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.

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.

Cellulose-based slow-release nitrogen fertilizers: Synthesis, properties, and effects on pakchoi growth.

The application of most slow-release fertilizers is limited by complex preparation processes and short slow-release periods. In this study, carbon spheres (CSs) were prepared by a hydrothermal method using cellulose as the raw material. Using CSs as the fertilizer carrier, three new carbon-based slow-release nitrogen fertilizers were prepared using direct mixing (SRF-M), water-soluble immersion adsorption (SRFS), and co-pyrolysis (SRFP) methods, respectively. Examination of the CSs revealed regular and ordered surface morphology, enrichment of functional groups on the surfaces, and good thermal stability. Elemental analysis showed that SRF-M was rich in nitrogen (total nitrogen content of 19.66 %). Soil-leaching tests showed that the total cumulative nitrogen release of SRF-M and SRF-S was 55.78 % and 62.98 %, respectively, which greatly slowed down the release of nitrogen. Pot experiment results revealed that SRF-M significantly promoted the growth of pakchoi and improved crop quality. Thus, SRF-M was more effective in practical applications than the other two slow-release fertilizers. Mechanistic studies showed that CN, -COOR, pyridine-N and pyrrolic-N participated in nitrogen release. This study thus provides a simple, effective, and economical method for the preparation of slow-release fertilizers, providing new directions for further research and the develop of new slow-release fertilizers.

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.

Preparation of N-doped cellulose-based hydrothermal carbon using a two-step hydrothermal induction assembly method for the efficient removal of Cr(VI) from wastewater.

Cr(VI) pollution is a growing problem that causes the deterioration of the environment and human health. We report the development of an effective adsorbent for the removal of Cr(VI) from wastewater. N-doped cellulose-based hydrothermal carbon (N-CHC) was prepared via a two-step hydrothermal method. The morphology and structural properties of N-CHC were investigated by various techniques. N-CHC has many O and N groups, which are suitable for Cr(VI) adsorption and reduction. Intermittent adsorption experiments showed that N-CHC had an adsorption capacity of 151.05 mg/g for Cr(VI) at pH 2, indicating excellent adsorption performance. Kinetic and thermodynamic analyses indicates that the adsorption of Cr(VI) on N-CHC follows a monolayer uniform adsorption process, which is a spontaneous endothermic process dominated by chemical interaction and limited by diffusion within particles. In a multi-ion system (Pb2+, Cd2+, Mn7+, Cl-, and SO42-), the selectivity of N-CHC toward Cr(VI) was 82.62%. In addition, N-CHC demonstrated excellent reuse performance over seven adsorption-desorption cycles; the Cr(VI) removal rate of N-CHC in 5-20 mg/L wastewater was >99.87%, confirming the potential of N-CHC for large-scale applications. CN/C-OR, pyridinic-N, and pyrrolic-N were found to play a critical role in the adsorption process. This study provides a new technology for Cr(VI) pollution control that could be utilized in large-scale production and other environmental applications.

Phosphorus acquisition strategies of wheat are related to biochar types added in cadmium-contaminated soil: Evidence from soil zymography and root morphology.

Biochar application for the remediation of cadmium (Cd)-contaminated soils may result in a relative deficiency of phosphorus (P) due to the disruption of soil nutrient balance. However, the P acquisition strategies of plants in such situation are still unclear. In this study, analyses on soil zymography and root morphology were combined for the first time to investigate the effects of pristine and P-modified biochars from apple tree branches on the P acquisition strategies of wheat under Cd stress. The results show that the application of pristine biochar exacerbated the soil's relative P deficiency. Wheat was forced to improve foraging for P by forming longer and thinner roots (average diameter 0.284 mm) as well as releasing more phosphatase to promote P mobilization in the soil. Moreover, bioavailable Cd affected the P acquisition strategies of wheat through stimulating the release of phosphatase from roots. The P-modified biochar maintained high levels of Olsen-P (>100 mg kg-1) in the soil over time by slow release, avoiding the creation of relative P deficiency in the soil; and increased the average root diameter (0.338 mm) and growth performance index, which promoted shoot growth (length and biomass). Furthermore, the P-modified biochar reduced DTPA-extracted Cd concentration in soils by 79.8 % (pristine biochar by 26.9 %), and decreased the Cd translocation factor from root to shoot as well as Cd concentration in the shoots. Therefore, P-modified biochar has a great potential to regulate the soil element balance (carbon, nitrogen, and P), promote wheat growth, and remediate the Cd-contaminated soil.

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.

Efficient removal of Remazol Brilliant Blue R from water by a cellulose-based activated carbon.

Due to its wide application and high toxicity, Remazol Brilliant Blue R (RBBR) has become a fatal contaminate in aquatic environment. In this study, to remove RBBR, a cellulose-based activated carbon (CAC) was synthesized at 800 °C with a cellulose-based hydrocarbon (CHC) activated by NaOH. The CHC was synthesized by the hydrothermal method with microcrystalline cellulose and urea as raw materials. The CAC possessed great amounts of N and O-containing functional groups and had well-developed pore structure. The BET specific surface area of CAC reached up to 1872.30 m2/g. The maximum adsorption capacity of CAC on RBBR was 653.19 mg/g during which chemical adsorption was the dominant mechanism. Adsorption thermodynamics indicated that the adsorption of RBBR by CAC was exothermic and spontaneous. Regeneration adsorption and ion competition experiments showed that the material could be used repeatedly and had good anti-interference ability. In addition, the removal rates of RBBR by CAC in actual water bodies, including river water and artificial lake water, were above 99.40%. Therefore, the novel CAC shows great potential for the remediation of printing and dyeing wastewater.

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.

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.

Adsorption of Cr(VI) from aqueous solutions using novel activated carbon spheres derived from glucose and sodium dodecylbenzene sulfonate.

Cr(VI) is a common wastewater pollutant. Various adsorbents including carbon-based materials are used for the removal of Cr(VI) owing to their high adsorption capacity. Chemical activation is an effective method to increase the specific surface area of adsorbents and, thus, further improve their adsorption capacity. However, research on the adsorption and removal of Cr(VI) from aqueous solutions by chemically activated carbon spheres is limited. Here, glucose and sodium dodecylbenzene sulfonate were used to produce carbon spheres (CSs) via hydrothermal synthesis. Activated carbon spheres (ACSs) were then derived using KOH. The adsorption of Cr(VI) in solution by CS and ACS was investigated through batch experiments. The results indicate that the specific surface area of the ACS was 1491.21 m2 g-1, which was much higher than that of the CS. The adsorption kinetics of the sorbent was consistent with the pseudo-second-order kinetic model and the adsorption isotherm followed the Langmuir model. This indicated that the adsorption process of the ACS with respect to Cr(VI) was mainly via single molecular layer adsorption and chemisorption. In a 200 mg L-1 Cr(VI) solution, the maximum amount of Cr(VI) adsorbed by the ACS was 230.15 mg g-1, and some of these adsorbed Cr(VI) were reduced to Cr(III). These results show that ACSs have strong potential for application in the removal of Cr(VI) from aqueous solutions.

Preparation of nitrogen-doped porous carbon material by a hydrothermal-activation two-step method and its high-efficiency adsorption of Cr(VI).

Nitrogen-doped carbon spheres (CSs-N) were synthesized by a hydrothermal method with glucose as the carbon source and urea as the nitrogen source. The synthesized nitrogen-doped carbon spheres were activated by KOH to prepare high performance nitrogen-doped porous carbon material (PCM-N) for adsorption of Cr(VI). SEM, TEM, BET, Raman spectroscopy, XRD, XPS, Zeta potential and elemental analysis techniques were used to characterize the materials, and the properties of the materials were tested by a batch adsorption method. The results show that the specific surface area of PCM-N is 1600.67 m2/g, and the maximum adsorption capacity of Cr(VI) is 402.9 mg/g, and the performance was better than that of a similar materials (Longan seed and Fox nutshell and so on). Furthermore, the adsorption capacity will increase with increasing temperature. In this study, the kinetics and isotherm model of adsorption parameters are fitted, and it is found that the adsorption process is in accordance with the Pseudo-second-order kinetic model and Freundlich model, thermodynamic parameters show that the adsorption of Cr(VI) onto the PCM-N was spontaneous endothermic process. The regeneration adsorption experiment showed that PCM-N has good reusability and high application value.

Hydrogel synthesis based on lignin/sodium alginate and application in agriculture.

A new green hydrogel has been synthesized by crosslinking lignosulfonate (L), sodium alginate (SA) and konjaku flour (KJ). We have optimized the ratio of the three synthesized polymers using an orthogonal design of experiments and characterized this hydrogel using SEM, BET and FTIR spectra. We have added the hydrogel into soil and investigated its degradability in soil and its influence on chemical and physical properties of soil, such as maximum water holding capacity, saturated hydraulic conductivity, water retention curve and nutrient retention and evaluated its performance when applied in drought stress tests on tobacco plants. The results show that the maximum water absorption of optimized L/KJ/SA is 41.23 g/g. Adding the L/KJ/SA hydrogel to soil reduces saturated hydraulic conductivity, increases available water capacity of soil and reduces leaching of soil nutrient. The L/KJ/SA hydrogel can improve the photosynthetic capability of tobacco plants under drought stress and the levels of osmotic regulators such as proline and reducing sugar, and could prolong the growth time of tobacco plants up to 14 days, which significantly increases its mass harvest. The L/KJ/SA hydrogel also has good degradability, which can degrade 20% when buried in soil for 120 days.