Synergetic treatment of dye contaminated wastewater using microparticles functionalized with carbon nanotubes/titanium dioxide nanocomposites

The highly efficient treatment of azo dye contaminated wastewater from the textile industry is an important but challenging problem. Herein, polydimethylsiloxane (PDMS) microparticles, incorporating multiple-walled carbon nanotubes/titanium dioxide (MWCNTs/TiO₂) nanocomposites, were successfully synthesized to treat wastewater containing Rhodamine B (RhB) dyes in a synergetic approach, by combining sorption and photocatalytic degradation. The surfactant wrapping sol–gel method was applied to synthesize MWCNTs/TiO₂ nanocomposites with TiO₂ nanoparticles evenly distributed on the surface of the MWCNTs. The PDMS microparticles were fabricated with an oil-in-water (O/W) single emulsion template, using needle-based microfluidic devices. MWCNTs/TiO₂ nanocomposites (at a weight ratio of 1%, and 2%, respectively) were mixed with the PDMS precursor as the dispersed phase, and an aqueous solution of polyvinyl alcohol (PVA) was used as the continuous phase. Highly monodispersed microparticles, with average diameters of 692.7 μm (Coefficient of Variation, CV = 0.74%) and 678.3 μm (CV = 1.04%), were formed at an applied flow rate of the dispersed and continuous phase of 30 and 200 μL min⁻¹, respectively. The fabricated hybrid microparticles were employed for the treatment of RhB, involving a dark equilibrium for 5 hours and UV irradiation for 3 hours. The experimental conditions of applied PDMS type, mass loading amount, treatment duration, photodegradation kinetics, initial concentration of pollutants and environmental pH values were investigated in this work. The PDMS microparticles with 2 wt% MWCNTs/TiO₂ nanocomposites can exhibit a removal efficiency of 85%. Remarkably, an efficiency of 70% can be retained after the microparticles have been recycled and reused for 3 cycles. The PDMS–MWCNTs/TiO₂ microparticles possess a superior performance over conventional treatment approaches for dye contaminated wastewater, especially in recyclability and the prevention of secondary pollution. This work provides a feasible and eco-friendly route for developing an efficient and low-cost microfluidic method for treating complicated water environmental systems.

PDMS–MWCNTs/TiO₂ microparticles made by microfluidics can achieve 85% removal efficiency of RhB pollutant in wastewater via synergetic treatment.     

Fast removal of methylene blue from aqueous solution using coal-based activated carbon

Coal-based activated carbons (CACs) were prepared from three long flame coals with different ash and volatile matter content. CACs prepared by coal with high ash (6.74%) and volatile matter content (34.31%) showed better adsorption efficiency towards MB (547.35 mg g⁻¹) due to higher surface area and pore volume. The effect of coal to activating agent ratio (CAR) was also investigated in a batch reactor. The porosity development is closely related to the CAR. The calculated monolayer adsorption amount (714.29 mg g⁻¹) was found on YLC-AC-3 with a surface area of 1212.50 m² g⁻¹. The equilibrium data were favorably described by the Langmuir and Freundlich isotherm models, and adsorption kinetics fitted well to the pseudo-second order model. The removal efficiency remains at 98.21% after five runs. The results of the present study suggest that CACs are potential and effective adsorbents in fast removal of dyes from aqueous solution.

A monolayer adsorption amount of MB (714.29 mg g⁻¹) was found on a coal-based activated carbon prepared by a simple method.     

Removal of Pb(ii) and Cd(ii) from wastewater using arginine cross-linked chitosan–carboxymethyl cellulose beads as green adsorbent

A one pot approach has been explored to synthesize crosslinked beads from chitosan (CS) and carboxymethyl cellulose (CM) using arginine (ag) as a crosslinker. The synthesized beads were characterized by FTIR, SEM, EDX, XRD, TGA and XPS analysis. The results showed that CS and CM were crosslinked successfully and the obtained material (beads) was analyzed for adsorption of Cd(ii) and Pb(ii) by using batch adsorption experiments; parameters such as temperature, contact time, pH and initial ion concentration were studied. Different kinetic and thermodynamic models were used to check the best fit of the adsorption data. The results revealed that the kinetics data of the adsorption of Pb(ii) and Cd(ii) ions shows the best fit with the pseudo second order model whereas the thermodynamics data shows the best fit with the Langmuir isotherm with maximum adsorption capacities of 182.5 mg g⁻¹ and 168.5 mg g⁻¹ for Pb(ii) ions Cd(ii) ions, respectively. For the recovery and the regeneration after the one use of the beads, several adsorption–desorption cycles were carried out to check the reusability and recovery of both the metal ion and the adsorbent without the loss of maximum adsorption efficiency.

Remediation of Pb(ii) and Cd(ii) containing wastewater by arginine crosslinked chitosan/carboxymethyl cellulose beads.     

Correction: Removal of Pb(ii) and Cd(ii) from wastewater using arginine cross-linked chitosan–carboxymethyl cellulose beads as green adsorbent

Correction for ‘Removal of Pb(ii) and Cd(ii) from wastewater using arginine cross-linked chitosan–carboxymethyl cellulose beads as green adsorbent’ by Kaiser Manzoor et al., RSC Adv., 2019, 9, 7890–7902.

The authors regret that an incorrect version of the SEM image shown in Fig. 3b was included in the original article. The correct version of Fig. 3 is presented below.Open in a separate windowFig. 3SEM micrographs of (a) CS, (b) CM, (c) CS-ag-CM, (d) Pb(II)/Cd(II)-CS-ag-CM(e) Pb(II)/Cd(II)-CS-ag-CM and EDX spectrum of (f) CS-ag-CM and (g) Pb(II)/Cd(II)-CS-ag-CM.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

Removal of atrazine from aqueous solutions onto a magnetite/chitosan/activated carbon composite in a fixed-bed column system: optimization using response surface methodology

In this study, a magnetite/chitosan/activated carbon (MCHAC) composite is proposed as an efficient adsorbent for the removal of atrazine from aqueous solutions. The prepared composite was characterized using Fourier-transform infrared (FTIR) and X-ray diffraction (XRD) methods. Response surface methodology (RSM) coupled with composite central design (CCD) were used to optimize the effects of the four independent variables, pH, initial concentration of atrazine (C₀), bed depth (H), and flow rate (Q), which influence the adsorption process. The experimental results modeled using response surface methodology (RSM) coupled with central composite design (CCD) (RSM–CCD) indicated a quadratic relationship with p < 0.0001 for adsorption capacity at saturation (q_s) and fraction of bed utilization (FBU). The results of the experiments performed under the optimized conditions, pH = 5.07, C₀ = 137.86 mg L⁻¹, H = 2.99 cm and Q = 1.038 mL min⁻¹, showed a q_s value of 62.32 mg g⁻¹ and FBU of 72.26%, with a deviation value of less than 0.05 from the predicted q_s and FBU values. The obtained breakthrough curves were fitted with four mathematical models, Thomas, Bohart–Adams, Yan and Yoon–Nelson, in order to determine the limiting step of the mass transfer of the atrazine adsorption onto the composite. A desorption study of the composite revealed the high reuse potential for MCHAC, thus, the prepared material could be used as a low-cost and efficient adsorbent for the decontamination of polluted wastewater.

In this study, a magnetite/chitosan/activated carbon (MCHAC) composite is proposed as an efficient adsorbent for the removal of atrazine from aqueous solutions.     

Differential pulse voltammetry detection of Pb(ii) using nitrogen-doped activated nanoporous carbon from almond shells

Almond shell-based charcoal was prepared by carbonizing almond shells in a nitrogen atmosphere. Nanoporous carbon (NPC) was formed via activating the obtained charcoal using potassium hydroxide as an activating agent, followed by the synthesis of nitrogen-doped nanoporous carbon (N-NPC) via a hydrothermal reaction using urea as the nitrogen source. The obtained N-NPC possessed a large surface area (1075 m² g⁻¹), narrow pore-size distribution (1–2 nm) and nitrogen content reaching 2.23 wt%. Using N-NPC with Nafion to modify a glassy carbon electrode, a highly sensitive electrochemical sensor was fabricated for the determination of Pb(ii) in aqueous solutions with differential pulse anodic stripping voltammetry (DPASV). The peak current of Pb(ii) showed linearity over concentrations from 2.0 to 120 μg L⁻¹ and the detection limit (S/N = 3) was estimated to be 0.7 μg L⁻¹ for Pb(ii), which was 15-fold lower than the guideline value of drinking water given by the World Health Organization (WHO). The experimental data indicated that this easy and low-cost method is an accurate and fast method for the detection of trace Pb(ii).

Almond shell-based charcoal was prepared by carbonizing almond shells in a nitrogen atmosphere.     

Preparation of activated carbon nanofibers using degradative solvent extraction products obtained from low-rank coal and their utilization in supercapacitors

In this study, low-rank coal was separated into three solid fractions by a degradative solvent extraction method. The high-molecular-weight extract (termed Deposit) had some outstanding properties such as high carbon content, almost no ash, high aromaticity, good thermoplasticity and high solubility in DMF. Therefore, Deposit with some proportion of polyacrylonitrile (PAN) was used to prepare activated carbon nanofibers by electrospinning and CO₂ activation. Moreover, the utilization of these carbon nanofibers as a supercapacitor electrode was preliminarily investigated. The results showed that the specific surface area of the Deposit-based carbon nanofibers (1005 m² g⁻¹) was significantly higher than that of the nanofibers obtained from pure PAN (688 m² g⁻¹). TGA simulations showed that this was caused by the different thermal decomposition behaviors of Deposit and PAN during the stabilization and activation processes. In addition, the Deposit-based carbon nanofibers showed a better specific capacitance (192.6 F g⁻¹ at 1 A g⁻¹) and cycling performance (retention rate of 89.8% after 1000 cycles at 5 A g⁻¹) in a 6 M KOH electrolyte. The factors, such as the enhanced surface area and pore volume and decreased average fiber diameter, affected the electrochemical properties of the carbon nanofibers. Thus, it has been proven that the high-molecular-weight extract obtained from low-rank coal by degradative solvent extraction is a promising precursor for the preparation of carbon nanofibers with unique electrochemical properties.

Activated carbon nanofibers for supercapacitor electrodes were prepared by the electrospinning method using degradative solvent extracts from low-rank coal and PAN.     

The removal of 3-monochloropropane-1,2-diol ester and glycidyl ester from refined-bleached and deodorized palm oil using activated carbon

Palm oil has fulfilled most of the oil needs in the food sector in the world. However, palm oil is indicated to contain small amounts of compounds that are harmful to humans, especially to infants. These toxic contaminants are 3-monochloropropanediol (3-MCPD) esters and glycidyl esters (GE), which are formed during the deodorization of palm oil at high temperatures. This study aims to reduce the 3-MCPD ester concentration in refined, bleached, and deodorized palm oil (RBDPO) through adsorption using activated carbon. The activated carbons were treated with heat and acid-washing using HCl at various concentrations and were characterized. The treatment altered the physicochemical characteristics of the activated carbon (surface area, pore volume, pH_PZC, and CEC), resulting in the enhancement of its adsorption characteristics (adsorption capacity). The activated carbon treated with 2 N HCl (AC 2 N) was chosen as the proper adsorbent, due to better surface area, better pore volume, highest CEC value, and better positive charge in RBDPO. The 3-MCPD and GE adsorption capacity of AC 2 N was 1.48 mg g⁻¹ and 29.68 mg g⁻¹, respectively. The adsorption ability of pretreated activated carbon towards 3-MCPD esters was examined in a batch system at various adsorption temperatures. The 3-MCPD ester concentration in RBDPO was successfully reduced by up to 80% at 35 °C using the activated carbon treated with 2 N HCl solution. On the other hand, the activated carbon was able to reduce the other contaminant of GE in RBDPO up to 97% from the initial concentration of GE.

The removal of 3-MCPD and GE from RBDPO was done through adsorption using activated carbon. The maximum 3-MCPD and GE removals result in 80% and 97%, respectively.     

活性炭与树脂对尿毒症患者中分子物质、甲状旁腺素的体外吸附研究

目的分析探讨活性炭和树脂对尿毒症患者体内的中分子物质总量(middle molecular substances,MMS)及甲状旁腺素(parathyroid hormone,PTH)的清除性能差异。方法取维持性透析患者的血液,随机分为4组,分别用AC活性炭、MR1、MR2、MR3树脂4种吸附剂进行体外吸附,检测吸附前后血液中的MMS和PTH,结合吸附剂的孔结构检测,分析活性炭与树脂对MMS、PTH的清除性能差异。结果同组内吸附前后比较,4组血样的MMS、PTH水平均显著降低(P<0.01;MMS指标P值分别为0.006、0.001、0.001、0.000,PTH指标P值均为0.000)。对MMS清除水平,AC组最高(32.73%±3.29%),MR1组(22.96%±7.18%)最低,且2组比较有统计学意义(P<0.05;P=0.027),而3种树脂间MMS清除水平差异无统计学意义。对PTH清除水平,MR1组最高(90.52%±4.05%),MR2组次之(77.43%±3.65%),MR3组较小(63.71%±1.49%),AC组最低(36.53%±4.95%),且4组差异显著(P<0.01;P值均为0.000)。结论活性炭由于孔径分布范围广,能吸附的毒素分子量范围更广,对中分子物质总量清除更有利;大孔吸附树脂具有较为集中的孔径分布,对以PTH为目标的单一中分子毒素清除更有利。     

Efficient removal of sulfamerazine (SMR) by ozonation in acetic acid solution after enrichment SMR from water using granular activated carbon

Sulfamerazine (SMR) as a persistent organic pollutant in waste streams is of growing environmental concern. This study explores the extraction SMR from water into an acetic acid (AA) solution using granular activated carbon (GAC), and removal of SMR by ozonation in AA solution. Systematic experiments have shown that GAC can be used as an adsorbent to transfer sulfamerazine from water to AA solution. SMR removal efficiency is 99.5% in 10% AA aqueous solution, which is better than in water. The removal rate of SMR in the AA solution decreased as the initial molar ratio of SMR and O₃ increased. The removal rate of SMR decreased with Fe³⁺ present in the reactive system. The removal of SMR is dominated by indirect ozonation in water, while the SMR removal is an effect of both direct and indirect ozonation in AA solution. It is a very efficient process for the degradation of SMR in micro polluted water when using combined GAC adsorption–desorption in AA solution and ozonation of the resulting solution.

Sulfamerazine (SMR) as a persistent organic pollutant in waste streams is of growing environmental concern.     

Removal of As(iii) and As(v) from water using green,silica-based ceramic hollow fibre membranes via direct contact membrane distillation

Arsenite [As(iii)] and arsenate [As(v)] removal by direct contact membrane distillation (DCMD) using novel hydrophobic green, silica-based ceramic hollow fibre membranes derived from agricultural rice husk was investigated in this work. The green ceramic hollow fibre membranes were prepared from amorphous (ASHFM) and crystalline (CSHFM) silica-based rice husk ash and modified to be hydrophobic via immersion fluoroalkylsilane (FAS) grafting of 1H,1H,2H,2H-perfluorodecyltriethoxysilane. Superhydrophobic contact angle values up to 157° and 161° were obtained for ASHFM and CSHFM, respectively. Remarkably, the membrane surface morphology mimicked a look-alike lotus-leaf structure with decrement in pore size after grafting via the silane agent for both membranes. The effect of arsenic pH (3–11), arsenic concentration (1–1000 ppm) and feed temperature (50–80 °C) were studied and it was found that feed temperature had a significant effect on the permeate flux. The hydrophobic CSHFM, with a flux of 50.4 kg m⁻² h⁻¹ for As(iii) and 51.3 kg m⁻² h⁻¹ for As(v), was found to be the best of the tested membranes. In fact, this membrane can reject arsenic to the maximum contaminant level (MCL) limit of 10 ppb under any conditions, and no swelling mechanism of the membranes was observed after testing for 4 hours.

Arsenite [As(iii)] and arsenate [As(v)] removal by direct contact membrane distillation (DCMD) using novel hydrophobic green, silica-based ceramic hollow fibre membranes derived from agricultural rice husk was investigated in this work.     

Simultaneous capture of methyl orange and chromium(vi) from complex wastewater using polyethylenimine cation decorated magnetic carbon nanotubes as a recyclable adsorbent

Most recently, the continuous deterioration of the aquatic environment triggered by both heavy metals and synthetic organic dyes has imparted serious threats to the ecosphere and drinking water safety. However, it is still extremely challenging to treat complex wastewater containing these two classes of pollutants via a one-step method owing to the significant differences in their physicochemical properties. In the current work, versatile magnetic MWCNTs decorated with PEI (denoted as MWCNTs@Fe₃O₄/PEI) was fabricated by a facile, rapid and reproducible strategy and applied to as a robust adsorbent for simultaneously removing methyl orange (MO) and Cr(vi) from aqueous solutions. The physicochemical properties of the as-designed nanohybrid were investigated using various analytical techniques, i.e. XRD, FT-IR, SEM, TEM, VSM, zeta potential, etc. It was found that the surface charge properties of the MWCNTs as well as its dispersion in aqueous solution were greatly changed after the introduction of PEI molecules. The resulting nanohybrid exhibited attractive adsorption capabilities toward anionic MO and Cr(vi). In the perspective of a mono-pollutant system, the time-dependent adsorption process matched well with a pseudo-second-order kinetics equation, the adsorption isotherm data at r.t. were well fitted by a Langmuir model with maximum monolayer uptake capacity of 1727.6 mg g⁻¹ for MO and 98.8 mg g⁻¹ for Cr(vi), and the removal process of both pollutants was thermodynamically spontaneous and exothermic. In the MO-Cr(vi) binary system, the uptake of Cr(vi) by the as-prepared adsorbent was evidently enhanced by the presence of MO, while the coexisting Cr(vi) exerted a small negative effect on the sorption of MO; which was attributed to the different adsorption mechanisms of both pollutants on the as-recommend adsorbent. The much better adsorbing performance of the resulting MWCNTs@Fe₃O₄/PEI for MO and Cr(vi) than that of the pristine MWCNTs or the MWCNTs/Fe₃O₄ composite was mainly ascribed to the high surface area of the MWCNTs, the high density of protonated N-rich groups of PEI as well as the excellent dispersion and solubility of the resulting nanocomposites. Moreover, the obtained nanohybrids can be easily recovered after being used by a permanent magnet and still retained high stability and excellent reusability after consecutive adsorption–desorption cycles, implying its great potential in practical applications. Therefore, the as-fabricated MWCNTs@Fe₃O₄/PEI composite could be recommended as a promising candidate adsorbent for the simultaneous capture of MO and Cr(vi) from complex wastewater via multiple uptake mechanisms (e.g. electrostatic attraction, π–π stacking and hydrogen bonding).

An MWCNTs@Fe₃O₄/PEI composite was facilely fabricated as a robust adsorbent for simultaneously capturing methyl orange (MO) and Cr(vi) from complex wastewater.     

Sustainable competitive adsorption of methylene blue and acid red 88 from synthetic wastewater using NiO and/or MgO silicate based nanosorbcats: experimental and computational modeling studies

The competitive adsorption of cationic and anionic model molecules; methylene blue (MB) and acid red 88 (AR88), respectively, in aqueous solutions onto NiO and/or MgO SBNs was studied. Adsorption isotherms, kinetics and pH effect were investigated in batch modes. Computational modeling was conducted on Acclerys Material Studio for MB and AR88 adsorption. pH study showed that the adsorption is strongly pH dependent, increases for MB while decreases for AR88 with increasing the pH from 4 to 11. Isotherm studies revealed that the Sips model was the best fit for both molecules in single cases, and thus the Extended-Sips model for the binary systems. The kinetics for the binary systems were well-described by the external mass transfer model; thus, film diffusion is the most dominant in the adsorption of both organic onto the SBNs. The adsorption uptakes in binary systems exceed 130 mg g⁻¹ for AR88 (167.7 MgO-SBNs, 132.93 NiO-SBNs, and 178.5 mg g⁻¹ NiO-MgO-SBN), while it reached an uptake of 76.2 MgO-SBNs, 81.5 NiO-SBNs, and 94.7 mg g⁻¹ NiO-MgO-SBNs for MB within the time needed to reach equilibrium (10 min). The adsorption of these two molecules in binary systems showed a synergistic effect onto the three types of SBNs, that enhanced the adsorption uptakes. Computational modeling confirmed the synergistic effect, the adsorption energy of binary systems was lower than that in single systems. Regeneration study was conducted over four adsorption cycles to confirm the sustainability of SBNs. They were stable under thermal oxidation at 400 °C, without any impact on the adsorption capacity.

Silica-based NiO and MgO nanosorbcats (SBNs) for competitive adsorption of methylene blue and acid red 88.     

Assessment and treatment of floodwater in the Vietnamese Mekong Delta using a simple filter system based on silver nanoparticles coated onto activated carbon derived from rice husk

The floods in the Vietnamese Mekong Delta have long caused a shortage of clean water supply, which has a significant impact on the indigenous people in the region. We have conducted a preliminary survey of the water quality of the Hau Giang River (one of the two main branches of the Mekong River) before, during, and after the flood season. The obtained results demonstrated that the water in the Hau Giang River was highly turbid and contaminated with a large number of harmful microorganisms. Thus, in this study, a simple filter system based on silver nanoparticles coated onto activated carbon derived from rice husk (AgNPs@AC) has been proposed for treating floodwater from the Hau Giang River. The optimal conditions for AgNPs@AC preparation were established. The prepared AgNPs@AC was then characterized using various surface analyses such as SEM, TEM, XRD, BET, FTIR, and DLS. The initial floodwater source would be pre-treated with polyaluminum chloride using the coagulation–sedimentation method to remove the suspended solids before being discharged into the filtration column containing AgNPs@AC. The results showed that the filter system based on AgNPs@AC performed well in removing turbidity, dissolved solids, suspended solids, color, and bacteria from the floodwater. In addition, it was determined that the filter column with a 30 mm thick AgNPs@AC layer could continuously process 1300 m³ of the floodwater and had a service life of more than two months. The findings of this study not only added to our understanding of the floodwater treatment capacity of activated carbon coated nanoparticles, but they also provided valuable information for water treatment plants along the Hau Giang River, aquatic ecosystem researchers, and public health researchers.

In this study, a simple filter system based on silver nanoparticles coated onto activated carbon derived from rice husk (AgNPs@AC) has been proposed for treating floodwater from the Hau Giang River.