Analysis of the role of various biochar in the remediation of heavy metals in contaminated water and its kinetics study

Biochar prepared from agricultural wastes has gained great attention as a cost-effective treatment for metal-contaminated water. In this study, the effectiveness of corn cob and sugarcane bagasse-derived biochar for metals (Pb, Ni, and Cu) removal from an aqueous medium was examined following their physical, chemical, and structural characterization. Batch sorption experiments were carried out by employing the Langmuir and Freundlich equations. The results indicated that separation factor (R_L) values lay in the range of 0 and 1 representing the productive adsorption. The optimum dosage for metal adsorption can be recommended as 30 g L^?1. The optimum adsorption conditions were found at 6.5 and 5.5 pH, 1.5 g adsorbent dose, and at 180 min equilibrium time, for both corn cob and sugarcane bagasse biochars. At pH 6.5, adsorption capacities of Pb, Ni, and Cu were found maximum i.e., 11.34, 15.71, and 11.96 mg kg^?1 for corn cob and 8.96, 15.46, and 12 mg kg^?1, for sugarcane bagasse biochars, respectively. The metal adsorption kinetics was analyzed via four different types of the pseudo-second-order kinetic model. Moreover, the corn cob biochar showed a more pronounced activity in the removal of metals compared to sugarcane bagasse biochar. Hence, it was concluded that corncob and sugarcane bagasse-derived biochars could be utilized as economical bio-adsorbents for the heavy metals removal from wastewater.     

Corncob-to-xylose residue (CCXR) derived porous biochar as an excellent adsorbent to remove organic dyes from wastewater

Biochar was prepared from corncob-to-xylose residue (CCXR) by KOH activation and anaerobic pyrolysis method. The effect of activation temperature on the microstructure of the biochar was studied. Results showed that the biochar prepared at 850°C (850NBC) possessed high specific surface area and exhibited excellent adsorption property. The maximum adsorption capacity of 2249 mg g⁻¹ was obtained when 850NBC was used for treating methylene blue (MB) solution. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable to 850NBC adsorption process, and the adsorption process was limited by adsorption site and the biochar surface functional groups. Furthermore, 850NBC showed good adsorption property when it was used to treat the other organic dyes of Congo red (751 mg g⁻¹), Orange II (735 mg g⁻¹), Indigo carmine (662 mg g⁻¹) and Methyl Orange (465 mg g⁻¹). Biochar 850NBC also possessed an acceptable recyclability which maintained 68.7% absorption capacity after 6 cycles when it was used to treat MB solution. These results proposed that 850NBC is expected to be a promising potential adsorbent for treating organic dyes waste water.     

Highly efficient removal of diazinon pesticide from aqueous solutions by using coconut shell-modified biochar

This study evaluates the adsorption of diazinon from aqueous solutions onto coconut shell-modified biochar using a batch system. The amount of dosage and initial pH are the main parameters being studied to obtain maximum adsorption capacity of the probe molecules. The carbonized coconut shell biochar (BC1), activated coconut shell biochar (BC2), chemically modified phosphoric acid (BC3) and sodium hydroxide coconut shell biochar (BC4) were prepared and tested as variables in the adsorption experiment. The characteristic of biochar via SEM, EDX and BET analysis revealed the large porous of surface morphology and slight changes in the composition with high surface area (405.97 – 508.07 m²/g) by following the sequence of BC3 > BC2 > BC4. Diazinon removal percentage as high as 98.96% was achieved at pH 7 with BC3 as adsorbent dosing at 5.0 g/L. The high coefficient of determination, R² with a small value of ERRSQ and χ² error analysis present the BC1 (0.9971) and BC2 (0.9999) are best fitted with Freundlich isotherm indicates multilayer sorption onto heterogeneous surface whereby the Langmuir isotherm model is the best fitting is described of monolayer adsorption process onto the homogenous surface of BC3 and BC4. The results indicated the maximum adsorption capacity (q_m) was achieved by BC3 with 10.33 mg/g, followed by BC2 (9.65 mg/g) in accordance to the Langmuir isotherm while Freundlich isotherm showed the highest adsorption capacity (k_F) with 1.73 mg/g (L/mg)^1/n followed by BC4 with 0.63 mg/g (L/mg)^1/n at favorable adsorption isotherm (1 ≤ n ≤ 10). Thus, the results obtained depicted that BC2 and BC3 are highly efficient adsorbents and both exhibit great potential in removing diazinon from aqueous solutions.     

Quality variations of poultry litter biochar generated at different pyrolysis temperatures

Producing biochar and biofuels from poultry litter (PL) through slow pyrolysis is a farm-based, value-added approach to recycle the organic waste. Experiments were conducted to examine the effect of pyrolysis temperature on the quality PL biochar and to identify the optimal pyrolysis temperature for converting PL to agricultural-use biochar. As peak pyrolysis temperature increased incrementally from 300 to 600 °C, biochar yield, total N content, organic carbon (OC) content, and cation exchange capacity (CEC) decreased while pH, ash content, OC stability, and BET surface area increased. The generated biochars showed yields 45.7–60.1% of feed mass, OC 325–380 g kg⁻¹, pH 9.5–11.5, BET surface area 2.0–3.2 m² g⁻¹, and CEC 21.6–36.3 cmol_c kg⁻¹. The maximal transformation of feed OC into biochar recalcitrant OC occurred at 500 °C, yet 81.2% of the feed N was lost in volatiles at this temperature. To produce agricultural-use PL biochar, 300 °C should be selected in pyrolysis; for carbon sequestration and other environmental applications, 500 °C is recommended.     

Sorption separation of Eu and As from single-component systems by Fe-modified biochar: kinetic and equilibrium study

The utilization of carbonaceous materials in separation processes of radionuclides, heavy metals and metalloids represents a burning issue in environmental and waste management. The main objective of this study was to characterize the effect of chemical modification of corncob-derived biochar by Fe-impregnations on sorption efficiency of Eu and As as a model compounds of cationic lanthanides and anionic metalloids. The biochar sample produced in slow pyrolysis process at 500 °C before (BC) and after (IBC) impregnation process was characterized by elemental, FTIR, SEM-EDX analysis to confirm the effectiveness of Fe-impregnation process. The basic physico-chemical properties showed differences in surface area and pH values of BC- and IBC-derived sorbents. Sorption processes of Eu and As by BC and IBC were characterized as a time- and initial concentration of sorbate-dependent processes. The sorption equilibrium was reached for both sorbates in 24 h of contact time. Batch equilibrium experiments revealed the increased maximum sorption capacities (Q _max) of IBC for As about more than 20 times (Q _max BC 0.11 and Q _max IBC 2.26 mg g^?1). Our study confirmed negligible effect of Fe-impregnation on sorption capacity of biochar for Eu (Q _max BC 0.89 and Q _max IBC 0.98 mg g^?1). The iron-impregnation of biochar-derived sorbents can be utilized as a valuable treatment method to produce stable and more effective sorption materials for various xenobiotics separation from liquid wastes and aqueous solutions.     

Performance and mechanisms of NaOH and ball-milling co-modified biochar for enhanced the removal of Cd2+ in synthetic water: A combined experimental and DFT study

A multifunction magnetic carbonaceous adsorbent (MBM/OH/BC) was synthesized by facile NaOH and ball-milling co-modified biochar, and applied for removing Cd²⁺ in water. The results showed MBM/OH/BC exhibited excellent adsorption capacity (183.59 mg/g for Cd²⁺), short equilibrium time (60 min) and good reusability (the declining efficiency <20% after four adsorption and desorption cycles) compared with pristine biochar. Meanwhile, the modification mechanisms of NaOH and ball-milling to biochar were explored by a series of characterizations (XRD, SEM-EDS, BET, XPS and FTIR, et al). The results indicated the remarkable adsorption performance of MBM/OH/BC was mainly attributed to the co-modification significantly increased the specific surface area, mineral content and cation exchange capacity of biochar, thereby further improving the precipitation, cation exchange and complexation with Cd²⁺. In addition, the results of adsorption mechanisms showed that the joint contribution proportion to the total adsorption capacity of precipitation, cation exchange and complexation was up to 90%, indicating the three mechanisms were the primary adsorption mechanism. To sum up, NaOH and ball-milling co-modification was an effective strategy to increase the adsorption capacity of the pristine biochar for heavy metals from water.     

Hierarchically porous tobacco midrib-based biochar prepared by a simple dual-templating approach for highly efficient Rhodamine B removal

High volatile matter contents in the feedstock could promote the development of porous structures and the reactivity of biochar. Herein, tobacco midrib with high volatile matter contents was used to prepare biochar by a dual-templating approach with mild activators (K₂C₂O₄·H₂O, CaCO₃). The characterizations of textural properties indicated that tobacco midrib-based biochar possessed numerous meso-, micro-, and macro-pores, specific surface area reached 1841.9 m² g^?1. As a dye adsorbent, the adsorption capacity of this biochar towards Rhodamine B reached 588.7 mg g^?1. After recycling 5 times, it still retained over 90% of its initial adsorption capacity. Moreover, thermodynamic parameters assessed with full vańt Hoff equation confirmed that dye molecules replace water molecules connected on biochar surface during the adsorption according to negative heat capacity change (-3.9 kJ mol^?1 K^?1), ΔH⁰ (–22.1 kJ mol^?1) and ΔS⁰ (0.3 kJ mol^?1) revealed that the adsorption process of Rh B by TMB was exothermic and the disorder of the solid–liquid interface increased. Overall, this research provides a mild and effective approach to modifying biochar from special tissue of agriculture waste and an insight into the process of dye adsorption on biochar from thermodynamics.     

Remediation of Cd2+ in aqueous systems by alkali-modified (Ca) biochar and quantitative analysis of its mechanism

Co-pyrolysis of straw and Ca(OH)₂ is a feasible modification method to improve the adsorption capacity of biochar for Cd. However, few studies have quantitatively analyzed the contribution of different adsorption mechanisms of alkali-modified biochar. In this study, the alkali-modified (Ca) biochar were prepared by co-pyrolyzing lime (Ca(OH)₂) and soybean straw (SBB) or rape straw (RSB) at 450 °C. The adsorption mechanism was investigated by a series of experiments and was provided by quantitative analysis. The maximum adsorption capacities of Cd²⁺ by Ca-SBB and Ca-RSB were calculated to be 78.49 mg g^?1 and 49.96 mg g^?1, which were 1.56 and 1.48 times higher than SBB (50.40 mg g^?1) and RSB (33.79 mg g^?1), respectively. Compared with the original biochar (SBB, RSB), alkali-modified biochar (Ca-SBB and Ca-RSB) were found to have faster adsorption kinetics and lower desorption efficiencies. The mechanism study indicated that Ca(OH)₂ modification effectively enhanced the contribution of ion exchange and decreased the contribution of functional groups complexation. After Ca(OH)₂ modification, precipitation and ion exchange mechanisms dominated Cd^2 + absorption on Ca-SBB, accounting for 49.85% and 34.94% of the total adsorption, respectively. Similarily ion exchange and precipitation were the main adsorption mechanism on Ca-RSB, accounting however for 61.91% and 18.47% of total adsorption, respectively. These results suggested that alkali-modified biochar has great potential to adsorp cadmium in wastewater.     

Nitrate removal from aqueous solution using watermelon rind derived biochar-supported ZrO2 nanomaterial: Synthesis,characterization, and mechanism

Recently, biochar has attracted tremendous research interest for environmental applications. In this study, biochar-derived watermelon rind (WM) was produced via optimal pyrolysis at 500 °C for 2 h, and then improved the adsorption capacity by Zirconium oxide nanoparticles (ZrO₂ NPs). The WM@ZrO₂ was characterized using X-ray diffraction (XRD), Scanning electron microscopic - Energy-dispersive X-ray spectroscopy (SEM-EDS), and Fourier transform infrared (FTIR). The adsorptive capacities of synthesized ZrO₂ NPs were investigated for nitrate as a function of pH, adsorbent dosage, contact time, initial adsorbate concentration, and pyrolysis temperature in the batch experiment. The results showed that a Langmuir isotherm and a pseudo-second-order kinetics model were the best-fit for experimental nitrate data in its non-linear form as correlation coefficients (R²) were 0.985 and 0.998, respectively. The maximum adsorption capacity for the Langmuir isotherm model was 15.196 mg g^?1. The proposed mechanism, including electrostatic attraction and ligand exchange, played a dominant role in nitrate adsorption. After testing with the real domestic wastewater, the removal of nitrate for WM@ZrO₂ was achieved at 78 %, which was equivalent to the adsorption capacity of 8.1 mg g^?1 of adsorbent. Overall, the WM@ZrO₂ is proposed as a promising, effective, and environmentally friendly adsorbent in removing nitrate from an aqueous solution.     

Adsorption-reduction performance of tea waste and rice husk biochars for Cr(VI) elimination from wastewater

In the current study tea waste and rice husk biochars were used for the elimination of Cr(VI) from wastewater with the objectives to study the effect of pH (3–10), shaking time (0.016–24 h), sorbent dose (0.1–1.3 g L⁻¹) and initial concentration of Cr(VI) (10–250 mg L⁻¹). The Cr(VI) sorption was studied under various factors in which solution pH played a main role and at pH 5.2, maximum 99.3% and 96.8% Cr(VI) were removed by tea waste biochar (TWB) and rice husk biochar (RHB), respectively. In comparison, 197.5 mg g⁻¹ and 195.24 mg g⁻¹ Cr(VI) were sorbed by TWB and RHB, respectively with 120 mg L⁻¹ initial Cr(VI) concentration. In contact time study, after 2 h, equilibrium was achieved for both biochars which indicated that the Cr(VI) elimination from aqueous medium is a fast process. Kinetic and isotherm modeling data showed that pseudo-second order model and Langmuir (monolayer sorption) models provided the best fit for sorption of Cr(VI) onto both biochars. The –OH, COO– and –NH₂ functional groups were involved in the sorption of Cr(VI) onto biochars according to FTIR. Biochars produced from both biomass effectively removed Cr(VI) from polluted water, however in comparison sorption capacity of TWB was slightly higher than RHB. It was concluded that TWB and RHB could provide a cost-effective and viable option for elimination of Cr(VI) from wastewater.     

Raw and treated marble wastes reuse as low cost materials for phosphorus removal from aqueous solutions: Efficiencies and mechanisms

Phosphorus removal from synthetic solutions by raw and calcined powdered marble wastes (RPMW and CPMW) has been investigated in batch mode under different experimental conditions. The results showed that RPMW and CPMW have high removal efficiencies, especially in acidic media. The maximum phosphorus removal capacities were evaluated to 103.9 and 181.2 mg·g⁻¹ at an initial pH and an aqueous concentration of 5 and 350 mg·L⁻¹, respectively. Phosphorus removal by RPMW occurred mainly through adsorption. However, for CPMW, phosphorus was removed not only by adsorption, but also by precipitation as calcium phosphate complexes. Specific analyses using scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Fourier transform infrared spectroscopy confirmed that this precipitate is most probably hydroxyapatite. On the other hand, CPMW have demonstrated an important ability in removing phosphorus from highly concentrated dairy wastewater (C_0,P = 1000 mg·L⁻¹) since only one dosage of 10 g·L⁻¹ was enough to ensure more than 97% of phosphorus removal.     

Copper removal from aqueous solution using biochar: Effect of chemical activation

The main aim of this study was to test the efficiency of biochar for Cu removal from synthetic and soil solutions, respectively.The biochar was produced from brewers draff via pyrolysis. Additionally, the prepared biochar was also activated using 2 M KOH to enhance its sorption efficiency to remove Cu from both solutions. Two different aqueous solutions were prepared for these experiments: (i) a synthetic using Cu-nitrate salt with 0.01 M NaNO₃ and (ii) soil solution obtained from a Cu-contaminated soil using 0.01 M CaCl₂ leaching procedure. Batch sorption and column experiments were used to evaluate the efficiency of both biochar (BC) and activated biochar (BC_act) to remove Cu from the solutions.Results showed that both biochar samples are pure amorphous carbon and the Cu sorption is thus mainly a result of physical sorption on the biochar surface. Next, chemical activation, using 2 M KOH, significantly increased the total volume of all pores in biochar (from 0.01 ± 0.002 to 8.74 ± 0.18 mL g⁻¹). On the other hand, the BET surface area was similar for both sorbents (BC = 9.80 ± 0.62 m² g⁻¹ and BC_act = 11.6 ± 0.4 m² g⁻¹). Results also demonstrate enhanced sorption efficiency of the BC_act (10.3 mg g⁻¹) in comparison with the BC (8.77 mg g⁻¹). Additionally, enhanced Cu removal during column retention test was observed for the BC_act in both synthetic and soil solutions, respectively.In summary, the results showed that biochar prepared from brewers draff was able to remove Cu from both aqueous solutions.     

Preparation and characterization of imprinted microspheres for clopyralid

In this work, the molecularly imprinted polymers (MIPs) and non-imprinted polymers (NIPs) for clopyralid (3,6-DCP) were successfully synthesized via precipitation polymerization using methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as crosslinker and a mixture of butanone (MEK) and n-heptane as porogen under the existence of azobisisobutyronitrile (AIBN). The morphologies, particle sizes, structures, adsorption properties and selective recognitions of polymers were investigated systematically. The average particle sizes of MIP3 and NIP3 were 2.76 μm and 2.15 μm. The apparent maximum binding amount (Q_max) of MIP3 and NIP3 were 67.50 mg·g^?1 and 65.02 mg·g^?1 in Scatchard analysis. Langmuir isotherm displayed that the Langmuir constant (K_l) of MIP3 and NIP3 were 0.015 L·mg^?1 and 0.0065 L·mg^?1, the saturation adsorption capacity (Q_max) of MIP3 and NIP3 were 63.23 mg·g^?1 and 58.17 mg·g^?1. Lagergren pseudo-second-order kinetic plot described that the adsorption process of MIP3 was visualized as chemical absorption. Selectivity analysis revealed that MIP3 possessed highly specific recognition for 3,6-DCP.     

Highly removal of anionic dye from aqueous medium using a promising biochar derived from date palm petioles: Characterization,adsorption properties and reuse studies

The present work investigates the preparation of promising biochar derived from date palm petioles powder (DPB) via a thermal treatment. DPB was characterized through various techniques to analyze the chemical (FTIR), morphological (SEM) and point of zero charges to investigate changes incorporated through the pyrolysis process.The adsorption of methyl orange (MO) onto the biochar was investigated using batch experiments according to different parameters which influence the adsorption process such as: initial dye concentration, equilibrium time, pH, and temperature. Isothermal and reuse studies of MO adsorption onto DPB were also investigated.Results of MO removal on DPB have demonstrated that the adsorption process was initial dye concentration-dependent, and equilibrium time was occurred in 60 min. The biochar presented high stability of MO adsorption capacity in a large domain of pH. Thermodynamic analysis of this process revealed that methyl orange adsorption was exothermic and spontaneous in nature.The experimental data were analyzed by pseudo-first-order, pseudo-second-order model, and the intraparticle-diffusion for kinetics and Langmuir, Freundlich, and Temkin models for isotherms.Kinetic adsorption followed the pseudo-second-order model and the intraparticle-diffusion within pores controlled the adsorption rate. The experimental data yielded good fits with in the following isotherms order: Langmuir > Temkin > Freundlich, The maximum adsorption capacity of MO on DPB was found 461 mg.g^?1. The reusability study reveals the possibility of the reuse of DPB for three (03) cycles of adsorption–desorption, a slight decrease in the ability of methyl orange adsorption has noticed with the increase of the number of adsorption–desorption cycles : 81.03 %, 67.84 %, and 51.72 %, respectively. The found results of the present study show that the biochar derived from date palm petioles have the potential to be used as a promising adsorbent for the treatment of MO dye.     

Engineered biochar modified with iron as a new adsorbent for treatment of water contaminated by selenium

The purpose of this study was to develop an efficient method of biochar modification for effective removal of Se(VI) ions from water. Commercially available biochar produced from wheat straw was impregnated by Fe(NO₃)₃ (0.8, 4 and 10% w/v) and pyrolyzed at 200 °C. Optimum pH, adsorption kinetics, and Se(VI) adsorption isotherms were determined for the studied biochars. The modification significantly increased biochar’s ability for Se(VI) adsorption. The biochar modified with 10% Fe(NO₃)₃ has the highest adsorption effectiveness. The experimentally determined maximum adsorption capacity for the biochar modified with 10% Fe(NO₃)₃ was 14.3 mg g⁻¹ for pH 5, which was the optimum pH value. X-Ray Photoelectron Spectroscopy (XPS) and Photoacoustic Fourier Transform Infrared Spectroscopy (FTIR-PAS) investigation confirmed the presence of iron oxides/hydroxides on the surface of the modified biochar. The modification also resulted in the formation of oxygen containing functional groups. The study proved that the proposed modification can be efficient in increasing the biochar effectiveness in removing Se(VI) from water.     

Isotherms,kinetics, and thermodynamics of boron adsorption on fibrous polymeric chelator containing glycidol moiety optimized with response surface method

A fibrous boron chelator containing glycidol moiety (PE/PP-g-PVAm-G) was prepared by radiation induced grafting of N-vinylformamide (NVF) onto polyethylene/polypropylene (PE/PP) non-woven sheet followed by hydrolysis and immobilization of glycidol moiety. The glycidol density was controlled by optimization of the reaction parameters using the Box-Behnken design of response surface methodology (RSM). The properties of the PE/PP-g-PVAm-G were evaluated using Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM) and energy dispersive x-ray (EDX) analysis, X-ray diffraction (XRD) and thermal gravimetric analysis (TGA). A maximum glycidol density yield of 5.0 mmol·g⁻¹ was obtained with 11.8 vol%, 78.9 °C and 109.4 min for glycidol concentration, reaction temperature and time, respectively. The isotherms, kinetics, and thermodynamic behavior of boron adsorption on the optimized chelator were investigated. The boron adsorption was pH-dependent and attained a maximum adsorption capacity of 25.7 mg·g⁻¹. The equilibrium isotherm proceeded by Redlich–Peterson model whereas the kinetics was best expressed by the pseudo-second-order equation. The thermodynamic analysis revealed that boron adsorption is endothermic and spontaneous. The fibrous chelator demonstrated high boron selectivity and strong resistance to foreign ions with uncompromised regeneration efficiency after five adsorption/desorption cycles. The PE/PP-g-PVAm-G chelator seems to be very promising for boron removal from aqueous media.     

Biomass valorization of walnut shell into biochar as a resource for electrochemical simultaneous detection of heavy metal ions in water and soil samples: Preparation,characterization, and applications

Lately, due to its accessibility and eco-friendliness, walnut shell biochar (WS-BC) is gaining attention as an electrode material component in the electrochemical detection of water pollutants. The overall performance of WS-BC is reliant on the nature of raw biomass and the production methods as well. In our concept, biochar, prepared from raw walnut shell (WS) by pyrolysis, was added to a carbon paste electrode (CPE), and poly-tyrosine (p-Tyr) was electrodeposited on the surface of the BC-doped electrode. The conditions of the elaboration of the electrode, such as pH, potential, and the number of deposition cycles, pH were optimized. The obtained p-Tyr-BC-CPE platform was tested for the determination of cadmium, lead, copper, and mercury ions in water and soil samples, using square wave voltammetry (SWV). The raw WS biomass and its BC were examined by thermal analysis (TG-DSC), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDX) techniques. The synergistic effects of the coexistence of the WS-BC and the thin film of p-Tyr, for the detection of traces of heavy metal ions were investigated by electrochemical tests. The electrochemical characterization of the unmodified and modified electrodes was performed using the cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods, while the Cd²⁺, Pb²⁺, Cu^2+, and Hg²⁺ detection experiments were studied using the CV and SWV techniques. The optimized experimental conditions for the p-Tyr-BC-CPE platform were evaluated. The obtained electrochemical results showed that the p-Tyr-BC-CPE platform produced excellent sensitivity toward the heavy metal ions: LOD of 0.086, 0.175, 0.246, and 0.383 nM for Cd(II), Pb(II), Cu(II) and Hg(II), respectively. The modified electrode platform displayed high selectivity, stability, and good reproducibility.     

Mesoporous hollow silicon spheres modified with manganese ion sieve: Preparation and its application for adsorption of lithium and rubidium ions

In this work, mesoporous hollow silicon spheres modified with 3‐aminopropyl‐ triethoxysilane (APTES) of loaded hydrogen manganese oxide lithium ion sieve (APTES/HMO‐ HS) was prepared. The structure and morphology of as‐prepared APTES/HMO‐HS were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, transmission electron microscopy and nitrogen adsorption‐desorption measurements. The Brunner‐Emmet‐Teller (BET) surface areas, pore diameters and pore volumes of APTES/HMO‐HS decreased gradually, while the Li:Mn:Si molar ratios range from 1:1:50 to 1:1:10. The obtained hierarchical porous APTES/50HMO‐HS has a high specific surface area (557.1694 m² g^‐1). The lithium and rubidium ions solutions were used to measure the adsorption performance of the APTES/HMO‐HS adsorbent. The pseudo‐first‐order and pseudo‐second‐order kinetics, Langmuir and Freundlich isotherms of APTES/HMO‐HS were investigated; suggesting that the adsorption kinetics can be described by the pseudo‐second‐order kinetic model and the adsorption isotherms well fits the Langmuir isotherm equation. The obtained results show that the prepared APTES/HMO‐HS exhibits excellent abilities to simultaneously and selectively recover Li⁺ and Rb⁺ (11.22 mg·g^‐1 and 8.31 mg·g^‐1) and have a promising application in the simultaneous adsorption of lithium and rubidium ions.     

Preparation of PSSS‐grafted polysulfone microfiltration membrane and its rejection and removal properties towards heavy metal ions

3‐Hydroxy‐N,N‐diethylaniline (HDEA) as a tertiary aromatic amine was introduced onto the surface of chloromethylated polysulfone (CMPSF) microfiltration membrane through modification reaction, resulting in the modified membrane PSF‐DEA. A redox surface‐initiating system (DEA/APS) was constituted by the bonded tertiary aromatic amine group DEA and ammonium persulfate (APS) in aqueous solution, and so, the free radicals formed on the membrane initiated sodium p‐styrenesulfonate (SSS) as an anionic monomer to produce graft polymerization, getting the grafting‐type composite microfiltration membrane, PSF‐g‐PSSS membrane. Subsequently, the adsorption property of PSF‐g‐PSSS membrane for three heavy metal ions, Pb²⁺, Zn²⁺, and Hg²⁺ ions, was fully examined, and the rejection performance of PSF‐g‐PSSS membrane towards the three heavy metal ions was emphatically evaluated via permeation experiments. The experimental results show that by the initiating of the surface‐initiating system of DEA/APS, the graft polymerization can smoothly be carried out under mild conditions. PSF‐g‐PSSS membrane as a functional microfiltration membrane has strong adsorption ability for heavy metal ions by right of strong electrostatic interaction (or ion exchange action) between the anionic sulfonate ions on the membrane and heavy metal ions. The order of adsorption capacity is Pb²⁺ > Zn²⁺ > Hg²⁺, and the adsorption capacity of Pb²⁺ ion gets up to 2.18 μmol/cm². As the volume of permeation solutions, in which the concentrations of the three metal ions are 0.2 mmol/L, are in a range of 50 to 70 mL, the rejection rate of PSF‐g‐PSSS membrane for the three heavy metal ions can reach a level of 95%, displaying a fine rejection and removing performance towards heavy metal ions.     

Tailoring biochar by PHP towards the oxygenated functional groups (OFGs)-rich surface to improve adsorption performance

In this work, a modification method of H₃PO₄ plus H₂O₂ (PHP) was introduced to targetedly form abundant oxygenated functional groups (OFGs) on biochar, and methylene blue (MB) was employed as a model pollutant for adsorption to reflect the modification performance. Results indicated that parent biochars, especially derived from lower temperatures, substantially underwent oxidative modification by PHP, and OFGs were targetedly produced. Correspondingly, approximately 21.5-fold MB adsorption capacity was achieved by PHP-modified biochar comparing with its parent biochar. To evaluate the compatibility of PHP-modification, coefficient of variation (CV) based on MB adsorption capacity by the biochar from various precursors was calculated, in which the CV of PHP-modified biochars was 0.0038 comparing to 0.64 of the corresponding parent biochars. These results suggested that the PHP method displayed the excellent feedstock compatibility on biochar modification. The maximum MB adsorption capacity was 454.1 mg/g when the H₃PO₄ and H₂O₂ fraction in PHP were 65.2% and 7.0%; the modification was further intensified by promoting temperature and duration. Besides, average 94.5% H₃PO₄ was recovered after 10-batch modification, implying 1.0 kg H₃PO₄ (85%) in PHP can maximally modify 2.37 kg biochar. Overall, this work offered a novel method to tailor biochar towards OFGs-rich surface for efficient adsorption.