Hierarchical build-up of vertically oriented lignin-based aerogel for photothermally assisted uranium uptake and recovery from acidic wastewater.

Developing the lignin-based functional materials for uranium uptake is extremely attractive, but challenging due to the complex structure, poor solubility and reactivity of lignin. Herein, a novel phosphorylated lignin (LP)/sodium alginate/ carboxylated carbon nanotube (CCNT) composite aerogel (LP@AC) with vertically oriented lamellar configuration was created for efficient uranium uptake from acidic wastewater. The successful phosphorylation of lignin by a facile solvent-free mechanochemical method achieved more than six-times enhancement in U(VI) uptake capacity of lignin. While, the incorporation of CCNT not only increased the specific surface area of LP@AC, but also improved its mechanical strength as a reinforcing phase. More importantly, the synergies between LP and CCNT components endowed LP@AC with an excellent photothermal performance, resulting in a local heat environment on LP@AC and further boosting the U(VI) uptake. Consequently, the light irradiated LP@AC exhibited an ultrahigh U(VI) uptake capacity (1308.87 mg g-1), 61.26% higher than that under dark condition, excellent adsorptive selectivity and reusability. After exposure to 10 L of simulated wastewater, above 98.21% of U(VI) ions could be rapidly captured by LP@AC under light irradiation, revealing the tremendous feasibility in industrial application. The electrostatic attraction and coordination interaction were considered as the main mechanism for U(VI) uptake.

Efficient extraction of uranium from seawater by reticular polyamidoxime-functionalized oriented holocellulose bundles.

A novel multi-layered reticular polyamidoxime (PAO)-functionalized holocellulose bundles (ML-r-PAO@HB) with abundant oriented micro-channels and high mechanical strength was created via a facile solvent-exchange strategy and used for the first time to capture uranium from seawater. Due to the hydrophobic interaction of PAO chains induced by the solvent-exchange, multi-layered reticular PAO was successfully self-assembled onto the oriented micro-channels of the HB, which greatly improved the accessibility to the adsorption sites by increasing the exposed surface of PAO. The ML-r-PAO@HB exhibited high uptake capacity (851.42 mg g-1 PAO) and excellent adsorptive selectivity for U(VI) ions. After exposure to 500-L natural seawater for 28 days, an ultra-high uranium extraction capacity (9.74 mg g-1 PAO) was achieved by ML-r-PAO@HB. The N and O atoms in the -C(NH2)N-OH group were the main coordination sites for U(VI) uptake. These wonderful performances render the ML-r-PAO@HB highly desirable for the large-scale uranium extraction from seawater.

High-efficiency capture and removal of phosphate from wastewater by 3D hierarchical functional biomass-derived carbon aerogel.

The development of functional biomass-based carbon aerogels (CAs) with excellent mechanical flexibility and ultra-high phosphate capture capacity is crucial for capture and recovery of phosphate from waste water. Herein, a functional biomass-derived CA (MgO@SL/CMC CA) with an ordered wave-shaped layered structure and excellent compressibility was fabricated with the aim of creating a material with efficient phosphate capture performance. The incorporation of sulfonomethylated lignin (SL) significantly improves the mechanical flexibility of MgO@SL/CMC CA. Numerous MgO nano-particles (NPs), which act as principal adsorption sites, were uniformly anchored on the MgO@SL/CMC CA. The prepared MgO@SL/CMC CA with high Mg content (20.34 wt%) exhibited an ultra-high phosphate capture capacity (218.51 mg P g-1 for adsorbent or 644.58 mg P g-1 for MgO), excellent adsorptive selectivity for phosphate and a wide pH range of application (2-8). Notably, more than 81.95% of the phosphate capture capacity was retained after six cyclic adsorption-desorption tests. A considerable effective treatment volume (468 BV) of actual wastewater (1.7 mg P L-1) could be achieved by the MgO@SL/CMC CA in the fixed-bed adsorption column. Research into the adsorption mechanism reveals that monolayer chemisorption of phosphate occurs on the MgO@SL/CMC CA through a ligand exchange process. The combination of favorable flexibility, green raw materials and superior phosphate capture performance endows MgO@SL/CMC CA with great application potential in the practical treatment of wastewater.

Removed heavy metal ions from wastewater reuse for chemiluminescence: Successive application of lignin-based composite hydrogels.

The novel sulfomethylated lignin-grafted-polyacrylic acid (SL-g-PAA) hydrogel was fabricated in this work via a facile and green synthetic strategy for the efficient removal of heavy metal ions from wastewater, and then successively reused for chemiluminescence (CL). The sulfomethylation of lignin was first performed to improve its water solubility and introduce numerous active sites for adsorption of heavy metal ions. The as-synthesized SL-g-PAA hydrogel with high content of lignin exhibited the highly efficient and rapid removal of various metal ions from simulated wastewater. More importantly, the spent hydrogel (M2+@SL-g-PAA) after adsorption was reused for the first time to develop a new CL system by an ingenious strategy, in which these metal ions adsorbed on M2+@SL-g-PAA act as heterogeneous catalytic sites to catalyze the CL reaction between N-(4-aminobutyl)-N-ethylisoluminol (ABEI) and H2O2. The resultant CL system displayed high CL intensity and long duration time, which could be observed by naked eye in the dark and lasted for > 24 h. The combination of facile fabrication process, renewable raw materials, and ingenious strategy for successive application in adsorption and CL endows this lignin-based composite hydrogel with a great potential for application in wastewater treatment, biological imaging and cold light sources.

Nitrogen-doped lignin-derived biochar with enriched loading of CeO2 nanoparticles for highly efficient and rapid phosphate capture.

Development of lignin-derived carbon adsorbents with ultrahigh phosphate adsorption activity and rapid adsorption kinetics is of great importance, yet limited success has been achieved. Herein, we develop a CeO2 functionalized N-doped lignin-derived biochar (Ce@NLC) via a cooperative modification strategy for effective and fast phosphate capture. The novel modification strategy not only contributes greatly to the loading of well-dispersed CeO2 nanoparticles with a smaller size, but also significantly increases the relative concentration of Ce(III) species on Ce@NLC. Consequently, an enhanced capture capacity for phosphate (196.85 mg g-1) as well as extremely rapid adsorption kinetics were achieved in a wide operating pH range (2-10). Interestingly, Ce@NLC exhibited a strong phosphate adsorption activity at even low-concentration phosphorus-containing water. The removal efficiency and final P concentration reached 99.87% and 2.59 µg P L-1 within 1 min at the phosphate concentration of 2 mg P L-1. Experiments and characterization indicated that Ce(III) species plays a predominant role for the phosphate capture, and ligand exchange, together with electrostatic attraction, are the main adsorption mechanism. This work develops not only an efficient carbon-based adsorbent for phosphate capture, but also promotes the high-value application of industrial lignin.

Recent advances and challenges on removal and recycling of phosphate from wastewater using biomass-derived adsorbents.

As the severe damage of phosphate enrichment in the water ecosystem and the supply shortage of phosphate rock, developing an efficient method for the removal and recycling of phosphate from wastewater is of great significance. To achieve this goal, adsorption technology has been widely investigated, and various adsorbents were developed. Among them, the biomass-derived adsorbents including biomass-derived carbon-based materials, biomass-based anion exchangers and metal-biomass composites have attracted increasing attention over the past years due to the low cost, abundant renewable raw materials and environmental friendliness. However, different adsorbents usually exhibit variable adsorption performances for phosphate, which highly depends on their design strategies, preparation methods and potential adsorption mechanisms. Thus, this review comprehensively summarizes the recent researches on the removal and recycling of phosphate from wastewater using the biomass-derived adsorbents. Especially, the design strategies, preparation methods, adsorption performances and mechanisms of these reported biomass-derived adsorbents are discussed in detail. Moreover, as the significant strategies to recover and recycling phosphate, the elution and direct use of phosphate-loaded adsorbents as fertilizers are also presented. Although the excellent adsorption performance has been obtained, some challenges are still existing, which should be given more attention in the following researches to facilitate the development and industrial application of biomass-derived adsorbents.

Enhanced adsorption activity for phosphate removal by functional lignin-derived carbon-based adsorbent: Optimization, performance and evaluation.

Design of carbon-based adsorbents derived from industrial lignin with superior phosphate adsorption performance is of great significance, yet limited researches have been reported. Here, we report a MgO-functionalized lignin-based bio-charcoal (MFLC) as an efficient adsorbent for phosphate removal. The obtained MgO nanoparticles were dispersed homogeneously on MFLC with particle size of 50-100 nm and higher loading content (28.41%). Benefiting from the favorable morphology of MgO nanoparticles, the MFLC exhibits excellent regeneration ability for phosphate adsorption, which can be applied in a wide range of pH values (2-10). The maximum adsorption capacity could reach to 906.82 mg g-1 for phosphate. Interestingly, the MFLC shows extremely high adsorption activity in the low concentration of phosphate (2 mg P L-1), and its phosphate removal efficiency achieves 99.76%. Furthermore, the results also indicated that the higher loading content of MgO together with smaller particle size can effectively enhance the phosphate adsorption activity of MFLC. The adsorption mechanism revealed that the adsorption of phosphate on the surface of MFLC belongs to single-layer chemisorption, and ligand exchange plays a crucial role during adsorption/desorption. This work not only develops a new strategy for the preparation of high-efficiency carbon-based adsorbents, but also facilitates the value-added utilization of industrial lignin.

Amination of biorefinery technical lignin by Mannich reaction for preparing highly efficient nitrogen fertilizer.

To develop a novel lignin-based highly efficient nitrogen fertilizer, the amination of the biorefinery technical lignin was conducted by Mannich reaction synergy with phenolation pretreatment. Subsequently, the structural transformations of lignin samples and the reaction mechanism were investigated in detail. The soil column leaching experiment was also performed to research the nitrogen release behavior of aminated lignin in soil. The results indicated that the amounts of active sites in lignin were significantly increased to 8.26 mmol/g from the original 2.91 mmol/g by phenolation. In addition, the Mannich reaction was highly selective for occurring at ortho- and para-positions of phenolic hydroxyl groups in the phenolated lignin, in which the latter was favored. Moreover, the nitrogen content in the aminated lignin was highly depended on the types of amination reagent instead of the proportion of reactants in this study. Under an optimal condition, aminated lignin with a high nitrogen content (10.13%) and low C/N ratio (6.08) could be obtained. Besides, it was especially noteworthy that the prepared APL in this study has a favorable nitrogen release behavior in soil. Thus, it is believed that these aminated lignin derivatives could be used for the preparation of various lignin-based highly efficient nitrogen fertilizer.