Silica-magnesium coupling in lignin-based biochar: A promising remediation for composite heavy metal pollution in environment.

Lignin hydrothermal silica-carbon material served as a backbone for MgCl2 activation to prepare lignin-based silicon/magnesia biochar (ALB/Si-Mg) for Cd2+, Pb2+, Cu2+, and Zn2+ removal from water and soil environment. Characterization studies revealed a 1017.71-fold increase in the specific surface area of ALB/Si-Mg compared to the original lignin biochar (ALB), producing abundant oxygen functional groups (OC-O, Si-O, Mg-O), and mineral matter (Mg2SiO4 and MgO). Crucially, batch adsorption experiments demonstrated that the adsorption capacity of ALB/Si-Mg for Cd2+, Pb2+, Cu2+, and Zn2+ was 848.17, 665.07, 151.84, and 245.78 mg/g, which were 29.09-140.45 times of the ALB. Soil remediation experiments showed that applying ALB/Si-Mg increased soil effective silicon (109.04%-450.2%) and soil exchangeable magnesium (276.41%-878.66%), enhanced plant photosynthesis, and notably reduced the bioavailability of heavy metals in soil as well as the content of heavy metals in Pakchoi, thereby promoting Pakchoi growth and development. The presence of oxygen-containing functional groups on ALB/Si-Mg, along with Mg2SiO4 and MgO nanoparticles, enhanced the adsorption capacity for heavy metals through the promotion of heavy metal precipitation, ion exchange, and complexation mechanisms. This study establishes the groundwork for the coupling of silica and magnesium elements in biochar and the remediation of composite heavy metal environmental pollution.

Two-stage hydrothermal oxygenation for efficient removal of Cr(VI) by starch-based polyporous carbon: Wastewater application and removal mechanism.

Cr(VI) is of concern because of its high mobility and toxicity. In this work, a two-stage hydrothermal strategy was used to activate the O sites of starch, and by inserting K-ion into the pores, starch-based polyporous carbon (S-PC) adsorption sites was synthesized for removal of Cr(VI). Physicochemical characterization revealed that the O content of the S-PC reached 20.66 % after activation, indicating that S-PC has excellent potential for adsorption of Cr(VI). The S-PC removal rate for 100 mg/L Cr(VI) was 96.29 %, and the adsorption capacity was 883.86 mg/g. Moreover, S-PC showed excellent resistance to interference, and an equal concentration of hetero-ions reduced the activity by less than 5 %. After 8 cycles of factory wastewater treatment, the S-PC maintained 81.15 % of its original activity, which indicated the possibility of practical application. Characterization and model analyses showed that the removal of Cr(VI) from wastewater by the S-PC was due to CC, δ-OH, ν-OH, and C-O-C groups, and the synergistic effect of adsorption and reduction was the key to the performance. This study provides a good solution for treatment of Cr(VI) plant wastewater and provides a technical reference for the use of biological macromolecules such as starch in the treatment of heavy metals.

Environmental applications of lignin-based hydrogels for Cu remediation in water and soil: adsorption mechanisms and passivation effects.

Heavy metal pollution, particularly the excessive release of copper (Cu), is an urgent environmental concern. In this study, sodium lignosulfonate/carboxymethyl sa-son seed gum (SL-Cg-g-PAA) designed for remediation of Cu-contaminated water and soil was successfully synthesized through a free radical polymerization method using lignin as a raw material. This hydrogel exhibits remarkable Cu adsorption capability when applied to water, with a maximum adsorption capacity reaching 172.41 mg/g. Important adsorption mechanisms include surface complexation and electrostatic attraction between Cu(Ⅱ) and oxygen-containing functional groups (-OH, -COOH), as well as cation exchange involving -COONa and -SO3Na. Furthermore, SL/Cg-g-PAA effectively mitigated the bioavailability of heavy metals within soil matrices, as evidenced by a notable 14.1% reduction in DTPA extracted state Cu (DTPA-Cu) content in the S4 treatment (0.7% SL/Cg-g-PAA) compared to the control group. Concurrently, the Cu content in both the leaves and roots of pakchoi exhibited substantial decreases of 55.19% and 36.49%, respectively. These effects can be attributed to the precipitation and complexation reactions facilitated by the hydrogel. In summary, this composite hydrogel is highly promising for effective remediation of heavy metal pollution in water and soil, with a particular capability for the immobilization of Cu(Ⅱ) and reduction of its adverse effects on ecosystems.

Enhancement of Cr(VI) adsorption on lignin-based carbon materials by a two-step hydrothermal strategy: Performance and mechanism.

Cr(VI) is a carcinogenic heavy metal that forms an oxygen-containing anion, which is difficult to remove from water by adsorbents. Here, industrial alkali lignin was transformed into a Cr(VI) adsorbent (N-LC) by using a two-step hydrothermal strategy. The characterization results of the adsorbent showed that O and N were uniformly distributed on the surface of the adsorbent, resulting in a favorable morphology and structure. The Cr(VI) adsorption of N-LC was 13.50 times that of alkali lignin, and the maximum was 326.10 mg g-1, which confirmed the superiority of the two-step hydrothermal strategy. After 7 cycles, the adsorption of N-LC stabilized at approximately 62.18 %. In addition, in the presence of coexisting ions, N-LC showed a selective adsorption efficiency of 85.47 % for Cr(VI), which is sufficient to support its application to actual wastewaters. Model calculations and characterization showed that N and O groups were the main active factors in N-LC, and CO, -OH and pyridinic-N were the main active sites. This study provides a simple and efficient method for the treatment of heavy metals and the utilization of waste lignin, which is expected to be widely applied in the environmental, energy and chemical industries.

Degradation of oxytetracycline by iron-manganese modified industrial lignin-based biochar activated peroxy-disulfate: Pathway and mechanistic analysis.

In this study, high-performance Fe-Mn-modified industrial lignin-based biochar (FMBC) was successfully prepared to facilitate the efficient degradation of oxytetracycline by its driven sulfate radical-based advanced oxidation process with 90% degradation within 30 min. The results showed that oxygenated functional groups (e. g. hydroxyl, carbonyl, etc.) in industrial lignin-based biochar, the synergistic effect of transition metals Fe and Mn, and defective structures were the active sites for activation of peroxy-disulfate. SO4·- produced during the degradation process assumed a key function. Significantly, 38 intermediates were innovatively proposed for the first time in the system, and oxytetracycline was degraded in 7 ways, including deamidation, demethylation, hydroxylation, secondary alcohol oxidation, ring opening, dehydration, and carbonylation. A new perspective on the application of industrial lignin in the advanced oxidative degradation of organic pollutants was provided by this study.

Amination-modified lignin recovery of aqueous phosphate for use as binary slow-release fertilizer.

To address the global phosphorus crisis and solve the problem of eutrophication in water bodies, the recovery of phosphate from wastewater for use as a slow-release fertilizer and to improve the slow-release performance of fertilizers is considered an effective way. In this study, amine-modified lignin (AL) was prepared from industrial alkali lignin (L) for phosphate recovery from water bodies, and then the recovered phosphorus-rich aminated lignin (AL-P) was used as a slow-release N and P fertilizer. Batch adsorption experiments showed that the adsorption process was consistent with the Pseudo-second-order kinetics and Langmuir model. In addition, ion competition and actual aqueous adsorption experiments showed that AL had good adsorption selectivity and removal capacity. The adsorption mechanism included electrostatic adsorption, ionic ligand exchange and cross-linked addition reaction. In the aqueous release experiments, the rate of nitrogen release was constant and the release of phosphorus followed a Fickian diffusion mechanism. Soil column leaching experiments showed that the release of N and P from AL-P in soil followed the Fickian diffusion mechanism. Therefore, AL recovery of aqueous phosphate for use as a binary slow-release fertilizer has great potential to improve the environment of water bodies, enhance nutrient utilization and address the global phosphorus crisis.

Performance and mechanism of starch-based porous carbon capture of Cr(VI) from water.

Cr(VI) pollution has seriously affected the survival of biological organisms and humans, so reducing the harm of Cr(VI) pollution is a significant scientific goal. Natural starch exhibits a low adsorption capacity for Cr(VI); thus, physical or chemical modification is needed to improve the adsorption and regeneration performance of starch. In this study, a novel starch-based porous carbon (SPC) was prepared to remove Cr(VI) from water by using soluble starch as a raw material. The characterization results show that the SPC shows a ratio surface area of 1325.39 m2/g. Kinetics suggest that the adsorption of Cr(VI) on SPC is dominated by chemisorption. The isotherm data demonstrated that the adsorption of Cr(VI) by SPC adhered to the Freundlich model. SPC exhibits a multimolecular layer adsorption structure, and the highest amount of adsorbed Cr(VI) in SPC was 777.89 mg/g (25 °C). Ion competition experiments show that SPC exhibits significant selectivity for Cr(VI) adsorption. In addition, the adsorption cycle experiment shows that SPC maintains a 63 % removal rate after 7 cycles. In this study, starch was transformed into high-quality adsorbent materials by hydrothermal and activation strategies, offering a new innovation for the optimization of starch-based adsorbents.

Three-dimensional lignin-based polyporous carbon@polypyrrole for efficient removal of reactive blue 19: A synergistic effect of the N and O groups.

Reactive blue 19 is one of the abundant carcinogens commonly used in industrial applications. This study transformed industrial lignin into a lignin-based polyporous carbon@polypyrrole (LPC@PPy) by a hydrothermal-activation-in situ polymerization strategy for removal of reactive blue 19. The hydrothermal reaction and polypyrrole polymerization provide abundant O and N groups, and the pore-making process promotes the even distribution of O and N groups in the 3D pore of LPC@PPy, which is favorable for the adsorption of reactive blue 19. The adsorption capacity of LPC@PPy for reactive blue 19 is 537.52 mg g-1, which is 2.04 times the performance of LPC (only hydrothermal and activation process, only have O groups) and 3.36 times that of LC (direct lignin activation, lack of O and N groups). After 8 cycles, LPC@PPy still maintained a high adsorption capacity of 92.14 % for reactive blue 19. In addition, this study found that N and O groups in the material played an important role in adsorption, mainly pyridinic-N, C-OH, -COOR, -C-O- and CC. This work provides a new strategy for the removal of reactive blue 19 and determines the groups that mainly interact with reactive blue 19, which provides a new reference for adsorption, catalysis and related fields.

High capacity adsorption of oxytetracycline by lignin-based carbon with mesoporous structure: Adsorption behavior and mechanism.

In this study, an adsorbent with mesoporous structure and PO/PO bonds is prepared by hydrothermal and phosphoric acid activation from industrial alkali lignin for the adsorption of oxytetracycline (OTC). The adsorption capacity is 598 mg/g, which is three times higher than that of the adsorbent with microporous structure. The rich mesoporous structure of the adsorbent provides adsorption channels and filling sites, and π-π attraction, cation-π interaction, hydrogen bonds, and electrostatic attraction provide adsorption forces at the adsorption sites. The removal rate of OTC exceeds 98 % over a wide range of pH values (3-10). It has high selectivity for competing cations in water, with higher than 86.7 % removal rate of OTC from medical wastewater. After 7 consecutive adsorption-desorption cycles, the removal rate of OTC remains as high as 91 %. This efficient removal rate and excellent reusability indicate the strong potential of the adsorbent for industrial applications. This study prepares a highly efficient, environmentally friendly antibiotic adsorbent that can not only efficiently remove antibiotics from water but also recycle industrial alkali lignin waste.

Effective adsorption of ammonium nitrogen by sulfonic-humic acid char and assessment of its recovery for application as nitrogen fertilizer.

Ammonium nitrogen (NH4+-N) is a form of N that is non-negligible in eutrophication water as well as an essential nutrient for plants growing. Carbon materials are considered superior for the adsorption recovery of excess NH4+-N in water bodies. The sulfonic-humic acid char (SHAC) was prepared from humic acid (HA) by pyrolysis and hydrothermal grafting with sodium allyl sulfonate. SEM-mapping, FTIR and XPS results indicated that sulfonic groups (-SO3H) were successfully grafted onto SHAC. The adsorption kinetic fitting displayed that the adsorption of NH4+-N by SHAC conformed to the pseudo-second-order kinetics and could reach equilibrium in about 100 min. The maximum adsorption of NH4+-N by SHAC was 77.24 mg/g, it was mainly contributed by electrostatic attraction, hydrogen bonding and pore volume sites. SHAC adsorption of NH4+-N resulted in the material SHAC-N, which desorption rate was considerably slower than that of commercially available ammonium chloride (NH4Cl) fertilizer and in accordance with the first order model. Wheat growth experiments revealed that the quality of wheat treated with SHAC-N (higher 100-grain weight and lower nitrate content) was better than that of NH4Cl fertilizer. In addition, the higher residual NH4+-N in the SHAC-N treatment soil facilitated subsequent crop planting. These results indicated that SHAC has excellent adsorption and slow release of NH4+-N, and has great potential application for N management in environment and agriculture.

Removal of Cd2+ from wastewater to form a three-dimensional fiber network using Si-Mg doped industrial lignin-based carbon materials.

In this study, SiMg doped industrial lignin-based carbon materials (SLCs) were prepared by water bath silicification and MgCl2 activation to remove Cd2+ from aqueous solutions. What's more, the doping of SiMg jointly promoted the excellent physicochemical properties of the material, e.g., high specific surface area, good pore volume, and numerous oxygen-containing groups. The Cd2+ batch adsorption experiments proved that SLCs have good Cd2+ removal capacity within pH 3-7, and the adsorption model demonstrated the adsorption process as a physicochemically complex process. The maximum adsorption of Cd2+ in the SLC was 665.35 mg/g, and the contributing factors to the removal of Cd2+ were as follows: ion exchange (59.36 %) > Cd2+ precipitation (24.93 %) > oxygen-containing functional group complexation (14.79 %) > Cd2+-π interactions (0.92 %). In addition, the complexation of SiO, MgO, and Cd precipitates allowed the formation of a three-dimensional fiber mesh structure. The application of SLCs has the potential to eliminate Cd2+ pollution in water bodies, and its preparation is simple and environmentally friendly. Finally, this study provides a theoretical basis for an in-depth understanding of the mechanism of heavy metal adsorption by inorganic nonmetals in combination with metal oxides.

Synthesis of honeycomb lignin-based biochar and its high-efficiency adsorption of norfloxacin.

In this study, honeycomb lignin-based biochar (HLB) was prepared by hydrothermal activation using industrial lignin as raw material to remove norfloxacin from water. Batch adsorption test results showed that HLB has a strong ability to remove norfloxacin at a wide pH. The maximum adsorption capacity was 529.85 mg/g at 298 K, which is 1.52-fold to 201.46-fold higher than that of other reported materials. HLB showed good selectivity and recycling ability for the adsorption of norfloxacin, the removal rate of NOR reached 99.5% in the presence of competitive ions and maintained at least 98% removal rate after 12 adsorption cycles. The removal rate of norfloxacin in different water reached more than 99% within 8 mins. Pore filling, electrostatic interaction, π-π interaction, and hydrogen bond contributed significantly to the removal of norfloxacin. Among them, the highly aromatized structure of HLB and the abundant oxygen-containing functional groups (OH, CO, etc.) promoted π-π interaction.

Lignin-based controlled release fertilizers: A review.

Lignin is the most abundant renewable aromatic resource on the planet, and it may be exploited to make the controlled release fertilizers (CRFs) that aid in human sustainable agriculture. Many researches on lignin-based CRFs have been conducted in recent years because of their exceptional controlled-release qualities. Lignin-based physically impeded CRFs can be produced by absorbing or wrapping nutrients and act as a longtime nutrient carrier, while chemically modified and chelated CRFs are produced by changing lignin structure to produce more active site and interaction between lignin and nutrients. In this review, lignin is evaluated on the basis of the manufacturing of various types of CRFs. The processes of lignin-based coated, chemically modified and chelated CRFs as well as lignin hydrogel-based CRFs are systematically summarized. Moreover, the general mechanism for controlled release of lignin-based CRFs is discussed. Finally, three common evaluation criteria of lignin-based CRFs efficiency are proposed. Overall, the use of lignin-based CRFs has the potential to greatly enhance resource efficiency and environmental protection.

Efficient Cr(VI) removal from wastewater by D-(+)-xylose based adsorbent: Key roles of three-dimensional porous structures and oxygen groups.

Reducing the harm of heavy metals to the environment has been a major scientific challenge. In this study, D-(+)-xylose was used to prepare an adsorbent with rich O groups and three-dimensional porous structures for Cr(VI) adsorption. What's more, the adsorption sites of many oxygen groups in the material were combined with the three-dimensionally connected porous structures, which made the adsorption sites fully in contact with Cr(VI). At the concentration of 300 mg/L, the removal rate of Cr(VI) was 94.50%, 6.4 times that of the non-porous treatment and 9.6 times that of the non-porous and O group treatment. The adsorbent showed a high adsorption capacity (910.10 mg/g) for Cr(VI), and the adsorption model proved that the adsorbent was a multi-molecular layer adsorbent. In addition, the adsorption was controlled by chemical reaction and diffusion, which was also attributed to the three-dimensional porous structure and abundant oxygen groups of the material. XPS and FTIR indicated that four O groups participated in the adsorption reaction (-OH, C-O-C, CO, and C-O), and C-O-C and C-O were the main reaction sites. After treating wastewater from electroplating plants with X-PC, the discharged water met international and domestic discharge standards (Cr(VI) removal rate> 99.90%). This work provides a new idea for the application of sugars in the environment and the design of porous adsorbents.

A novel lignin-based hierarchical porous carbon for efficient and selective removal of Cr(VI) from wastewater.

A novel lignin-based hierarchical porous carbon (L-HPC) was prepared to remove Cr(VI) from water by using industrial alkali lignin through simple hydrothermal-induced assembly and alkali activation strategy. The adsorbent were characterized by SEM-EDS mapping, TEM, BET, XPS, FTIR, Raman spectroscopy and zeta potential. The characterization results indicated that L-HPC contained three-dimensional connected channels and many adsorbing N, O and other adsorption groups, which is very beneficial for Cr(VI) adsorption. The kinetics showed that the L-HPC adsorption of Cr(VI) was chemical adsorption and mainly controlled by intraparticle diffusion. The isotherm and thermodynamics indicated that L-HPC adsorption of Cr(VI) conforms to the Freundlich model, L-HPC is a kind of multimolecular layer adsorbent, and the adsorption capacity of Cr(VI) by L-HPC was 887.8 mg/g, which was significantly higher than values for other adsorbents. Ion competition simulation and actual water body tests showed that L-HPC exhibits high selectivity for Cr(VI) adsorption, adsorption cycle experiments show that L-HPC maintains over 83% performance after 12 cycles. Cost analysis shows that L-HPC is suitable for mass production. Therefore, L-HPC is a Cr(VI) adsorbent with high efficiency, high selectivity, and high reusability, which is broadly applicable and shows favorable prospects.

Mechanism of a double-channel nitrogen-doped lignin-based carbon on the highly selective removal of tetracycline from water.

A high-performance nitrogen-doped lignin-based carbon material (ILAC-N) was synthesized using industrial lignin and urea by hydrothermal and activation, as an absorbent of tetracycline hydrochloride (TC). The results showed that the ILAC-N comprises a double-channeled structure with micro and mesopores. It exhibits an excellent adsorption capacity of TC across a wide pH range (pH 2-11), with the highest adsorption capacity of 1396 mg g-1 at 323 K. Tests in actual wastewater showed that the TC removal rate by ILAC-N exceeded 97.4%. Moreover, it maintained a removal rate of 84% after 10 regeneration cycles, revealing its high reusability. Mechanisms suggested that pore filling and π-π interaction played a critical role in this process. In conclusion, ILAC-N can be broadly applied to livestock manure and pharmaceutical wastewater treatment, owing to its high adsorption capacity, good adsorption properties across a wide pH range, excellent reusability. Furthermore, this research opens a new path for lignin utilization.

A novel glucose-based highly selective phosphate adsorbent.

Industrial wastewater discharge leads to serious eutrophication of water bodies, but most of the adsorbents are difficult to selectively remove phosphorus and are difficult to use multiple times, therefore, developing an efficient and reusable material for removal phosphate is extremely necessary. In this work, a kind of highly selective phosphate adsorbent, microporous carbon material (MCM), based on glucose was synthesized by hydrothermal and activation method. The MCM were characterized by SEM, XPS, BET, element analysis, et al. The phosphate adsorption mechanism of MCM were investigated by batch adsorption experiment and model calculation. Results showed that MCM had a high adsorption capacity for phosphate in a wide range of pH (1.5-10). Langmuir model and pseudo-second-order kinetic revealed that the process was endothermic and involved both physical and chemical adsorption. The main phosphate adsorption mechanisms of MCM are electrostatic attraction, ion complexation, hydrogen bonding, and physical adsorption. The ions competition simulation experiment indicated that the MCM was highly selective for phosphate removal. Furthermore, the phosphate adsorption tests were carried out on five kinds of water, and the removal rates were all above 99.98%. The 20 regenerative cycles experiment revealed that the MCM had high reusability. Therefore, this kind of novel glucose-based highly selective phosphate adsorbent with multi-cycle phosphorus removal performance can improve the eutrophication of water. This study provides a new idea for phosphate removal and expands the application range of glucose-based carbon materials.

The Eco-Friendly Biochar and Valuable Bio-Oil from Caragana korshinskii: Pyrolysis Preparation, Characterization, and Adsorption Applications.

Carbonization of biomass can prepare carbon materials with excellent properties. In order to explore the comprehensive utilization and recycling of Caragana korshinskii biomass, 15 kinds of Caragana korshinskii biochar (CB) were prepared by controlling the oxygen-limited pyrolysis process. Moreover, we pay attention to the dynamic changes of microstructure of CB and the by-products. The physicochemical properties of CB were characterized by Scanning Electron Microscope (SEM), BET-specific surface area (BET-SSA), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), and Gas chromatography-mass spectrometry (GC-MS). The optimal preparation technology was evaluated by batch adsorption application experiment of NO3-, and the pyrolysis mechanism was explored. The results showed that the pyrolysis temperature is the most important factor in the properties of CB. With the increase of temperature, the content of C, pH, mesoporous structure, BET-SSA of CB increased, the cation exchange capacity (CEC) decreased and then increased, but the yield and the content of O and N decreased. The CEC, pH, and BET-SSA of CB under each pyrolysis process were 16.64-81.4 cmol·kg-1, 6.65-8.99, and 13.52-133.49 m2·g-1, respectively. CB contains abundant functional groups and mesoporous structure. As the pyrolysis temperature and time increases, the bond valence structure of C 1s, Ca 2p, and O 1s is more stable, and the phase structure of CaCO3 is more obvious, where the aromaticity increases, and the polarity decreases. The CB prepared at 650 °C for 3 h presented the best adsorption performance, and the maximum theoretical adsorption capacity for NO3- reached 120.65 mg·g-1. The Langmuir model and pseudo-second-order model can well describe the isothermal and kinetics adsorption process of NO3-, respectively. Compared with other cellulose and lignin-based biomass materials, CB showed efficient adsorption performance of NO3- without complicated modification condition. The by-products contain bio-soil and tail gas, which are potential source of liquid fuel and chemical raw materials. Especially, the bio-oil of CB contains α-d-glucopyranose, which can be used in medical tests and medicines.

Phosphorus recovery by core-shell γ-Al2O3/Fe3O4 biochar composite from aqueous phosphate solutions.

Biochar can act as an adsorbent for phosphate removal from water sources, which can be highly beneficial in limiting eutrophication and recycling elemental phosphorus (P). However, it is difficult to use a single biochar material to overcome problems such as low adsorption efficiency, difficulty in reuse, and secondary pollution. This study addresses these challenges using a novel core-shell structure γ-Al2O3/Fe3O4 biochar adsorbent (AFBC) with significant P uptake capabilities in terms of its high adsorption capacity (205.7 mg g-1), magnetic properties (saturation magnetization 24.70 emu g-1), and high reuse stability (91.0% removal efficiency after five adsorption-desorption cycles). The highest partition coefficient 1.04 mg g-1 µM-1, was obtained at a concentration of 322.89 µM. Furthermore, AFBC exhibited strong regeneration ability in multiple cycle trials, making it extremely viable for sustainable resource management. P removal mechanisms, i.e., electrostatic attraction and inner-sphere complexation, were explained using Fourier transform infrared (FT-IR) spectra and X-ray photoelectron spectroscopy (XPS) measurements. A surface complexation model was established by considering the formation of monodentate mononuclear and bidentate binuclear surface complexes of P to illustrate the adsorption process. Owing to its high adsorption efficiency, easy separation from water, and environmental friendliness, AFBC is a potential adsorbent for P recovery from polluted waters.