Comparing different versions of the Yoon-Nelson model in describing organic micropollutant adsorption within fixed bed adsorbers.

The Yoon-Nelson model serves as a widely used tool for describing the breakthrough behavior of organic micropollutants within fixed bed adsorbers. This study aims to augment its modeling efficacy through two proposed refinements found in the literature: a logarithmic transformation and the incorporation of steric hindrance effects. We systematically evaluated the original Yoon-Nelson model alongside the modified versions, using breakthrough data associated with micropollutant adsorption on solid materials. Three distinct cases were scrutinized: (1) caffeine adsorption on activated carbon; (2) tetracycline adsorption on hierarchical porous carbon; and (3) diclofenac adsorption on organoclay. While all three models demonstrated comparable performance with highly symmetric breakthrough data in case 1, their efficacy diverged significantly when confronted with strongly asymmetric breakthrough data in cases 2 and 3. The original Yoon-Nelson model and the logarithmically modified version fell short in accurately representing these intricate breakthrough curves. In contrast, the version incorporating steric hindrance effects showcased substantial accuracy, outperforming other models in capturing the complexities of asymmetric breakthrough data. This advancement markedly enhances the modeling accuracy and versatility of the Yoon-Nelson model, particularly in assessing the dynamic behavior of organic micropollutants within fixed bed adsorbers.

Rooting out faulty adsorption models. Comment on "Magnetic Prussian blue nanoshells are controllable (sic) anchored on the surface of molybdenum disulfide nanosheets for efficient separation of radioactive cesium from water".

This correspondence critically examines and rectifies modeling deficiencies identified in a recent article published in this journal. Our analysis covers a range of models and issues, including the Temkin isotherm, the Flory-Huggins isotherm, the pseudo-first-order kinetic model, the pseudo-second-order kinetic model, the intraparticle diffusion model, the Elovich kinetic model, and the computation of thermodynamic parameters. The elucidation and correction of these modeling issues contribute to a more accurate and reliable understanding of the studied phenomena, thereby enhancing the scientific rigor of the subject paper.

Comment on "Algal mediated intervention for the retrieval of emerging pollutants from aqueous media".

Addressing inaccuracies in review articles is essential to prevent the proliferation of misinformation. This communication is dedicated to rectifying factual errors identified in a recent review article featured in this journal, with a specific emphasis on addressing errors related to the Temkin, Flory-Huggins, Sips, and Baudu isotherm models. By elucidating and clarifying these inaccuracies, we aim to uphold the integrity of scientific discourse and ensure the accurate dissemination of information within the scholarly community.

Palm Raceme as a Promising Biomass Precursor for Activated Carbon to Promote Lipase Activity with the Aid of Eutectic Solvents.

This study concerns the role of activated carbon (AC) from palm raceme as a support material for the enhancement of lipase-catalyzed reactions in an aqueous solution, with deep eutectic solvent (DES) as a co-solvent. The effects of carbonization temperature, impregnation ratio, and carbonization time on lipase activity were studied. The activities of Amano lipase from Burkholderia cepacia (AML) and lipase from the porcine pancreas (PPL) were used to investigate the optimum conditions for AC preparation. The results showed that AC has more interaction with PPL and effectively provides greater enzymatic activity compared with AML. The optimum treatment conditions of AC samples that yield the highest enzymatic activity were 0.5 (NaOH (g)/palm raceme (g)), 150 min, and a carbonization temperature of 400 °C. DES was prepared from alanine/sodium hydroxide and used with AC for the further enhancement of enzymatic activity. Kinetic studies demonstrated that the activity of PPL was enhanced with the immobilization of AC in a DES medium.

Bifunctional Ionic Deep Eutectic Electrolytes for CO2 Electroreduction.

CO2 is a low-cost monomer capable of promoting industrially scalable carboxylation reactions. Sustainable activation of CO2 through electroreduction process (ECO2R) can be achieved in stable electrolyte media. This study synthesized and characterized novel diethyl ammonium chloride-diethanolamine bifunctional ionic deep eutectic electrolyte (DEACl-DEA), using diethanolamine (DEA) as hydrogen bond donors (HBD) and diethyl ammonium chloride (DEACl) as hydrogen bond acceptors (HBA). The DEACl-DEA has -69.78 °C deep eutectic point and cathodic electrochemical stability limit of -1.7 V versus Ag/AgCl. In the DEACl-DEA (1:3) electrolyte, electroreduction of CO2 to CO2 •- was achieved at -1.5 V versus Ag/AgCl, recording a faradaic efficiency (FE) of 94%. After 350 s of continuous CO2 sparging, an asymptotic current response is reached, and DEACl-DEA (1:3) has an ambient CO2 capture capacity of 52.71 mol/L. However, DEACl-DEA has a low faradaic efficiency <94% and behaves like a regular amine during the CO2 electroreduction process when mole ratios of HBA-HBD are greater than 1:3. The electrochemical impedance spectroscopy (EIS) and COSMO-RS analyses confirmed that the bifunctional CO2 sorption by the DEACl-DEA (1:3) electrolyte promote the ECO2R process. According to the EIS, high CO2 coverage on the DEACl-DEA/Ag-electrode surface induces an electrochemical double layer capacitance (EDCL) of 3.15 × 10-9 F, which is lower than the 8.76 × 10-9 F for the ordinary DEACl-DEA/Ag-electrode. COSMO-RS analysis shows that the decrease in EDCL arises due to the interaction of CO2 non-polar sites (0.314, 0.097, and 0.779 e/nm2) with that of DEACl (0.013, 0.567 e/nm2) and DEA (0.115, 0.396 e/nm2). These results establish for the first time that a higher cathodic limit beyond the typical CO2 reduction potential is a criterion for using any deep eutectic electrolytes for sustainable CO2 electroreduction process.

Electroreduction of CO2 and Quantification in New Transition-Metal-Based Deep Eutectic Solvents Using Single-Atom Ag Electrocatalyst.

Deep eutectic solvents (DESs) are efficient media for CO2 capture, and an electroreduction process using the deterministic surface of single-atom electrocatalysts is a facile way to screen gas absorption capacities of novel DESs. Using newly prepared transition-metal-based DESs indexed as TDESs, the interfacial mechanism, detection, quantification, and coordination modes of CO2 were determined for the first time. The CO2 has a minimum detection time of 300 s, whereas 500 s of continous ambient CO2 saturation provided ZnCl2/ethanolamine (EA) (1:4) and CoCl2/EA (1:4) TDESs with a maximum CO2 absorption capacity of 0.2259 and 0.1440 mmol/L, respectively. The results indicated that CO2 coordination modes of η1 (C) and η2 (O, O) with Zn in ZnCl2/EA (1:4) TDESs are conceivable. We found that the transition metals in TDESs form an interface at the compact layer of the electrocatalyst, while CO2 •-/CO2 reside in the diffuse layer. These findings are important because they provide reliable inferences about interfacial phenomena for facile screening of CO2 capture capacity of DESs or other green solvents.

Simulation of Deep Eutectic Solvents' Interaction with Membranes of Cancer Cells Using COSMO-RS.

Deep eutectic solvent (DES) affinities with cellular membranes structures dictate the degree of cytotoxicity that results from these interactions. The physicochemical properties of choline chloride (ChCl)-DESs suggest non-negligible cytotoxicities that were attested by published researches. In this study, the profiles of novel N,N-diethylammonium chloride (DAC)-based-deep eutectic solvents (DESs) prepared with various hydrogen bond donors (urea, glycerol, ethylene glycol, malonic acid, and zinc chloride) were compared to those of ChCl-DESs by using HelaS3, AGS, MCF-7, and WRL-68 cancer cell lines. The molecular interactions between salts and cellular membranes were investigated to explain the observed cytotoxicity. The results show that ChCl-based DESs (279 ≤ IC50 ≥ 1260 mM) were less toxic than DAC-based DESs (37 ≤ IC50 ≥ 109 mM). COSMO-RS analysis emphasized the importance of salt hydrophobicity with regards to DESs cytotoxicity. Malonic acid increased hydrophobicity and cytotoxicity in general, thus highlighting the potential of ammonium salt-based DESs as anticancer agents.

Growth and optimization of carbon nanotubes in powder activated carbon for an efficient removal of methylene blue from aqueous solution.

This work demonstrated the synthesis of carbon nanotubes (CNTs) on powder activated carbon (PAC) impregnated with Ni-catalyst through chemical vapour deposition. The optimized effects of reaction temperature, time and feedstock flow rates on CNT growth were examined. Potassium permanganate (KMnO4) and potassium permanganate in acidic solution (KMnO4/H2SO4) were used to functionalize CNTs samples. A primary screening of methylene blue (MB) adsorption was conducted. The chemical, physical and morphological properties of the adsorbent with the highest removal efficiency were investigated using FESEM, EDX, TEM, BET surface area, RAMAN, TGA, FTIR, and zeta potential. The resulting carbon nanotube-loaded activated carbons possessed abundant pore structure and large surface area. The MB removal by the as-synthesized CNTs was more remarkable than that by the modified samples. Adsorption studies were carried out to evaluate the optimum conditions, kinetics and isotherms for MB adsorption process. The response surface methodology-central composite design (RSM-CCD) was used to optimize the adsorption process parameters, including pH, adsorbent dosage and contact time. The investigation of the adsorption behaviour demonstrated that the adsorption was well fitted with the pseudo-second-order model and Langmuir isotherm with the maximum monolayer adsorption capacity of 174.5 mg/g. Meanwhile, the adsorption of MB onto adsorbent was driven by the electrostatic attraction and π-π interaction. Moreover, the as-obtained CNT-PAC exhibited good reusability after four repeated operations. In view of these empirical findings, the low-cost CNT-PAC has potential for removal of MB from aqueous solution.

The formation of hybrid carbon nanomaterial by chemical vapor deposition: an efficient adsorbent for enhanced removal of methylene blue from aqueous solution.

In this study, carbon species were grown on the surface of Ni-impregnated powder activated carbon to form a novel hybrid carbon nanomaterial by chemical vapor deposition. The carbon nanomaterial was obtained by the precipitation of the methane elemental carbon atoms on the surface of the Ni catalyst. The physiochemical properties of the hybrid material were characterized to illustrate the successful growth of carbon species on the carbon substrate. The response surface methodology was used for the evaluation of adsorption parameters effect such as pH, adsorbent dose and contact time on the percentage removal of MB dye from aqueous solution. The optimum conditions were found to be pH = 11, adsorbent dose = 15 mg and contact time of 120 min. The material we prepared showed excellent removal efficiency of 96% for initial MB concentration of 50 mg/L. The adsorption of MB was described accurately by the pseudo-second-order model with R2 of 0.998 and qe of 163.93 (mg/g). The adsorption system showed the best agreement with Langmuir model with R2 of 0.989 and maximum adsorption capacity (Qm) of 250 mg/g.

Optimization of the Synthesis of Superhydrophobic Carbon Nanomaterials by Chemical Vapor Deposition.

Demand is increasing for superhydrophobic materials in many applications, such as membrane distillation, separation and special coating technologies. In this study, we report a chemical vapor deposition (CVD) process to fabricate superhydrophobic carbon nanomaterials (CNM) on nickel (Ni)-doped powder activated carbon (PAC). The reaction temperature, reaction time and H2/C2H2 gas ratio were optimized to achieve the optimum contact angle (CA) and carbon yield (CY). For the highest CY (380%) and CA (177°), the optimal reaction temperatures were 702 °C and 687 °C, respectively. However, both the reaction time (40 min) and gas ratio (1.0) were found to have similar effects on CY and CA. Based on the Field emission scanning electron microscopy and transmission electron microscopy images, the CNM could be categorized into two main groups: a) carbon spheres (CS) free carbon nanofibers (CNFs) and b) CS mixed with CNFs, which were formed at 650 and 750 °C, respectively. Raman spectroscopy and thermogravimetric analysis also support this finding. The hydrophobicity of the CNM, expressed by the CA, follows the trend of CS-mixed CNFs (CA: 177°) > CS-free CNFs (CA: 167°) > PAC/Ni (CA: 65°). This paves the way for future applications of synthesized CNM to fabricate water-repellent industrial-grade technologies.

Unraveling the cytotoxicity and metabolic pathways of binary natural deep eutectic solvent systems.

In this study, the anticancer potential and cytotoxicity of natural deep eutectic solvents (NADESs) were assessed using HelaS3, PC3, A375, AGS, MCF-7, and WRL-68 hepatic cell lines. NADESs were prepared from choline chloride, fructose, or glucose and compared with an N,N-diethyl ethanolammonium chloride:triethylene glycol DES. The NADESs (98 ≤ EC50 ≥ 516 mM) were less toxic than the DES (34 ≤ EC50 ≥ 120 mM). The EC50 values of the NADESs were significantly higher than those of the aqueous solutions of their individual components but were similar to those of the aqueous solutions of combinations of their chief elements. Due to the uniqueness of these results, the possibility that NADESs could be synthesized intracellularly to counterbalance the cytotoxicity of their excess principal constituents must be entertained. However, further research is needed to explore this avenue. NADESs exerted cytotoxicity by increasing membrane porosity and redox stress. In vivo, they were more destructive than the DES and induced liver failure. The potential of these mixtures was evidenced by their anticancer activity and intracellular processing. This infers that they can serve as tools for increasing our understanding of cell physiology and metabolism. It is likely that we only have begun to comprehend the nature of NADESs.

Applications of deep eutectic solvents in biotechnology and bioengineering-Promises and challenges.

Deep eutectic solvents (DESs) have been touted recently as potential alternatives to ionic liquids (ILs). Although they possess core characteristics that are similar to those of ILs (e.g., low volatility, non-flammability, low melting points, low vapor pressure, dipolar nature, chemical and thermal stability, high solubility, and tuneability), DESs are superior in terms of the availability of raw materials, the ease of storage and synthesis, and the low cost of their starting materials. As such, they have become the subject of intensive research in various sectors, notably the chemical, electrochemical, and biological sectors. To date, the applications of DESs have shown great promise, especially in the medical and biotechnological fields. In spite of these various achievements, the safety concern for these mixtures must be sufficiently addressed. Indeed, in order to exploit the vast array of opportunities that DESs offer to the biological industry, first, they must be established as safe mixtures. Hence, the biotechnological applications of DESs only can be implemented if they are proven to have negligible or low toxicity profiles. This review is the first of its kind, and it discusses two current aspects of DES-based research. First, it describes the properties of these mixtures with ample focus on their toxicity profiles. Second, it provides an overview of the breakthroughs that have occurred and the foreseeable prospects of the use of DESs in various biotechnological and biological applications.

Allyl triphenyl phosphonium bromide based DES-functionalized carbon nanotubes for the removal of mercury from water.

Recently, deep eutectic solvents (DESs) have shown their new and interesting ability for chemistry through their involvement in variety of applications. This study introduces carbon nanotubes (CNTs) functionalized with DES as a novel adsorbent for Hg2+ from water. Allyl triphenyl phosphonium bromide (ATPB) was combined with glycerol as the hydrogen bond donor (HBD) to form DES, which can act as a novel CNTs functionalization agent. The novel adsorbent was characterized using Raman, FTIR, XRD, FESEM, EDX, BET surface area, TGA, TEM and Zeta potential. Response surface methodology was used to optimize the removal conditions for Hg2+. The optimum removal conditions were found to be pH 5.5, contact time 28 min, and an adsorbent dosage of 5 mg. Freundlich isotherm model described the adsorption isotherm of the novel adsorbent, and the maximum adsorption capacity obtained from the experimental data was 186.97 mg g-1. Pseudo-second order kinetics describes the adsorption rate order.

Remediation of Arsenic Contaminated Soil Using Phosphate and Colloidal Gas Aphron Suspensions Produced from Sapindus mukorossi.

Phosphate and colloidal gas aphrons (CGAs) generated from saponin extracted from Sapindus mukorossi fruit, were evaluated for washing low levels of arsenic from an iron rich soil. Phosphate is one of the most commonly dispersed chemicals that increases arsenic mobility in soil due to their structural similarities, making it an important factor in arsenic removal process. Column washing experiments were performed with CGAs in down flow and up flow modes on soil of pH 5 and 6. Soapnut CGAs, when paired with phosphate removed up to 95 % arsenic while soapnut CGAs alone could only remove up to 70 % arsenic. The presence of phosphate improved efficiency of soapnut solution by up to 35 %. SEM image of washed soil revealed minor corrosion of soil surface while using phosphate with soapnut. Therefore, the addition of phosphates would have positive impact on soil washing using soapnut saponin.

Enhanced removal of lead from contaminated soil by polyol-based deep eutectic solvents and saponin.

Deep eutectic solvents (DESs) are a class of green solvents analogous to ionic liquids, but less costly and easier to prepare. The objective of this study is to remove lead (Pb) from a contaminated soil by using polyol based DESs mixed with a natural surfactant saponin for the first time. The DESs used in this study were prepared by mixing a quaternary ammonium salt choline chloride with polyols e.g. glycerol and ethylene glycol. A natural surfactant saponin obtained from soapnut fruit pericarp, was mixed with DESs to boost their efficiency. The DESs on their own did not perform satisfactory due to higher pH; however, they improved the performance of soapnut by up to 100%. Pb removal from contaminated soil using mixture of 40% DES-Gly and 1% saponin and mixture of 10% DES-Gly and 2% saponin were above 72% XRD and SEM studies did not detect any major corrosion in the soil texture. The environmental friendliness of both DESs and saponin and their affordable costs merit thorough investigation of their potential as soil washing agents.

Superoxide Ion: Generation and Chemical Implications.

Superoxide ion (O2(•-)) is of great significance as a radical species implicated in diverse chemical and biological systems. However, the chemistry knowledge of O2(•-) is rather scarce. In addition, numerous studies on O2(•-) were conducted within the latter half of the 20th century. Therefore, the current advancement in technology and instrumentation will certainly provide better insights into mechanisms and products of O2(•-) reactions and thus will result in new findings. This review emphasizes the state-of-the-art research on O2(•-) so as to enable researchers to venture into future research. It comprises the main characteristics of O2(•-) followed by generation methods. The reaction types of O2(•-) are reviewed, and its potential applications including the destruction of hazardous chemicals, synthesis of organic compounds, and many other applications are highlighted. The O2(•-) environmental chemistry is also discussed. The detection methods of O2(•-) are categorized and elaborated. Special attention is given to the feasibility of using ionic liquids as media for O2(•-), addressing the latest progress of generation and applications. The effect of electrodes on the O2(•-) electrochemical generation is reviewed. Finally, some remarks and future perspectives are concluded.

Remediation of Pb/Cr co-contaminated soil using electrokinetic process and approaching electrode technique.

Electrokinetic process has emerged as an important tool for remediating heavy metal-contaminated soil. The process can concentrate heavy metals into smaller soil volume even in the absence of hydraulic flow. This makes it an attractive soil pre-treatment method before other remediation techniques are applied such that the chemical consumption in the latter stage can be reduced. The present study evaluates the feasibility of electrokinetic process in concentrating lead (Pb) and chromium (Cr) in a co-contaminated soil using different types of wetting agents, namely 0.01 M NaNO3, 0.1 M citric acid and 0.1 M EDTA. The data obtained showed that NaNO3 and citric acid resulted in poor Pb electromigration in this study. As for Cr migration, these agents were also found to give lower electromigration rate especially at low pH region as a result of Cr(VI) adsorption and possible reduction into Cr(III). In contrast, EDTA emerged as the best wetting agent in this study as it formed water-soluble anionic complexes with both Pb and Cr. This provided effective one-way electromigration towards the anode for both ions, and they were accumulated into smaller soil volume with an enrichment ratio of 1.55-1.82. A further study on the application of approaching cathode in EDTA test showed that soil alkalisation was achieved, but this did not provide significant enhancement on electromigration for Pb and Cr. Nevertheless, the power consumption for electrokinetic process was decreased by 22.5%.

The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents.

The temperature dependence of the density, dynamic viscosity and ionic conductivity of several deep eutectic solvents (DESs) containing ammonium-based salts and hydrogen bond donvnors (polyol type) are investigated. The temperature-dependent electrolyte viscosity as a function of molar conductivity is correlated by means of Walden's rule. The oxidation of ferrocene (Fc/Fc+) and reduction of cobaltocenium (Cc+/Cc) at different temperatures are studied by cyclic voltammetry and potential-step chronoamperometry in DESs. For most DESs, chronoamperometric transients are demonstrated to fit an Arrhenius-type relation to give activation energies for the diffusion of redox couples at different temperatures. The temperature dependence of the measured conductivities of DES1 and DES2 are better correlated with the Vogel-Tamman-Fulcher equation. The kinetics of the Fc/Fc+ and Cc+/Cc electrochemical systems have been investigated over a temperature range from 298 to 338 K. The heterogeneous electron transfer rate constant is then calculated at different temperatures by means of a logarithmic analysis. The glycerol-based DES (DES5) appears suitable for further testing in electrochemical energy storage devices.

Functionalization of graphene using deep eutectic solvents.

Deep eutectic solvents (DESs) have received attention in various applications because of their distinctive properties. In this work, DESs were used as functionalizing agents for graphene due to their potential to introduce new functional groups and cause other surface modifications. Eighteen different types of ammonium- and phosphonium-salt-based DESs were prepared and characterized by FTIR. The graphene was characterized by FTIR, STA, Raman spectroscopy, XRD, SEM, and TEM. Additional experiments were performed to study the dispersion behavior of the functionalized graphene in different solvents. The DESs exhibited both reduction and functionalization effects on DES-treated graphene. Dispersion stability was investigated and then characterized by UV-vis spectroscopy and zeta potential. DES-modified graphene can be used in many applications, such as drug delivery, wastewater treatment, catalysts, composite materials, nanofluids, and biosensors. To the best of our knowledge, this is the first investigation on the use of DESs for graphene functionalization.