Recent advancements in graphene adsorbents for wastewater treatment: Current status and challenges

From emerging pollutants to emerged threat, researchers are continuously looking for promising technologies for wastewater treatment. Adsorption has been identified as the most convenient approach for treating wastewater at low-cost and with high-efficiency. Recently, graphene and its derivatives have gained heightened attention as novel adsorbents because of their unique molecular structure and outstanding physicochemical properties. Heavy metals, dyes, polycyclic aromatic hydrocarbons (PAHs) and other pollutants, which are widely concerned recently, all show different adsorption behaviors. Numerous functional groups, resonating and delocalized π-electron system of graphene derivatives lead to the formation of various adsorptive interactions i.e., π-π interactions, electrostatic interactions, H-bonding, etc. with these venomous pollutants, and quarantine them in solution. The pristine form of graphene subsidiaries tends to exhibit low sorption efficiency due to high propensity of agglomeration, lack of selectivity, hydrophobicity and difficulty in phase separation after treatment. Therefore, designing of efficient graphene composites through the surface modification with numerous functional groups, polymers or nanoparticles is an ongoing challenge. Complex graphene composites are increasingly reported, but the fate of pollutants and adsorption mechanisms are still far to be fully clarified. This review summarizes the recent progresses in the application of graphene-based adsorbents for eliminating a wide range of organic and inorganic pollutants from wastewater. A critical explanation is provided on the synthesis of graphene adsorbents, systematic adsorption and desorption mechanisms along with their pollutant removal performances under different experimental conditions. A brief perspective on upcoming research needs and challenges involved in the designing of high-quality graphene-based adsorbents are highlighted.     

NaOH浓度对Cu_2O结构及甲醛乙炔化性能的影响

以CuCl_2·2H_2O为铜源,NaOH为沉淀剂,L-抗坏血酸钠为还原剂,采用液相还原法制备了Cu_2O,并将其应用于甲醛乙炔化反应制1,4-丁炔二醇.借助傅里叶变换红外光谱(FT-IR)、拉曼光谱(Raman)、X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和H_2程序升温还原(H2-TPR)等手段研究了NaOH浓度对Cu_2O结构、性质及催化性能的影响.结果表明,调变NaOH浓度改变了Cu2O的结晶度与粒径,从而使Cu_2O表现出不同的炔化性能.低NaOH浓度时,Cu_2O结晶度低,粒径小,易被还原为非活性的金属Cu;高浓度时,Cu_2O结晶度过高,粒径大,难以转化为活性物种炔化亚铜,两者均造成催化剂活性较低.而中等浓度的NaOH使Cu_2O具有了适宜的结晶度与粒径大小,Cu_2O可高效转化为炔化亚铜活性物种,表现出最优的炔化性能.     

Dechlorination of poly(vinylidene chloride) in NaOH/ethylene glycol as a function of NaOH concentration, temperature, and solvent

The wet dechlorination treatment of poly(vinylidene chloride) (PVDC) was evaluated at atmospheric pressure in a solution of NaOH in ethylene glycol (EG), as a function of NaOH concentration, temperature, and solvent. Hydroxide ion from NaOH was required for dechlorination with EG acting solely as a solvent. The wet treatment exhibited significantly enhanced dechlorination efficiency over traditional thermal techniques, with a reaction efficiency as high as 92.8% in 1.0 M NaOH at 190 °C. Dechlorination reactions of PVDC in both NaOH/EG and NaOH/H₂O were expressed by an apparent first-order reaction. At 190 °C, the apparent rate constant in 1.0 M NaOH/EG was approximately 1.4 times larger than in 1.0 M NaOH/H₂O, with an apparent activation energy of 82.8 kJ mol⁻¹, indicating that the reaction proceeded under chemical control. The degree of dechlorination increased with increasing reaction temperature, favouring the elimination of HCl over the hydroxyl substitution of chloride.     

Formation of gold and silver nanostructures within polyvinylpyrollidone (PVP) gel

Study on reduction of Au(III) and Ag(I) and the formation of Au and Ag nanostructures was performed on the gels of metal precursor and PVP polymer mixture. Some comparing samples were prepared for better understanding the role of reactants on the reduction of metal ions and further growth of nanocrystals. The results suggest that, in addition to its function of generating stable colloids, PVP not only has a reducing effect on metal ions, but also acts as a crystal growth modifier. At low temperatures, the reducing effect of PVP is strong on Ag(I) ions in AgNO₃, while the reduction of complex Au(III) ions in HAuCl₄ is slow, involving two steps of Au(III)→Au(I)→Au. In the study of temperature disturbance on crystal growth, Au nanoplates of new and well-defined star shape were observed. The differences in the size and shape of nanoparticles are discussed from the colloid chemistry.     

Study of the influence of NaOH treatment on the pyrolysis of different leather tanned using thermogravimetric analysis and Py/GC-MS system

This paper presents a study of the influence of a NaOH treatment on leather samples tanned using different tanning agents. Thermogravimetric analysis (TG/DTG) and flash pyrolysis (Py/GC-MS) was carried out on treated samples, and the results were compared with those obtained with the untreated samples. Treatment with sodium hydroxide seemed to decrease the temperature of maximum leather decomposition rate between 4 and 27 °C, depending on the tanning agent, and increased the range of temperatures where leather degradation occurs. From flash pyrolysis experiments, it was found that the volatile products obtained from NaOH-treated samples contain higher amounts of nitrogen compounds than those obtained from untreated samples. The results of a multivariate analysis applied to pyrolytic products obtained in the flash pyrolysis of samples showed greater similarity between the results obtained in all treated samples than between treated and untreated samples produced with the same tanning process.     

Progress and challenges in molecularly imprinted polymers for adsorption of heavy metal ions from wastewater

Molecularly imprinted polymers (MIPs), prepared by the interaction forces such as forming covalent or non-covalent bonds by crosslinkers and initiators, are new types of specific recognition polymers with particular cavities. This is an ideal class of materials for wastewater treatment because of the particular holes left by the elution process. This review discusses the development process, classification, synthesis principles, systems, and polymerization methods of MIPs. At the same time, the adsorption mechanism of Copper (Cu), Mercury (Hg), Chromium (Cr), Silver (Ag), and Lead (Pb) in the MIPs technique are studied. Finally, some suggestions and prospects for the future development of MIPs are also put forward.     

A study of irradiation in the treatment of wastewater

A grafting copolymer of starch and acrylamide was prepared by ⁶⁰Co-γ pre-irradiation. After purification, the copolymer was modified by a cationic reaction to form a cationic copolymer. The structure of the cationic copolymer was identified by IR and NMR spectroscopy. Using the industrial and sanitary municipal wastewater from the Factory of Wastewater Treatment of Gaobeidian in Beijing as the study sample, three-treatment methods: flocculation deposition, flocculation deposition combined with γ irradiation and the direct irradiation were carried out. COD was applied to evaluate the treatment effect. The preliminary results show that the method of flocculation deposition combined with γ irradiation was effective than the other two.     

Porous magnetic manganese oxide nanostructures: synthesis and their application in water treatment

Magnetic manganese oxide nanostructures are fabricated at room temperature by mixing a KMnO(4) solution and oleic acid capped Fe(3)O(4) particles. Oleic acid molecules capped Fe(3)O(4) particles are oxidized by potassium permanganate (KMnO(4)) in an aqueous solution to produce porous magnetic manganese oxide nanostructures. The synthesis technique can be extended to other MnO(x) structures with composition of different nanocrystals, such as quantum dots, noble metal crystals which may have important applications as catalysts, adsorbents, electrodes and advanced materials in many scientific disciplines. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption measurements are employed to characterize the structures. As an adsorbent in water treatment, the nanostructures possess a large adsorption capability and high organic pollutant removal rates due to the large surface area and pore volume. The nanostructures are recyclable as their adsorption capability can be recovered by combustion. Furthermore, the strong magnetism exhibited by the structures provides an easy and efficient separation means in wastewater treatment under an external magnetic field.     

Metal content variation in wastewater and biosludge from Bangkok's central wastewater treatment plants

The objectives of this study were to determine the metal contents and their variations in influent, effluent and biosludge, and to evaluate the potential environmental impact of biosludge generated from the Bangkok, Thailand central wastewater treatment plants. The variation in influent metal content was site-specific and could be related to the economic activities of small-scale companies. An activated sludge process could remove some level of the metal content via a combination of biological and physicochemical processes. The variation in metal removal efficiencies strongly depended upon the influent wastewater characteristics and composition. Metal occurrence in biosludge was similar to the metals found in the influent. Iron was the most abundant while Cd had the lowest occurrence. A longer excess sludge operational condition and storage time may increase metal contents in biosludge due to the decomposition of biodegradable organic matter by microorganisms. According to the speciation results, the biosludge studied had a low mobility and availability index, except the RK plant biosludge. Most trace metals of interest were in the less mobile and bioavailable forms. The most mobile exchangeable and moderately mobile carbonate fractions of Cd, Mn, Ni and Zn were relatively low (5–30%). Biosludge from RK had a total Cu concentration higher than the limits, and to some extent exchangeable and carbonate fractions that were relatively high (∼ 40%).     

Removal of Cu(II) and Zn(II) from industrial wastewater by acid-activated montmorillonite-illite type of clay

An acid-activated montmorillonite-illite type of clay collected from the Gulbarga region of Karnataka, India was examined for removing copper and zinc ions from industrial wastewater containing Cu(II), Zn(II) and minor amounts of Pb(II). Langmuir, Freundlich, Brunauer-Emmett-Teller (BET), and competitive Langmuir (two competing ions) isotherms were fitted to experimental data and the goodness of their fit for adsorption was compared. The shapes of isotherms obtained indicated multilayer adsorption of Cu(II) and monolayer adsorption of Zn(II) on the acid-activated clay. Competitive adsorption was found to be significant due to the presence of Cu(II) in the wastewater.     

Activated carbon blended with grape stalks powder: Properties modification and its application in a dye adsorption

In this study, activated carbon was blended with grape stalks powder to adsorb methylene blue (MB) dye with various concentrations from a wastewater. For this purpose, five independent variables involving pH (2–13), contact time (5–270 min), grape stalks powder dosage (0.1–10 g/l), methylene blue initial concentration (20–300 mg/l), and activated carbon dosage (0.1–10 g/l) for methylene blue adsorption were studied. The Central Composite Design (CCD) under Response Surface Methodology (RSM) was applied to estimate the independent variables effects on the methylene blue adsorption. The pseudo- first order, pseudo-second order, Elovich and intraparticle diffusion models were employed to study the adsorption kinetics and isotherm. The Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models were applied to investigate the adsorption isotherm. It was concluded that the intraparticle diffusion isotherm and pseudo-second order kinetic models could show the best results. Furthermore, some data such as physical adsorption (by analyzing FTR and applying some standard equations) and mean free energy (E) were discovered in this research. Finally, activated carbon blended with grape stalks powder as an effective bio-adsorbent for the methylene blue reduction from a wastewater was introduced.     

Dechlorination of poly(vinyl chloride) using NaOH in ethylene glycol under atmospheric pressure

A solution of NaOH dissolved in ethylene glycol (EG) was effective in the dechlorination of poly(vinyl chloride) (PVC) at atmospheric pressure. The degree of dechlorination increased with increasing temperature, reaching a maximum of 97.8% at 190 °C. The dechlorination proceeded under chemical control and exhibited first-order kinetics with an apparent activation energy of 170 kJ mol⁻¹. The apparent rate constant for dechlorination in 1.0 M NaOH/EG was approximately 150 times greater than that in 1.0 M NaOH/H₂O. In addition, dechlorination was faster at atmospheric pressure in NaOH/EG than under high pressure in NaOH/H₂O. The dechlorination reaction occurs via a combination of E2 and S_N2 mechanisms.     

Self‐assembled three‐dimensional flower‐like α‐Fe2O3 nanostructures and their application in catalysis

Three‐dimensional flower‐like α‐Fe₂O₃ nanostructures have been successfully synthesized by a simple surfactant‐free environmental friendly solvolthermal process. The as‐prepared products were investigated by X‐ray powder diffraction, transmission electron microscopy, and field emission scanning electron microscopy. By adjusting the synthetic parameters, the shape of the α‐Fe₂O₃ nanostructures can be controlled. The three‐dimensional flower‐like α‐Fe₂O₃ nanostructures were found to be highly active as catalysts for phenol alkylation. The effects of various parameters, such as reaction temperature, reaction time and the amount of catalyst, were studied. The catalyst was stable and could be reused three times in normal atmosphere without suffering appreciable loss in catalytic activity. Copyright © 2009 John Wiley & Sons, Ltd.     

Dissolution and regeneration of cellulose in NaOH/thiourea aqueous solution

A novel cellulose solvent, 1.5 M NaOH/0.65 M thiourea aqueous solution, was used to dissolve cotton linters having a molecular weight of 10.1 × 10⁴ to prepare cellulose solution. Regenerated cellulose (RC) films were obtained from the cellulose solution by coagulating with sulfuric acid (H₂SO₄) aqueous solution with a concentration from 2 to 30 wt %. Solubility of cellulose, structure, and mechanical properties of the RC films were examined by infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, ¹³C NMR, and tensile tests. ¹³C NMR analysis indicated that the novel solvent of cellulose is a nonderivative aqueous solution system. The presence of thiourea enhanced significantly the solubility of cellulose in NaOH aqueous solution and reduced the formation of cellulose gel; as a result, thiourea prevented the association between cellulose molecules, leading to the solvation of cellulose. The RC film obtained by coagulating with 5 wt % H₂SO₄ aqueous solution for 5 min exhibited higher mechanical properties than that with other H₂SO₄ concentrations and a homogenous porous structure with a mean pore size of 186 nm for free surface in the wet state. The RC film plasticized with 10% glycerin for 5 min had a tensile strength of 107 MPa and breaking elongation of 10%, and about 1% glycerin in the RC film plays an important role in the enhancement of the mechanical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1521–1529, 2002     

Wastewater treatment by cyclodextrin polymers and noble metal/mesoporous TiO2 photocatalysts

Pollution of water from a wide range of organic pollutants is a serious environmental problem. Conventional water treatment technologies are not very effective for reducing the concentration of these pollutants to a desirable level. The aim of this work was to evaluate the efficiency of two technologies in reducing the pollutant concentration of two wastewater samples. Therefore, cross-linked cyclodextrin (CD) polymers were synthesized and their adsorption capacities were evaluated. An emerging oxidation process using doped TiO₂ was also evaluated. For both technologies, we observed a decrease in the total organic carbon (TOC) content due either to the adsorption of pollutants by CD polymers or to the mineralization of pollutants by photocatalysis.     

Identification of toxic compounds in wastewater treatment plants during a field experiment

Chemical analysis and toxicity bioassays were used in conjunction to determine the toxic compounds present in wastewater. This combined methodology was applied to wastewater samples collected at two wastewater treatment plants (WWTP) from the area of Barcelona (Spain), during a field experiment carried out from 1-4 April 2000. The efficiency of the WWTP was evaluated by collecting and analyzing samples at various stages of the water treatment process. The samples corresponded to the raw influent, from first settlement—before biological treatment—and from the effluent.Two bioluminescence inhibition assays: ToxAlert^®10 and ToxAlert^®100 from Merck both based on the bioluminescence inhibition of Vibrio fischeri (marine bacterial specie) were used. ToxAlert^®10 is a portable device with no temperature control and uses freeze-dried bacterial reagent and ToxAlert^®100 uses liquid-dried bacterial reagent and the incubation takes place at controlled temperature. Both tests showed similar results.Besides the toxicity studies, the wastewater samples were characterized by various analytical protocols involving the use of solid phase extraction (SPE) followed by liquid chromatography-mass spectrometry (LC-MS). Phenols, non-ionic surfactants, linear alkyl benzene sulphonates, benzene and naphthalene sulphonates and micro-pollutants with high endocrine-disrupting effects like estradiol and ethynyl estradiol were identified at the WWTP.The toxic responses obtained for the samples collected at WWTP were defined by the 50% effective concentration (EC₅₀), the Toxicity Units (TU) and the toxicity impact index (TII₅₀). The toxic effect at the different steps of the WWTP was attributed to the compounds identified and quantified by LC-MS like transformation products of nonylphenol polyethoxylate such as nonylphenol and nonylphenol carboxylate.     

Odour-causing organic compounds in wastewater treatment plants: evaluation of headspace solid-phase microextraction as a concentration technique

Odorous emissions from wastewater collection systems and treatment facilities affecting quality of life have given local populations reasons to complain for decades. In order to characterise the composition of such malodorous emissions, a method based on headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC-MS) has been developed to determine a list of compounds belonging to different chemical families, which have been previously described as potentially responsible for odour complaints, in wastewater matrices. Some parameters affecting the chromatographic behaviour of the target compounds were studied (e.g. splitless time). Experimental conditions affecting the extraction process (temperature, time and salt content) were evaluated by applying a factorial design at two levels. Using a DVB/CAR/PDMS fibre and the optimised HS-SPME conditions, calibration curves were constructed with detection limits in the range of 0.003-0.6 μg L(-1). Recovery values higher than 70% and relative standard deviation values between 5 and 16% (n=5) were obtained for all compounds and found to be satisfactory. In wastewater samples, a decrease in the concentration of the analysed compounds through the different treatments was observed. Most of the target analytes were found in influent samples while only octanal and carvone were detected in samples from the plant effluent.     

Synthesis and characterization of cellulose derivatives prepared in NaOH/urea aqueous solutions

We successfully synthesized hydroxypropylcellulose (HPC) and methylcellulose (MC) in high yields from cellulose in 6 wt % NaOH/4 wt % urea aqueous solutions at 25 °C. The cellulose derivatives were characterized with NMR, size exclusion chromatography/laser light scattering, gas chromatography (GC), ultraviolet, and solubility measurements in different solvents. According to the results of solution ¹³C NMR and GC, the individual degree of substitution (DS; i.e., the average number of substituted hydroxyl groups in the monomer unit) at C‐2 hydroxyl groups was slightly higher than the DS values at C‐3 and C‐6 hydroxyl groups for HPC and MC. In comparison with traditional systems, NaOH/urea aqueous solutions were proved to be a stable and more homogeneous reaction medium for preparing cellulose ether with a more uniform microstructure. The low limits for the average number of moles of the substituent groups per monomer unit and the DS value of water‐soluble HPC were 1.03 and 0.85, respectively. MC (DS = 1.48) had good solubility in both water and organic solvents, and the precipitation point occurred at about 67 °C for a 2% (w/v) aqueous solution. In this way, we could provide a simple, pollution‐free, and homogeneous aqueous solution system for synthesizing cellulose ethers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5911–5920, 2004     

Synthesis and application of a molecularly imprinted polymer in the solid-phase extraction of ketoprofen from wastewater

Ketoprofen is a nonsteroidal anti-inflammatory drug widely consumed by humans as it possesses analgesic activities. A selective molecularly imprinted polymer (MIP) for ketoprofen was synthesized and applied as a solid-phase extraction sorbent. MIP was synthesized using 2-vinylpyridine, ethylene glycol dimethacrylate, 1,1′-azobis(cyclohexanecarbonitrile), toluene/acetonitrile (9:1, v/v), and ketoprofen as a functional monomer, cross-linker, initiator, porogenic mixture, and template, respectively. The polymerization was performed at 60 °C for 16 h, and thereafter the temperature was increased to 80 °C for 24 h to achieve a solid monolith polymer. Nonimprinted polymer was synthesized in a similar manner with the omission of ketoprofen. Characterization with thermogravimetric analysis and X-ray diffraction showed that the synthesized polymers were thermally stable and amorphous. Solid-phase extraction cartridges packed with MIP were used with high-performance liquid chromatography for quantitative analysis of ketoprofen in wastewater. The analytical method gave detection limits of 0.23, 0.17, and 0.09 μg/L in wastewater influent, effluent, and deionized water, respectively. The recovery for the wastewater influent and effluent spiked with 5 μg/L of ketoprofen was 68%, whereas 114% was obtained for deionized water. The concentrations of ketoprofen in the influent and effluent samples were in the ranges of 22.5–34.0 and 1.14–5.33 μg/L, respectively. Overall, the analytical method for the analysis of ketoprofen in wastewater was rapid, affordable, accurate, precise, sensitive, and selective.