Stepwise Ethanol-Water Fractionation of Enzymatic Hydrolysis Lignin to Improve Its Performance as a Cationic Dye Adsorbent.

In this work, lignin fractionation is proposed as an effective approach to reduce the heterogeneity of lignin and improve the adsorption and recycle performances of lignin as a cationic dye adsorbent. By stepwise dissolution of enzymatic hydrolysis lignin in 95% and 80% ethanol solutions, three lignin subdivisions (95% ethanol-soluble subdivision, 80% ethanol-soluble subdivision, and 80% ethanol-insoluble subdivision) were obtained. The three lignin subdivisions were characterized by gel permeation chromatography (GPC), FTIR, 2D-NMR and scanning electron microscopy (SEM), and their adsorption capacities for methylene blue were compared. The results showed that the 80% ethanol-insoluble subdivision exhibited the highest adsorption capacity and its value (396.85 mg/g) was over 0.4 times higher than that of the unfractionated lignin (281.54 mg/g). The increased adsorption capacity was caused by the enhancement of both specific surface area and negative Zeta potential. The maximum monolayer adsorption capacity of 80% ethanol-insoluble subdivision by adsorption kinetics and isotherm studies was found to be 431.1 mg/g, which was much higher than most of reported lignin-based adsorbents. Moreover, the 80% ethanol-insoluble subdivision had much higher regeneration yield (over 90% after 5 recycles) compared with the other two subdivisions. Consequently, the proposed fractionation method is proved to be a novel and efficient non-chemical modification approach that significantly improves adsorption capacity and recyclability of lignin.

Carbon-based single-atom catalysts derived from biomass: Fabrication and application.

Single-atom catalysts (SACs) with active metals dispersed atomically have shown great potential in heterogeneous catalysis due to the high atomic utilization and superior selectivity/stability. Synthesis of SACs using carbon-neutral biomass and its components as the feedstocks provides a promising strategy to realize the sustainable and cost-effective SACs preparation as well as the valorization of underused biomass resources. Herein, we begin by describing the general background and status quo of carbon-based SACs derived from biomass. A detailed enumeration of the common biomass feedstocks (e.g., lignin, cellulose, chitosan, etc.) for the SACs preparation is then offered. The interactions between metal atoms and biomass-derived carbon carriers are summarized to give general rules on how to stabilize the atomic metal centers and rationalize porous carbon structures. Furthermore, the widespread adoption of catalysts in diverse domains (e.g., chemocatalysis, electrocatalysis and photocatalysis, etc.) is comprehensively introduced. The structure-property relationships and the underlying catalytic mechanisms are also addressed, including the influences of metal sites on the activity and stability, and the impact of the unique structure of single-atom centers modulated by metal/biomass feedstocks interactions on catalytic activity and selectivity. Finally, we end this review with a look into the remaining challenges and future perspectives of biomass-based SACs. We expect to shed some light on the forthcoming research of carbon-based SACs derived from biomass, manifestly stimulating the development in this emerging research area.

Novel metal-lignin assembly strategy for one-pot fabrication of lignin-derived heteroatom-doped hierarchically porous carbon and its application in high-performance supercapacitor.

The conversion of renewable lignin with low-cost and high carbon content properties into porous carbon materials for supercapacitor applications has caught considerable interest. Herein, two dimensional lignin-derived carbon nanosheets (N-LHPC) with hierarchically porous structures were facilely synthesized via a novel metal-lignin assembly strategy and their performances for supercapacitor applications were investigated. During the carbonization process, the uniformly distributed Zn facilitates the coordinating development of micropores structure and the generated MgO embedded in the carbon matrix acts as a template to produce mesoporous structure after acid washing. Moreover, the melamine addition promotes the development of mesopores by formation of lamellae structure and realizes the N doping in the carbon materials. Therefore, the obtained N-LHPC presents an excellent specific capacitance of 235.75 F/g at 0.5 A/g owing to its hierarchical pore structure as well as the N/O functional groups. Moreover, at the power density of 450 W/kg, the N-LHPC achieves a maximum energy density of 14.75 Wh/kg, showing great application potential in energy storage. The metal-lignin assembly strategy followed by N-doping proposed in this paper provides N-LHPC materials with hierarchical nanostructure, good electron/ion transfer properties, and abundant pseudocapacitive active species, which improve the capacitance performances of the N-LHPC.

Reduction of lignin heterogeneity using aqueous two-phase system: A facile and universal "one-step-three-fractions" approach.

As the most abundant aromatic biopolymer, lignin presents great potential to produce valuable materials and chemicals. However, its large-scale value-added application is still facing many practical challenges and one of them is the unstable properties caused by lignin heterogeneity. Herein, we developed a novel "one-step-three-fractions" fractionation strategy to reduce lignin heterogeneity using aqueous two-phase system (ATPS) composed of (NH4)2SO4 and ethanol. In contrast to conventional step-wise fractionation processes, the proposed process subdivided heterogeneous lignin into three homogeneous fractions in only one step: the first fraction (F1) dissolved in the ethanol-rich top layer; the second fraction (F2) dissolved in the salt-rich bottom layer and the last fraction (F3) insoluble in both two layers. F2 presented the lowest molecular weight followed by F1 while F3 showed the highest molecular weight. With the increase of molecular weight, the contents of guaiacyl unit and ß-O-4 linkage increased while the content of hydrophilic groups (carboxyl and aromatic hydroxyl) decreased significantly. Moreover, the ATPS exhibited satisfactory recyclability and the fractionation approach could be applied to different types/sources of lignin. Consequently, the work indicates that ATPS is a novel and effective way to fractionate lignin and reduce its molecular weight polydispersity and structural heterogeneity in one step.

Subdivision of bamboo kraft lignin by one-step ethanol fractionation to enhance its water-solubility and antibacterial performance.

Over the recent years, the exploitation of antibacterial performance of lignin and its subsequent usage as bacteriostatic additives has gained increasing interests. However, due to the restriction from structural heterogeneity, the antibacterial activity of lignin is always modest and unstable (especially against Gram-negative bacteria). In this regard, we proposed a facile one-step ethanol fractionation process to decrease the heterogeneity of lignin and, therefore, improve its antibacterial activity. Two fractions (Fs and Fi, 95% ethanol soluble and insoluble fraction, respectively) were obtained from bamboo kraft lignin (BKL) and their antibacterial effectiveness was compared. The results showed that the antibacterial activity of Fs increased significantly compared to that of BKL. On the contrary, Fi barely exhibited inhibitory effect on the growth of two Gram-positive bacteria and even promoted the growth of two Gram-negative bacteria. The much lower phenolic-OH content in Fi was an important reason for the absence of antibacterial activity. Besides, the growth promotion of Gram-negative bacteria by Fi was possibly caused by the formation of insoluble carriers for bacteria growth due to the poor water-solubility of Fi. Accordingly, after the elimination of Fi, the one-step fractionation significantly enhanced the antibacterial activity of lignin against both Gram-positive and Gram-negative bacteria.