Young's modulus and tensile strength of 2K-WPU/CNWs nanocomposites were reinforced by the addition of CNWs. Thermo-stability of 2K-WPU/CNWs nanocomposites decreased slightly with the increase of CNWs content, which could be attributed to the increased thermal conductivity of the material after adding CNWs.

Antibacterial/antifungal activity and synergistic interactions between polyprenols and other lipids isolated from Ginkgo biloba L. leaves.

Polyprenols separated from lipids are promising new components from Ginkgo biloba L. leaves (GBL). In this paper, ginkgo lipids were isolated by extraction with petroleum ether, saponification, and molecular distillation. Eight known compounds: isophytol (1), nerolidol (2), linalool (3), ß-sitosterol acetate (4), ß-sitosterol (5), stigmasterol (6), ergosterol (7), ß-sitosterol-3-O-ß-D-glucopyranoside (8) and Ginkgo biloba polyprenols (GBP) were separated from GBL by chromatography and identified mainly by NMR. The separated and identified compounds 1, 2 and 3 are reported here for the first time in GBL. The 3D-DAD-HPLC-chromatogram (190-232 nm) of GBP was recorded. This study provides new evidence as there are no previous reports on antibacterial/antifungal activities and synergistic interactions between GBP and the compounds separated from GBL lipids against Salmonella enterica, Staphylocococus aureus and Aspergillus niger. Nerolidol (2) showed the highest activity among all the tested samples and of all mixture groups tested the GBP with isophytol (1) mixture had the strongest synergistic effect against Salmonella enterica among the three tested strains. A proportion of isophytol and GBP of 38.19%:61.81% (wt/wt) was determined by mixture design as the optimal proportion for the synergistic effect of GBP with isophytol against Salmonella enterica.