Lignocellulosic-biomass-derived transparent nanopaper is an emerging substrate or functional component for next-generation green optoelectronics. The fabrication of such transparent nanopaper typically needs the delignification of lignocellulose; however, delignification not only is environmentally unfriendly but also impairs the nanopaper properties such as water stability and UV-shielding capacity. In this study, we present a green and facile lignin modification method instead of delignification to fabricate transparent nanopaper from agro-industrial waste with the combined intriguing properties of lignin and cellulose. Because lignin modification selectively removes chromophores without affecting the bulk lignocellulosic structures, the as-prepared lignocellulose nanopaper (LNP) achieved a comparable optical transmittance (∼90%) but superior UV-blocking ability and haze (∼46%) compared with previously reported cellulose (or delignified) nanopaper. The well-preserved lignin structures endowed the transparent LNP with a low surface energy and a small mesoporous size and volume. In addition to a high thermal stability, the transparent LNP exhibited excellent water stability, evidenced by an up to 103° initial water contact angle, a low equilibrium water absorption (<60 wt %), and a high wet mechanical strength (nearly 40% tensile strength and 92% toughness retained in the wet state). Furthermore, we fabricated a GaAs solar cell with the transparent LNP as an advanced light-management layer that leads to significantly improved power conversion efficiency, even under damp conditions. This work sheds light on the conversion of agro-industrial waste to nanopaper with desirable performances for optoelectronics and brings us a step closer toward the scalable production and application of LNP.
The separation and extraction of chrysin from active ingredients of natural products are of great significance, but the existing separation and extraction methods have certain drawbacks. Here, chrysin molecularly imprinted nanofiber membranes (MINMs) were prepared by means of electrospinning using chrysin as a template and polyvinyl alcohol and natural renewable resource rosin ester as membrane materials, which were used for the separation of active components in the natural product. The MINM was examined using Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The adsorption performance, adsorption kinetics, adsorption selectivity, and reusability of the MINM were investigated in static adsorption experiments. The analysis results show that the MINM was successfully prepared with good morphology and thermal stability. The MINM has a good adsorption capacity for chrysin, showing fast adsorption kinetics, and the maximum adsorption capacity was 127.5 mg·g−1, conforming to the Langmuir isotherm model and pseudo-second-order kinetic model. In addition, the MINM exhibited good selectivity and excellent reusability. Therefore, the MINM proposed in this paper is a promising material for the adsorption and separation of chrysin.
The exploration of functional films using sustainable cellulose-based materials to replace plastics has been of much interest. In this work, two kinds of lignin nanoparticles (LNPs) were mixed with cellulose nanofibrils (CNFs) for the fabrication of composite films with biodegradable, flexible and ultraviolet blocking performances. LNPs isolated from p-toluenesulfonic acid hydrolysis was easily recondensed and deposited on the surface of composite film, resulting in a more uneven surface; however, the composite film consisting of CNFs and LNPs isolated from maleic acid hydrolysis exhibited a homogeneous surface. Compared to pure CNF film, the composite CNF/LNP films exhibited higher physical properties (tensile strength of 164 MPa and Young’s modulus of 8.0 GPa), a higher maximal weight loss temperature of 310 °C, and a perfect UVB blocking performance of 95.2%. Meanwhile, the composite film had a lower environmental impact as it could be rapidly biodegraded in soil and manmade seawater. Overall, our results open new avenues for the utilization of lignin nanoparticles in biopolymer composites to produce functional and biodegradable film as a promising alternative to petrochemical plastics.
Lignocellulose nanopaper (LNP) assembled from lignocellulose nanofibrils (LCNFs) is an emerging eco-friendly structural material applicable to a variety of fields. Lignin serves as a crucial functional component in the LNP matrix; however, it negatively affects the interfacial hydrogen-bonding behaviors among LCNFs and consequently the inferior mechanical performance of LNP. In this study, a mild ozone-oxidation strategy was used to modify lignin macromolecules in situ without significant degradation of carbohydrate polymers (i.e., cellulose and hemicellulose) in LCNFs whereupon the interfacial hydrogen-bond energy was dramatically improved in the assembly and deformation process of LNP as validated by molecular dynamics simulation. Consequently, the lignin-modified LNP exhibited significantly enhanced tensile strength (from 83 to 140 MPa) and toughness (from 1.9 to 7.1 J/m 3 ), which even surpassed those of conventional cellulose nanopaper. Benefiting from the well-preserved lignocellulosic structure, lignin-modified LNP maintained its inherent favorable water and thermal stability and intriguing optical performance, which supported our developed LNP to be a multifunctional structural material for diversified fields, for example, flexible electronic applications. Additionally, the estimated production cost for our developed LNP was approximately half of that for conventional cellulose nanopaper due to its significantly lower resource inputs such as the material, water, and energy. Overall, our study provides a site-specific macromolecular modulation strategy for the economically and environmentally feasible fabrication of highperformance lignocellulosic nanomaterials toward advanced structural applications.
In this work, rosin-based composite membranes (RCMs) were developed as selective sorbents for the preparation of dencichine for the first time. The rosin-based polymer microspheres (RPMs) were synthesized using 4-ethylpyridine as a functional monomer and ethylene glycol maleic rosinate acrylate as a crosslinking. RCMs were prepared by spinning the RPMs onto the membranes by electrostatic spinning technology. The optimization of various parameters that affect RCMs was carried out, such as the ratio concentration and voltage intensity of electrospinning membrane. The RCMs were characterized by SEM, TGA and FT-IR. The performances of RCMs were assessed, which included adsorption isotherms, selective recognition and adsorption kinetics. The adsorption of dencichine on RCMs followed pseudo-second-order and adapted Langmuir–Freundlich isotherm model. As for the RCMs, the fast adsorption stage appeared within the first 45 min, and the experimental maximum adsorption capacity was 1.056 mg/g, which is much higher than the previous dencichine adsorbents reported in the literature. The initial decomposition temperature of RCMs is 297 °C, the tensile strength is 2.15 MPa and the elongation at break is 215.1%. The RCMs have good thermal stability and mechanical properties. These results indicated that RCMs are a tremendously promising adsorbent for enriching and purifying dencichine from the notoginseng extracts.
Chrysin is a natural bioactive molecule with various groups, and it has been a challenge to separate and enrich chrysin from natural products. Molecularly imprinted polymers have been widely used in the extraction of natural products, but the number and type of functional monomers limits the separation effect. The synergistic action of multiple functional monomers can improve the separation effect. In this paper, molecularly imprinted polymers (Bi-MIPs) were prepared using methacrylic acid and acrylamide as binary functional monomers for the separation and enrichment of chrysin. The Bi-MIPs were characterized using thermogravimetric analyzer (TGA), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM). The performances of Bi-MIPs were assessed, which included adsorption isotherms, selective recognition and adsorption kinetics. The experimental results show that Bi-MIPs are shaped as a uniform sphere with an abundant pocket structure on its surface. The adsorption of chrysin on the Bi-MIPs followed a pseudo-second-order and adapted Langmuir–Freundlich isotherm models. The adsorption performance of the Bi-MIPs was determined at different temperatures, and the Bi-MIPs showed excellent adsorption performance at 30 °C. The initial decomposition temperature of the Bi-MIPs was 220 °C. After five times of adsorption and desorption, the adsorption performance of the Bi-MIPs decreased by only 7%. In contrast with single functional monomer molecularly imprinted polymers (Si-MIPs), the Bi-MIPs showed excellent specificity, with an imprinting factor of 1.54. The Bi-MIPs are promising materials in the separation and enrichment of chrysin for their high adsorption capacity, low cost and being environmentally friendly.
The accumulation of dissolved and colloidal substances (DCS) in the increasingly closed paper circulating water system can seriously lower the productivity and safety of papermaking machines, and it has been a challenge to develop an adsorbent with low cost, high adsorption efficiency and large adsorption capacity for DCS removal. In this study, cationic lignocellulose nanofibers (CLCNF) were obtained by cationic modification of agricultural waste bagasse in deep eutectic solvents (DES) followed by mechanical defibrillation, and then CLCNF were employed as an adsorbent for DCS model contaminant polygalacturonic acid (PGA) removal. CLCNF was characterized by transmission electron microscopy, Fourier transform infrared, elemental analysis, X-ray diffraction, and thermogravimetric analysis. The analytical results confirmed the successful preparation of CLCNF with 4.6–7.9 nm diameters and 0.97–1.76 mmol/g quaternary ammonium groups. The effects of quaternary ammonium group contents, pH, contact time and initial concentration of PGA on the adsorption were investigated in a batch adsorption study. According to the results, the cationic modification significantly enhanced the adsorption of PGA by CLCNF and the adsorption performance increased with the increase of the quaternary ammonium group contents. The adsorption of PGA on CLCNF followed the pseudo-second-order and the fitted Langmuir isotherm model. The adsorption showed fast initial kinetics and the experimental maximum adsorption capacity was 1054 mg/g, which is much higher than PGA adsorbents previously reported in the literature. Therefore, CLCNF with high cationic group content developed in this paper is a promising adsorbent for DCS removal.
Mineral ions (mainly calcium ions) from sugarcane juice can be trapped inside the heating tubes of evaporators and vacuum boiling pans, and calcium ions are precipitated. Consequently, sugar productivity and yield are negatively affected. Calcium ions can be removed from sugarcane juice using adsorption. This paper described the experimental condition for the batch adsorption performance of rosin-based macroporous cationic resins (RMCRs) for calcium ions. The kinetics of adsorption was defined by the pseudo-first-order model, and the isotherms of calcium ions followed the Freundlich isotherm model. The maximal monolayer adsorption capacity of calcium ions was 37.05 mg·g−1 at a resin dosage of 4 g·L−1, pH of 7.0, temperature of 75 °C, and contact time of 10 h. It appeared that the adsorption was spontaneous and endothermic based on the thermodynamic parameters. The removal rate of calcium ions in remelt syrup by RMCRs was 90.71%. Calcium ions were effectively removed from loaded RMCRs by 0.1 mol·L−1 of HCl, and the RMCRs could be recycled. The dynamic saturated adsorption capacity of RMCRs for calcium ions in remelt syrup was 37.90 mg·g−1. These results suggest that RMCRs are inexpensive and efficient adsorbents and have potential applications for removing calcium ions in remelt syrup.
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