A pH-Sensitive Lignin-Based Material for Sustained Release of 8-Hydroxyquinoline.

The fabrication of pH-sensitive lignin-based materials has received considerable attention in various fields, such as biomass refining, pharmaceuticals, and detecting techniques. However, the pH-sensitive mechanism of these materials is usually depending on the hydroxyl or carboxyl content in the lignin structure, which hinders the further development of these smart materials. Here, a pH-sensitive lignin-based polymer with a novel pH-sensitive mechanism was constructed by establishing ester bonds between lignin and the active molecular 8-hydroxyquinoline (8HQ). The structure of the produced pH-sensitive lignin-based polymer was comprehensively characterized. The substituted degree of 8HQ was tested up to 46.6% sensitivity, and the sustained release performance of 8HQ was confirmed by the dialysis method, the sensitivity of which was found to be 60 times slower compared with the physical mixed sample. Moreover, the obtained pH-sensitive lignin-based polymer showed an excellent pH sensitivity, and the released amount of 8HQ under an alkaline condition (pH = 8) was obviously higher than that under an acidic condition (pH = 3 and 5). This work provides a new paradigm for the high-value utilization of lignin and a theory guidance for the fabrication of novel pH-sensitive lignin-based polymers.

Designed synthesis of multifunctional lignin-based adsorbent for efficient heavy metal ions removal and electromagnetic wave absorption.

Multifunctional lignin-based adsorbents, which have shown great application prospect, have attracted widespread attention. Herein, a series of multifunctional lignin-based magnetic recyclable adsorbents were prepared from carboxymethylated lignin (CL), which was rich in carboxyl group (-COOH). After optimizing the mass ratio of CL to Fe3O4, the prepared CL/Fe3O4 (3:1) adsorbent showed efficient adsorption capacities for heavy metal ions. The kinetic and isotherm nonlinear fitting studies revealed that the adsorption process followed the second-order kinetic and Langmuir models, and the maximum adsorption capacities (Qmax) of CL/Fe3O4 (3:1) magnetic recyclable adsorbent for Pb2+, Cu2+ and Ni2+ ions reached 189.85, 124.43 and 106.97 mg/g, respectively. Meanwhile, after 6 cycles, the adsorption capacities of CL/Fe3O4 (3:1) for Pb2+, Cu2+ and Ni2+ ions could keep at 87.4 %, 83.4 % and 82.3 %, respectively. In addition, CL/Fe3O4 (3:1) also exhibited excellent electromagnetic wave absorption (EMWA) performance with a reflection loss (RL) of -28.65 dB at 6.96 GHz under the thickness of 4.5 mm, and its effective absorption bandwidth (EAB) achieved 2.24 GHz (6.08-8.32 GHz). In short, the prepared multifunctional CL/Fe3O4 (3:1) magnetic recyclable adsorbent with outstanding adsorption capacity for heavy metal ions and superior EMWA capability opens a new avenue for the diversified utilization of lignin and lignin-based adsorbent.

Preparation of activated lignin with high hydroxyl content using lewis acid as demethylation reagent.

Activation of lignin by demethylation for improving the reactivity has attracted extensive attentions. However, it still faces many challenges, such as the unsatisfied increase of hydroxyl content and the undesired cracking of linear linkages. Here, the efficient demethylations for significantly increasing the hydroxyl content and protecting the structure of industrial lignin were explored using lewis acid as modification reagent. As BBr3 was used, the phenolic hydroxyl content (Ar-OH) was increased by 80.65 %, but the lignin structure might be destroyed. About 75 % of the ß-O-4 linkages could be fortunately retained by using AlCl3. This method could also be used for the demethylation of alkaline poplar lignin with up to 171.67 % increase of Ar-OH (from 1.80 to 4.89 mmol/g). After activation, the antioxidant properties were improved 4.64-fold and 2.58-fold for 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals, respectively. This work would provide a theory guidance for activation of lignin and facilitate its high-value application.

Fabricating lignin-based carbon nanofibers as versatile supercapacitors from food wastes.

Recently, the high-value utilization of food wastes has attracted great interest in sustainable development. Focusing on the major application of electrochemical energy storage (ECES), light-weight lignin-based carbon nanofibers (LCNFs) were controllably fabricated as supercapacitors from melon seed shells (MSS) and peanut shells (PS) through electrospinning and carbonizing processes. As a result, the optimal specific capacitance of 533.7 F/g in three-electrode system, energy density of 69.7 Wh/kg and power density of 780 W/Kg in two-electrode system were achieved. Surprisingly, the LCNFs also presented a satisfied electromagnetic absorption property: The minimum reflection loss (RL) value reached -37.2 dB at an absorbing frequency of 7.98 GHz with an effective frequency (RL < 10 dB) of 2.24 GHz (6.88 to 9.12 GHz) at a thickness of 3.0 mm. These features make the multifunctional LCNFs highly attractive for light-weight supercapacitor electrodes and electromagnetic wave absorbers applications.

Effective fractionation strategy of sugarcane bagasse lignin to fabricate quality lignin-based carbon nanofibers supercapacitors.

Lignin is recommended to a tempting alternative precursor of petroleum for fabricating carbon nanofibers (CNFs) due to its high carbon content, low-cost and renewable resources. However, the property of lignin-based carbon nanofibers (LCNFs) is inferior owing to the heterogeneity and 3D-network structure of lignin, which hinders its application in supercapacitors. The latest developments in fractionation technology have shown great potential for overcoming the aforementioned shortcomings. However, most of fractionation methods mainly rely on expensive chemicals and complex reaction process, such as enzymes, multiple solvents, membranes, and dialysis tubes. Herein, we proposed a controllable and effective strategy to fractionate lignin by only changing the ratio of ethanol/water (V/V) as mixture solvent. This gradient extraction method effectively removed the part of lignin with small molecular and branching structure, thus selectively getting the fractionated lignin with high molecular weight, narrow polydispersity index, and good linear structure. Fortunately, when the ratio of ethanol/water was 6:4, the corresponding LCNFs (LCNFs-L60) was obtained with large specific surface area, independent filamentous morphology networks and excellent electrochemical property. Its specific capacitance was up to 405.8 F/g. This way features controllable and sustainable for preparing high-quality LCNFs supercapacitors.