Non-functionalized oil palm waste-derived reduced graphene oxide for methylene blue removal: Isotherm,kinetics, thermodynamics,and mass transfer mechanism

The discharge of colored effluents from industries is one of the significant sources of water pollution. Therefore, there is a growing demand for efficient and low-cost treatment methods. An adsorption process with reduced graphene oxide (rGO) synthesized using a novel double carbonization and oxidation method from the natural precursor of oil palm empty fruit bunch (OPEFB) as adsorbent is a promising approach for addressing the problem. In this study, OPEFB biochar was mixed with ferrocene with a ratio of 5:1 (m/m) and oxidized under nitrogen flow at a temperature of 300 °C for 20 min, which resulted in 75.8 wt% of yield. The potential of the synthesized rGO as an effective adsorbent for dye removal from water and wastewater was explored using methylene blue (MB) as a model. Several factors were investigated, including adsorbent dosage, initial concentration, contact time, and pH, to obtain the optimum adsorption condition through batch studies. The physical and chemical characteristics of the rGO in terms of functional groups, surface morphology, elemental composition, and crystallinity phase were determined through characterization. The nonlinear isotherms were appropriated using several error functions to describe the adsorption isotherm with a maximum adsorption capacity of 50.07 mg/g. The kinetic study demonstrates that MB’s adsorption fits the PFO kinetic model and agrees with Bangham’s interpretation of pore diffusion. The adsorption mechanism was found to be physisorption on the multilayer heterogeneous surface of the rGO involving π-π interaction, hydrophobic association, and electrostatic interaction. The thermodynamics study showed that the process was spontaneous and exothermic. The mass transfer mechanism study shows that the adsorption is controlled by intraparticle diffusion and involves complex pathways. The study found that the novel non- functionalized rGO could remove cationic dyes from water and wastewater.     

粉煤灰合成Na-X沸石去除废水中镍离子的研究

粉煤灰通过碱熔融 水热法合成了Na-X型沸石,研究了Na-X型沸石的用量、吸附时间、溶液pH值、初始镍离子浓度和温度对废水中镍离子去除效果的影响。结果表明,Na-X型粉煤灰沸石对镍离子的去除性能与化学原料合成的13X相当,明显优于粉煤灰。在20℃,pH值为6,沸石用量10g/L,吸附15min时,对初始浓度为20mg/L~150mg/L的镍离子去除率均可达90%以上。镍离子的吸附过程符合Langmiur吸附等温方程式,其单层吸附量为11.2×10^-3。粉煤灰沸石重复使用5次,对废水中镍离子的去除率仍高达95%,再生性能良好。     

纳米分子筛的合成及硫化氢吸附性能

利用无模板水热法合成纳米尺寸的小孔SOD型和大孔X型分子筛, 并考察了其硫化氢脱除性能. 通过对比两种分子筛的硫化氢吸附性能, 证实分子筛对硫化氢的吸附主要集中于孔道内和可及的活性位. 考察了晶粒尺寸、 体积空速和吸附温度等因素对硫化氢吸附的影响, 发现纳米尺寸X型分子筛具有更大的硫容, 并且在低温和低空速下分子筛中的硫化氢分子易于脱除. 随后对纳米X型分子筛进行了金属离子交换改性, 发现Cu改性的分子筛硫容优于其它离子改性的吸附剂, 能达到20.6 mg/g. NaX-N和Cu-NaX-N再生后的硫容分别为新鲜分子筛的62.4%和78.5%.     

Functionalization effect of Fe-type MOF for methylene blue adsorption

Water pollutant such as dyes had danger the water quality. Todays, porous materials are great potential for dye adsorption from water bodies. In this study, the iron-based metal–organic framework (MOF-Fe) of MIL-101 is synthesized through a facile solvothermal method. The amine-functionalization effect of the MOF-Fe (amine-MOF-Fe) is evaluated for the adsorptive removal of methylene blue (MB) from aqueous solution. The adsorption behaviour had shown a rapid MB adsorption within the first hour of the process due to the pore-filling mechanism of the porous MOF-Fe structure. The electrostatic interaction between the amino group of amine-MOF-Fe and MB had contributed to the high adsorption capacity. The amine-functionalization effect also found the amine-MOF-Fe is having two times higher adsorption capacity when used with the loading two times lower than non-functionalized MOF-Fe. The maximum equilibrium adsorption capacities were measured at 149.25 and 312.5 mg/g with optimum MOFs loading of 0.8 and 0.4 g/L for MOF-Fe and amine-MOF-Fe, respectively. The adsorption mechanism proposed includes the electrostatic interaction, pore filling, hydrogen bonding, and π–π stacking. The regeneration study showed the MOFs could be recycled without interfering with the removal efficiency. Hence, the results indicate that the MOFs had desirable reusability for the practical adsorption of cationic dyes with its features of fast adsorption and high capacity.     

Fabrication of carboxymethyl functionalized β-cyclodextrin-modified graphene oxide for efficient removal of methylene blue

In this study, a novel carboxymethyl functionalized β-cyclodextrin-modified graphene oxide (CM-β-CD-GO) adsorbent was designed and fabricated. The CM-β-CD-GO was applied to remove methylene blue (MB) from aqueous solutions. The adsorption mechanism was discussed in detail through the study of pH effect, kinetics, and isotherm models. The adsorption of CM-β-CD-GO for MB displayed high removal rates at the pH range of 6.0–10.0, and the removal efficiency is over 90% within 20 min. The pseudo-second-order model could well describe the kinetic process of MB adsorption, and the adsorption was determined by the multi-step process. The maximum uptake capability of CM-β-CD-GO towards MB was 245.70 mg g⁻¹ at 25 °C according to Langmuir isotherm model. A possible adsorption mechanism that electrostatic attraction, π-π interaction, and host-guest supramolecular interactions supported MB adsorption was proposed. The adsorption capacity of CM-β-CD-GO showed no significant change after five cycles. The structure and morphology of CM-β-CD-GO were characterized by XPS, FT-IR, TGA, PXRD, AFM, SEM, zeta (ζ) potential determination, and Raman spectroscopy. This work provides valuable information for the design of novel adsorbents that specifically and efficiently adsorb cationic dyes contaminants.     

Recent advances on hydrogels based on chitosan and alginate for the adsorption of dyes and metal ions from water

In contemporary times, water resources have become increasingly scarce and suffer from anthropogenic pollution sources with an organic and inorganic origin that are products of industrial, agricultural, and everyday waste. Contamination with heavy metals and dyes in wastewater is considered a risk for water sources that can leak into underground and surface sources, leading to increased biological and chemical contamination. The pollutant removal process is performed by adsorption treatment methods, which is the most common method, and it is considered an effective method with a high and economical removal rate.In this review, we discuss the use of biobased hydrogel adsorbents in the removal of organic dyes and metal ions from water. The literature indicates that hydrogels exhibit rapid absorption kinetics and a dye removal absorption capacity that can reach more than 100 mg/g and sometimes more than 2000 mg/g, with a metal adsorption capacity ranging from 38 mg/g to more than 440 mg/g. These results are discussed and compared by taking into account hydrogel materials that contain biopolymers such as alginate, chitosan or both. In general, absorption depends mainly on biobased materials, which have a natural origin and can be utilized to synthesize hydrogels to remove pollutants, dyes and heavy metals. Chitosan and alginate are prominent materials for this use and they can be incorporated with other components to obtain hydrogels or nanocomposite materials with different efficacies to remove dyes and metal ions.     

A simple method for removal of toxic dyes such as Brilliant Green and Acid Red from the aquatic environment using Halloysite nanoclay

This project explains an easy, simple and eco-friendly method to remove some toxic dyes like Brilliant Green and Acid Red from aquatic solution by technique of solid-phase extraction that uses Halloysite nanoclay eco-friendly solid phase as absorbent surface for adsorption of dye. The physical properties of the HNC such as scanning electron microscopy, transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and surface area analysis were studied. The best conditions like pH of the solution, HNC weight, contact shaking time, the temperature of the solution, and ionic strength were investigated for removal effectiveness. The experimental data of the adsorption process showed that HNC can remove most of the dyes within 30 min, with an adsorption capacity of 12.5 mg/g for A.R dye and 13.9 mg/g for B.G dye on HNC solid phase at optimum conditions. The removal process of dyes on HNC was studied kinetically and thermodynamically, and the data confirms that the pseudo-second-order kinetic model was able to describe the adsorption process. Thermodynamic data confirms the process was spontaneous andexothermic in nature for A.R dye, while was spontaneous and endothermic in nature for B.G dye. Finally, the effectiveness of HNC was inspected by removing dyes from three various real samples, and the results showed high performance in removing dyes on HNC for four consecutive cycles.     

Adsorptive properties of X zeolites modified by transition metal cation exchange

The ionic exchange of the NaX zeolite by Ni²⁺ and Cr³⁺ cations was progressively driven and studied by adsorption of nitrogen and carbon dioxide. For each cation-exchanged X zeolite sample, the development of characteristics such as profile of isotherms, RI criterion, isosteric adsorption heat and microporous volume using both the Dubinin–Radushkevich (DR) equation and the t-plot, was followed through the nitrogen adsorption. Results show that the cationic exchange process, in the case of Cr³⁺ introduced at middle degree, is accompanied by a textural damage for Cr(x)X, in contrast to Ni²⁺-exchanged X zeolites. This degradation occurs without significant presence of mesopores, because the RI criterion values were found to be much lower than 2.2. The CO₂ adsorption isotherms were measured at intervals of 30 K from 273 K and the equilibrium pressures ranged from 0.5 to 600 Torr. The experimental data were correlated by the Toth model. The associated three adjustable parameters were estimated by nonlinear least-squares analysis. The effect of temperature on the model parameters and the Henry’s law slope, K _H , represented by the product of Toth parameters, are discussed.     

Modification of microcrystalline cellulose with pyridone derivatives for removal of cationic dyes from aqueous solutions

Microcrystalline cellulose (MCC) was modified with pyridone derivatives such as pyridone diester (PDE) and pyridone diacid (PDA) by using succinic acid anhydride as a linker. The modified MCCs were characterized by the fourier transform infrared spectroscopy, scanning electron microscopy, thermal gravimetric analysis, elemental analysis and solid state ¹³C NMR. The adsorption capacities of the modified MCCs to cationic dyes were examined by using methylene blue (MB) as a model dye. It was found that the kinetic adsorption data followed the pseudo-second-order kinetic model, and the adsorption equilibriums were reached less than 10 min. The isothermal adsorption data were fitted with the Langmuir isotherm model very well, from which the maximum adsorption capacities of the MCCs modified with PDE and PDA were determined to be 101.01 and 142.86 mg/g, respectively. Further investigation showed that the modified MCCs were pH-dependent for adsorption of MB in aqueous solutions. The modified MCCs could be used for removal of MB from an aqueous solution at pH 8, and reused by regeneration in an acidic solution. It was tested that the modified MCCs had a high reusability for removal of MB from aqueous solutions, and still maintained high adsorption capacities even after multiple cycles of desorption–adsorption processes. Hence, the MCCs modified with PDE and PDA could be an effective and efficient approach to removal of cationic dyes from aqueous solutions.     

表面活性剂改性有机沸石对废水中亚甲基蓝的吸附行为

用表面活性剂十六烷基三甲基溴化铵(CTMAB)和十二烷基硫酸钠(SDS)复合改性沸石,制备了阴阳离子表面活性剂改性沸石,利用X射线衍射和红外吸收光谱表征了改性前后沸石的结构,并研究了改性沸石对亚甲基蓝的吸附行为.结果表明,改性后沸石的吸附性能明显增强;在溶液pH 8、常温,吸附时间100 min、改性沸石用量20 g/...     

Theoretical study of the adsorption of ethylene on alkali‐exchanged zeolites

The structures of alkali‐exchanged faujasite (X–FAU, X = Li⁺ or Na⁺ ion) and ZSM‐5 (Li–ZSM‐5) zeolites and their interactions with ethylene have been investigated by means of quantum cluster and embedded cluster approaches at the B3LYP/6‐31G(d, p) level of theory. Inclusion of the Madelung potential from the zeolite framework has a significant effect on the structure and interaction energies of the adsorption complexes and leads to differentiation of different types of zeolites (ZSM‐5 and FAU) that cannot be drawn from a typical quantum cluster model, H₃SiO(X)Al(OH)₂OSiH₃. The Li–ZSM‐5 zeolite is predicted to have a higher Lewis acidity and thus higher ethylene adsorption energy than the Li–FAU zeolites (16.4 vs. 14.4 kcal/mol), in good agreement with the known acidity trend of these two zeolites. On the other hand, the cluster models give virtually the same adsorption energies for both zeolite complexes (8.9 vs. 9.1 kcal/mol). For the larger cation‐exchanged Na–FAU complex, the adsorption energy (11.6 kcal/mol) is predicted to be lower than that of Li–FAU zeolites, which compares well with the experimental estimate of about 9.6 kcal/mol for ethylene adsorption on a less acidic Na–X zeolite. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 333–340, 2003     

Fe3O4-CuO-activated carbon composite as an efficient adsorbent for bromophenol blue dye removal from aqueous solutions

Dye wastewater from industries is posing tremendous health hazards. The lethal dyes can be eliminated using nanomaterials and scientific approach like adsorption which is facile, cheap, safe as well as ecofriendly. Fe₃O₄-CuO-AC composite was prepared by a hydrothermal method and used for the removal of dyes in wastewater. The composite material was characterized by various techniques such as XRD, SEM, EDS, TEM and FT-IR. The Fe₃O₄-CuO-AC composite was used to treat five types of dyes in water. Fe₃O₄-CuO-AC composite showed the highest adsorption capability for bromophenol blue (BPB) dye. The effects of initial concentration, pH, the amount of adsorbent and temperature were also studied. The optimum conditions were found to be 20 ppm dye concentration, pH 9, an adsorbent dose of 0.06 gL^─1 at 65 °C. A removal efficiency of 97% was obtained for BPB dye during 120 min of adsorption. Kinetic studies indicated that a pseudo-second order is the most suitable model for the adsorption process. The Fe₃O₄-CuO-AC composite showed better adsorption capacity as compare to Fe₃O₄-AC except for the Methyl green dye. The maximum adsorption capacity was found to be 88.60 mg/g for BPB. Additionally, the thermodynamic parameters (ΔS°, ΔH° and ΔG°) showed that the process was spontaneous and exothermic. All the above results revealed that the Fe₃O₄-CuO-AC compositecan be an effective adsorbent for removing dyes from wastewater.     

Zeolite synthesis from waste fly ash and its application in CO<Subscript>2</Subscript> capture from flue gas streams

Zeolite A and A + X mixtures were prepared from coal-fly ash procured from China by using an alkali fusion method. X-ray diffraction showed that both the materials were crystalline and reproducible. Scanning Microscopy revealed that pure zeolite A particles have cubic morphology while the mixture shows intergrowth of cubic and pyramidal crystals. The surface area for A + X mixture was around 330 m²/g which is higher than zeolite A, however, lower than typical X zeolite. CO₂ and N₂ adsorption isotherms were measured and the data was fitted by the Dual Site Langmuir equation. These zeolites were then tested for CO₂ capture at different temperatures in a process with a nine step cycle. When compared with 13X zeolites at higher temperature (∼90 °C), both the zeolite A + X mixture and zeolite A prepared from fly ash showed better performance in CO₂ capture from flue gas because they have higher selectivity of CO₂ over N₂.     

Mechanistic insights into methylene blue removal via olive stone-activated carbon: A study on surface porosity and characterization

Global attention is increasingly focused on the adverse health and environmental impacts of textile dyes, marking the necessity for effective and sustainable dye remediation strategies in industrial wastewater. This study introduces a novel, eco-friendly activated carbon produced from olive stones (OLS), a readily available by-product of the olive oil industry. The OLS was chemically activated with H₃PO₄ and KOH, creating two materials: OLS-P and OLS-K, respectively. These were then utilized as cost-effective adsorbents for the removal of methylene blue (MB) dye. The activated materials were characterized via X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR), iodine number, and pHpzc analysis, with the zero-point charge determined as approximately pH 1 for OLS-P and pH 8 for OLS-K. Batch adsorption experiments conducted at various temperatures revealed that adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model. Temperature was found to significantly impact adsorption performance, with OLS-K demonstrating a substantial increase in adsorption capacity (q_e) from 6.27 mg/g at 23˚C to 94.7 mg/g at 32 ˚C. Conversely, OLS-P displayed a decrease in q_e from 16.78 mg/g at 23 ˚C to 3.67 mg/g at 32 ˚C as temperature increased. The study highlights the potential of KOH-treated olive stones as a promising, cost-efficient adsorbent for methylene blue remediation from wastewater.     

Specific features of adsorption of azo dyes on fly ash

A possibility to utilize fly ash (FA) formed at coal-fired power plants as a cheap adsorbent for the purification of wastewater containing azo dyes methylene blue (MB) and methyl red (MR) was considered. The effect of an FA additive on the adsorption capacity of active carbon was studied. The efficiency of FA as an adsorbent for the purification of aqueous solutions from MB and MR was shown. The adsorption is also fairly efficient when active carbon is partially replaced by FA. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 545–548, March, 2007.     

Differential calorimetric enthalpies of adsorption ofp-xylene andm-xylene on y faujasites at 25°C

The differential enthalpies of adsorption ofp-xylene andm-xylene on NaY, KY and BaY zeolites were measured by isothermal calorimetry coupled with isothermal volumetry at 25C. Whatever the zeolite, the enthalpies of adsorption ofp-xylene andm-xylene at low filling were of the same order of magnitude. They did not show significantly the effect of the dipolar moment ofm-xylene. Their absolute values varied in the sequence Q ₀(pX/NaY)<Q ₀(pX/KY) =Q ₀(mX/KY)<Q ₀(pX/BaY)<Q ₀(mX/NaY) =Q ₀(mX/BaY)During the adsorption of the third molecule of xylene per -cage, BaY zeolite exhibited specific behaviour: the differential enthalpies of adsorption decreased with the filling of the -cages in such a way that they became lower than those of the other two zeolites. Some arguments concerning the structures of the zeolite and xylene molecules can explain such behaviour. Whatever the zeolite, the adsorption capacity of the -cages was 3.5 molec.^–1. For relative pressures ranging from 0.2 to 0.5, an additional adsorption of about 0.1 molec.^–1 occurred on the external surface.     

Novel dye removing agent based on CTS-g-P(AA-co-NIPAM)/GO composite

A novel composite Chitosan graft poly (acrylic acid-co-N-isopropylacrylamide)/graphite oxide (CTS-g-P(AA-co-NIPAM/GO) is synthesized and used to remove methylene blue (MB) and fuchsin basic (FB) from aqueous solutions by adsorption. Small amount of GO brings about great improvement of the thermostability together with the adsorption amount. Adsorption capacities of MB and FB increase from 842.1 and 633.7 mg/g, respectively, to 1496.3 and 1000.8 mg/g, respectively, with 0.02 g intercalation amount of GO. The interactions between GO and main body of CTS-g-P(AA-co-NIPAM) graft copolymer are hydrogen and amide bonds, whereas that between dye molecules and CTS-g-P(AA-co-NIPAM)/GO composite is hydrogen bond as well as electrostatic interaction. Effect of various conditions on the adsorption capacities is discussed. Adsorption isotherms and thermodynamics are studied. The adsorption of both MB and FB are spontaneous and satisfy the Redlich-Peterson equation. Kinetic study shows that the adsorption of both dyes is in accordance with the Pseudo first-order kinetic model.     

Characterization of Biosorption Process of Acid Orange 7 on Waste Brewery’s Yeast

The use of cheap, high-efficiency, and ecofriendly adsorbent has been studied as an alternative way for the removal of dyes from wastewater. This paper investigated the use of waste brewery’s yeast for the removal of acid orange 7 from aqueous solution. The optimum removal of acid orange 7 was found to be 3.561 mg/g at pH 2.0, 10 mg/L initial concentration and 303 K. The kinetic studies indicated that the biosorption process of acid orange 7 agreed well with the pseudo-second-order model. The external diffusion is the rate-controlling step of the initial fast adsorption (<20 min) and then the intraparticle diffusion dominated the mass transfer process. Langmuir, Freundlich, and Dubinin–Radushkevich models were applied to describe the biosorption isotherm of acid orange 7 by waste brewery’s yeast. Langmuir isotherm model fits the equilibrium data, at all the studied temperatures, better than the other isotherm models which indicates monolayer dye biosorption process. The highest monolayer biosorption capacity was found to be 2.27 × 10⁻³ mol/g at 303 K. The calculated thermodynamic parameters (ΔG, ΔS, ΔH) showed the biosorption process to be spontaneous and exothermic in nature. Amine or amino, amide, carboxyl, phosphate groups are responsible for the dyes biosorption based on the result of Fourier transform infrared analysis.     

Study of adsorption sites heterogeneity in zeolites by means of coupled microcalorimetry with volumetry

Adsorption of CO₂ as probe molecule on alkali-metal zeolites of MFI structure was investigated by joint volumetry–calorimetry. Consideration was given to the interpretation of the heat evolved when a probe molecule is adsorbed on the surface. In particular, the number and the strength of adsorption sites are discussed as functions of zeolite structure, concentration, and nature of extra-framework cation. The adsorption heats (q _iso) of CO₂ interaction with alkali-metal cations decrease for MFI zeolite with high Si/Al in the sequence Li⁺ > Na⁺ > K⁺ from 54 kJ/mol to 49 and 43 kJ/mol, respectively. In addition, the adsorption heats are influenced by concentration of Al in the framework. This phenomenon is attributed to formation of bridged CO₂ adsorption complexes formed between two cations. On the base of quantitative analysis of adsorption processes, presence of geminal adsorption complexes was suggested for adsorption at higher equilibrium pressures.