Adsorption Of Cations Research Articles

Specific Adsorption of Alkaline Cations Enhances CO–CO Coupling in CO2 Electroreduction

Specific Adsorption of Alkaline Cations Enhances CO–CO Coupling in CO₂ Electroreduction

Preparation and characterisation of chitosan/bacterial Escherichia coli biocomposite for malachite green dye removal: modeling and optimisation of the adsorption process

ABSTRACT Herein, a new biocomposite was obtained by loading a bacterial suspension of Escherichia coli onto a chitosan matrix to produce a unique biocomposite (chitosan – E. coli) with effective properties for biosorption of malachite green dye from water. The physicochemical characteristics of the chitosan – E. coli biocomposite were studied by employing XRD, FTIR, FESEM-EDX and pHpzc. The optimisation of biosorption conditions was achieved using a Box-Behnken Design (RSM-BBD) to assess the effect of variables on the dye removal: biocomposite dose (0.02–0.1 g/100 mL), pH (4–8) and contact time (10–300 min). The optimal conditions for dye removal (84.3%) were achieved with a chitosan – E. coli dose of 0.1 g/100 mL, and a contact time of 160 minutes with a pH of 8. The equilibrium and kinetic experimental findings show the biosorption of malachite green dye by chitosan – E. coli follows the Langmuir and pseudo-second-order models, respectively. The maximum dye adsorption capacity (q max ) of malachite green for the chitosan – E. coli biocomposite was 164.7 mg/g, where the dye adsorption mechanism was attributed to several effects such as hydrogen bonding, n-π interactions, and electrostatic attraction. Thermodynamic analysis indicated that the biosorption process was spontaneous and endothermic, with a positive enthalpy change (ΔH° = 40.9 kJ/mol) and a negative Gibbs free energy (ΔG°) at all tested temperatures. The biocomposite chitosan – E. coli adsorbent exhibits favourable cationic dye adsorption that is anticipated to have utility for remediation of dye effluent in industrial wastewater.

Comment on Zhou et al. Adsorption Behaviors of Lanthanum (III) and Yttrium (III) Ions on Gibbsite. Minerals 2023, 13, 1530

We compare trends in experimental observations reported by Zhou et al. to relevant results from numerous previously published studies. Based on these comparisons, we question the reliability of the gibbsite titration data and consider the cation uptake curves to be incomplete and questionable as well. The adsorption edges in Zhou et al. are too flat compared to the typical adsorption edges reported in hundreds of studies. Finally, we are convinced that trends of cation adsorption with NaNO3 content not only disagree with relevant, previously published results, but are even opposite to trends expected with increasing ionic strength, whenever such effects are observed. Finally, we discuss other inconsistencies in the experimental data.

Distribution and Co-Enrichment Factors of Arsenic and Fluoride in the Groundwater of the Plain Area of the Aksu River Basin, Xinjiang, PR China

The Aksu River Basin is located in the western region of the middle part of the southern foothills of the Tianshan Mountains and the northwestern edge of the Tarim Basin in Xinjiang, China. High-arsenic (As)/high-fluoride (F) groundwater is widely distributed in this area and is harmful to the life of local residents and to agricultural production. It is of great importance to understand the distribution and causes of As-F co-enrichment in the groundwater in this area. Based on the test results of 138 groundwater samples in the plain area of the Aksu River Basin, the hydrochemical characteristics of groundwater and the spatial distribution of As-F co-enrichment groundwater were analyzed under the following conditions: a single-structure phreatic aquifer (SSPA), a phreatic aquifer in a confined groundwater area (PACGA), a shallow confined aquifer (SCA), and a deep confined aquifer (DCA), all in a recharge area, transition area, and an evaporation area. The hydrogeochemical processes affecting the source, migration, and enrichment of As-F in the groundwater were revealed. The results showed that the chemical types of groundwater in the study area were mainly HCO3·SO4-Ca·Mg and SO4·Cl-Na·Mg. Horizontally, high-As-F groundwater was mainly distributed in the transition area and evaporation area in the middle and lower reaches of the Aksu River Basin. The area is close to the edge of the desert, where the groundwater runoff is sluggish and in an alkaline-reducing groundwater environment. Vertically, high-As groundwater was mainly distributed in the PACGA at a depth of 10–20 m and in the SCA at a depth of 80–100 m. High-F groundwater was mainly concentrated in the PACGA at a depth of 10–30 m and in the SCA at a depth of 80–100 m, and As-F co-enrichment groundwater was mainly concentrated in the PACGA at a depth of 10–20 m and in the SCA at a depth of 80–100 m. The hydrochemical characteristics of the groundwater in the Aksu River Basin were closely related to geological conditions, hydrogeological conditions, and the hydrochemical environment of the groundwater. As-F co-enriched groundwater was mainly affected by the combination of a small topographic gradient, a shallow groundwater burial depth, a weak reducing alkaline groundwater environment, strong evaporation and concentration, the weathering and dissolution of evaporated salt rock, and the alternating adsorption of cations.

A DFT Study of Band-Gap Tuning in 2D Black Phosphorus via Li+, Na+, Mg2+, and Ca2+ Ions.

Black phosphorus (BP) and its two-dimensional derivative (2D-BP) have garnered significant attention as promising anode materials for electrochemical energy storage devices, including next-generation fast-charging batteries. However, the interactions between BP and light metal ions, as well as how these interactions influence BP's electronic properties, remain poorly understood. Here, we employed density functional theory (DFT) to investigate the effects of monovalent (Li+ and Na+) and divalent (Mg2+ and Ca2+) ions on the valence electronic structure of 2D-BP. Molecular orbital analysis revealed that the adsorption of divalent cations can significantly reduce the band gap, suggesting an enhancement in charge transfer rates. In contrast, the adsorption of monovalent cations had minimal impact on the band gap, suggesting the preservation of 2D-BP's intrinsic electrical properties. Energetic and charge analyses indicated that the extent of charge transfer primarily governs the ability of ions to modulate 2D-BP's electronic structure, especially under high-pressure conditions where ions are in close proximity to the 2D-BP surface. Moreover, charge polarization calculations revealed that, compared with monovalent cations, divalent cations induced greater polarization, disrupting the symmetry of the pristine 2D-BP and further influencing its electronic characteristics. These findings provide a molecular-level understanding of how ion interactions influence 2D-BP's electronic properties during ion-intercalation processes, where ions are in close proximity to the 2D-BP surface. Moreover, the calculated diffusion barrier results revealed the potential of 2D-BP as an effective anode material for lithium-ion, sodium-ion, and magnesium-ion batteries, though its performance may be limited for calcium-ion batteries. By extending our understanding of interactions between ions and 2D-BP, this work contributes to the design of efficient and reliable energy storage technologies, particularly for the next-generation fast-charging batteries.

Preparation and characterization of oat hulls-filled-sodium alginate biocomposite microbeads for the effective adsorption of toxic methylene blue dye

In this work, the performance of oat hull-filled sodium alginate (SA-O) biocomposite microbeads in the adsorptive removal of methylene blue (MB) dye was examined. First, oat hulls were pulverized and biocomposite gels containing different weight ratios of oat hulls (10 %, 20 %, and 30 %, concerning the SA amount) were prepared by dispersing them in SA solution by ultrasonic homogenization method. Finally, gels were cross-linked by dropping into a 2 % CaCl2 solution. The study revealed that the optimal adsorbent dosage was 0.025 g/50 mL, pH was roughly 6–8, and the contact time was 120 min. According to isotherm models, the non-linear Sips and Langmuir model was more appropriate compare to other isotherms from error analysis, with a maximum adsorption capacity of 687.65 mg/g and 757.57 mg/g at 298 K, respectively. Furthermore, the non-linear kinetic data and error analyzes demonstrated that the process followed the pseudo-second-order kinetic. The adsorption process was exothermic (∆H°=−17.71 kJ/mol) and spontaneous (∆G°=−26.23 kJ/mol) at 298 K, based on thermodynamic characteristics. Furthermore, reusability investigations demonstrated that the adsorbent retained its performance with no major changes in characteristics. This work reveals that highly efficient, low-cost, sustainable, and eco-friendly SA-O composites with properties might be useful adsorbents for cationic dye adsorption.

Chemical Characteristics and Water Quality Assessment of Groundwater in the Dongjiang-Hanjiang River Basin, China

Groundwater plays an important role in the rapid economic development of the Dongjiang-Hanjiang River Basin. This paper uses the Gibbs model, ionic ratio coefficient analysis, factor analysis, water quality index method and human health risk assessment model to estimate the chemical properties and quality of groundwater in the Dongjiang-Hanjiang Basin. The ion concentration and proportion of SO42- water in the Hanjiang River Basin are higher than those in the Dongjiang River Basin. The groundwater ions come mainly from the dissolution of carbonate rocks, silicate rocks and saline rocks, some of which come from human activities such as industry and mining. Groundwater composition is controlled by rock dissolution, alternating cation adsorption, and human activities. The proportion of rock dissolution is the greatest, but the influence of human activities is obvious. The intensity of human activities such as industry, mining and agriculture is greater in the Hanjiang River Basin than in the Dongjiang River Basin. The overall groundwater quality is poor, and the Dongjiang River Basin is better than the Hanjiang River Basin. The above-standard factors are mainly pH, I−, NO3−, NH4+, As and Pb2+. Nitrate pollution in groundwater is harmful to health and the health risk of children from nitrate is higher than that of adults. The health risk in the Hanjiang River Basin is higher than that in the Dongjiang River Basin. This can serve as a vital reference for similar areas worldwide, offering guidance for groundwater management, pollution prevention and control.

Adsorption of Imidazolium‐Based Ionic Liquid On Pt(111) Surface Studied Using Density Functional Theory

AbstractThe strength and nature of adsorption of imidazolium‐based tetraflouroborate ionic liquid (IL) on platinum surface has been investigated via first principle‐based density functional theory method. Adsorption of both IL cation and IL ion‐pair as a function of increasing alkyl chain length is taken into consideration. Three different orientations of ionic liquid cations are found to be stable with higher adsorption energy noticed for the alkyl chain parallel to the platinum surface. The anions are found to stabilize the IL cation orientation where the alkyl chain is oriented perpendicular the platinum surface. These results are further corroborated by the charge transfer analysis and electron density difference maps. The significant charge transfer between the ionic liquid pair and the surface indicates electrochemical applications for systems involving electrolytes and metal surface, where electrostatic interactions play a major role. The results of this investigation can be helpful for further analysis of electrode–electrolyte systems as well as the development of force field parameters for these systems.

Microstructural Evaluation and Linkage to the Engineering Properties of Metal-Ion-Contaminated Clay.

The rapid progress of urbanization and industrialization has led to the accumulation of large amounts of metal ions in the environment. These metal ions are adsorbed onto the negatively charged surfaces of clay particles, altering the total surface charge, double-layer thickness, and chemical bonds between the particles, which in turn affects the interactions between them. This causes changes in the microstructure, such as particle rearrangement and pore morphology adjustments, ultimately altering the mechanical behavior of the soil and reducing its stability. This study explores the effects of four common metal ions, including monovalent alkali metal ions (Na+, K+) and divalent heavy metal ions (Pb2+, Zn2+), with a focus on how ion valence and concentration impact the soil's microstructure and mechanical properties. Microstructural tests show that metal ion incorporation reduces particle size, increases clay content, and transforms the structure from layered to honeycomb-like. Small pores decrease while large pores dominate, reducing the specific surface area and pore volume, while the average pore size increases. Although cation exchange capacity decreases, cation adsorption density per unit surface area increases. Monovalent ions primarily disperse the soil structure, while divalent ions induce coagulation. Macro-mechanical tests reveal that metal ion contamination reduces porosity under loading, with compressibility rises as the ion concentration increases. Soils contaminated with alkali metal ions shows higher compression coefficients at all loads, while heavy metal ions cause higher compression under lower loads. Shear strength, the internal friction angle, and cohesion in metal-ion-contaminated clay decrease compared to uncontaminated field-state clay, with greater declines at higher ion concentrations. The Micropore Morphology Index and hydro-pore structural parameter effectively characterize both micro- and macrostructural properties, establishing a quantitative relationship between HPSP and the engineering properties of metal-ion-contaminated clay.

Electrospinning of Sodium Alginate/Copper Oxide Nanofibrous Composite Membrane and Its Application of Cationic Dye Adsorption

AbstractDye wastewater is becoming one of the most significant sources of water pollution, and its impact on human survival is immeasurable. In this study, we successfully synthesized a nanofiber membrane with environmentally friendly and efficient properties using electrospinning of a mixture of sodium alginate (SA) and copper oxide (CuO) nanoparticles, aimed at effective dye removal. The adsorption performance of the SA/CuO nanofiber membrane was evaluated using the cationic dye methylene blue (MB). The maximum adsorption capacity of the nanofiber membrane was increased significantly with the addition of CuO nanoparticles, reaching a maximum value of 1633.4 mg g−1, almost twice as much as that of pure SA membrane. The adsorption kinetics follows the pseudo‐second‐order model, where chemisorption acts as the rate‐limiting step. The adsorption isotherm data indicate that the adsorption is monolayer. The nanofibrous membranes showed better dye removal under an alkaline environment. After four cycles of adsorption/desorption, the MB removal efficiency remained at 70.1% of the original adsorption capacity. The addition of CuO nanoparticles facilitated the adsorption of MB dyes, while the form of the nanofibrous membrane is easily recoverable and reusable. Therefore, the as‐prepared SA/CuO nanofibrous composite membrane is a potentially favorable adsorbent material for wastewater treatment applications.

On the Parasitic Surface Adsorption of Pyrrolidinium and Phosphonium-based Ionic Liquids Preventing Accurate Differential Capacitance Measurements

Abstract Differential capacitance measurements are known to provide vital information regarding electrical double layer charging as well as interfacial structuring of ionic liquids and ionic liquid-based electrolytes. Several hurdles have prevented these types of measurements from becoming widely used, including the fact that there exists no real consensus as to how the measurement needs to be performed and the results analyzed. To add to the difficulty, some ionic liquids are known to display a hysteresis process, thus inducing measurement variabilities. In this report, we study pyrrolidinium and phosphonium-based ionic liquid electrolytes and show that hysteresis processes indeed exist and that these are mostly the consequence of cationic adsorption on the surface. Atomic force microscopy experiments reveal that pyrrolidinium-based systems display a much denser degree of ionic compaction at the interface, compared to the phosphonium-based systems, a fact that we correlate with the much more intense hysteresis measured in pyrrolidinium-based systems. We further propose a new method for the measurement of differential capacitance and compare it with other methods in use. It is found that the proposed method allows to minimize hysteresis phenomena, thereby leading to better accuracy.

Multifunctional property of N,N-bis (carboxymethyl) glutamic acid modified biomass material: adsorption and degradation removals of cationic dyes in wastewater

As a common type of pollutants in industrial wastewater, cationic dyes have attracted great attentions. Using biodegradable N,N-di (carboxymethyl) glutamic acid (GLDA) as ligand and corn stalk (CS) as matrix, a novel and green biomass modified material GLDA-CS was successfully prepared. The multifunctional property of GLDA-CS for removing methylene blue (MB), malachite green (MG) and alkaline red 46 (R-46) from wastewater was evaluated. The dyes were removed by the electrostatic adsorption based on the cationic adsorption properties of GLDA-CS. The removal rates of MB, MG and R-46 can quickly reach 90.4%, 96.8% and 94.8% in short time. especially for MG and R-46 even only 20 min. The adsorption capacities of the dyes still remain more than 86.5% of the initial values after 5 cycles. In a heterogeneous system, the dyes were removed by Fenton-like degradation based on the metal chelating property of GLDA-CS. 100% degradation rates of the dyes can be achieved in 35 min under the acidic region. Even if at pH 7, degradation rates are 44.1%, 47.1% and 56.6% higher than those under the conventional homogeneous system, and the degradation rate remained at 83.7% after 5 cycles. Regardless of the adsorption or degradation, GLDA-CS shows strong anti-anion interference ability. The potential mechanisms of adsorption and degradation for the dyes by GLDA-CS were deduced by quantization calculation. It is concluded that the adsorption removal of the dyes by GLDA-CS follows MG > R-46 > MB, and mainly depends on the electrostatic interaction between -COOH in GLDA-CS and -N- in the dye molecules. Based on the degradation mechanism of Fenton-like reaction, the possible active sites of the dyes attacked by free radicals and their possible degradation intermediates were predicted by the calculations of Fukui function.

Ceftriaxone Removal with Sulfonic-phosphoric Acid Resin Based on Cation Adsorption Characteristic

Ceftriaxone Removal with Sulfonic-phosphoric Acid Resin Based on Cation Adsorption Characteristic

Interdisciplinary Project-Based Learning of Fine Chemical Technology for Applied Chemistry Majors: Preparation of High Cationic Degree Cotton-Based Adsorbent

Interdisciplinary Project-Based Learning of Fine Chemical Technology for Applied Chemistry Majors: Preparation of High Cationic Degree Cotton-Based Adsorbent

Enhanced pozzolanic reactivity in hydrogen-form zeolites as supplementary cementitious materials

Pozzolans rich in silica and alumina react with lime to form cementing compounds and are incorporated into portland cement as supplementary cementitious materials (SCMs). However, pozzolanic reactions progress slower than portland cement hydration, limiting their use in modern construction due to insufficient early-age strength. Hence, alternative SCMs that enable faster pozzolanic reactions are necessary including synthetic zeolites, which have high surface areas and compositional purity that indicate the possibility of rapid pozzolanic reactivity. Synthetic zeolites with varying cation composition (Na-zeolite, H-zeolite), SiO2/Al2O3 ratio, and framework type were evaluated for pozzolanic reactivity via Ca(OH)2 consumption using ion exchange and in-situ X-ray diffraction experiments. Na-zeolites exhibited limited exchange reactions with KOH and Ca(OH)2 due to the occupancy of acid sites by Na+ and hydroxyl groups. Meanwhile, H-zeolites readily adsorbed K+ and Ca2+ from a hydroxide solution by exchanging cations with H+ at Brønsted acid sites or cation adsorption at vacant acid sites. By adsorbing cations, the H-zeolite reduced the pH and increased Ca2+ solubility to promote pozzolanic reactions in a system where Ca(OH)2 dissolution/diffusion was a rate limiting factor. High H-zeolite reactivity resulted in 0.8 g of Ca(OH)2 consumed per 1 g of zeolites after 16 h of reaction versus 0.4 g of Ca(OH)2 consumed per 1 g of Na-zeolite. The H-zeolite modulated the pore fluid alkalinity and created a low-density amorphous silicate phase via mechanisms analogous to two-step C-S-H nucleation experiments. Controlling these reaction mechanisms is key to developing next generation pozzolanic cementitious systems with comparable hydration rates to portland cement.

Enhancing Sodium-Ion Transport in LTA Zeolite/PEO Composite Polymer Electrolytes through Cation Adsorption

Enhancing Sodium-Ion Transport in LTA Zeolite/PEO Composite Polymer Electrolytes through Cation Adsorption

Metal-Cation-Induced Tiny Ripple on Graphene.

Ripples on graphene play a crucial role in manipulating its physical and chemical properties. However, producing ripples, especially at the nanoscale, remains challenging with current experimental methods. In this study, we report that tiny ripples in graphene can be generated by the adsorption of a single metal cation (Na+, K+, Mg2+, Ca2+, Cu2+, Fe3+) onto a graphene sheet, based on the density functional theory calculations. We attribute this to the cation-π interaction between the metal cation and the aromatic rings on the graphene surface, which makes the carbon atoms closer to metal ions, causing deformation of the graphene sheet, especially in the out-of-plane direction, thereby creating ripples. The equivalent pressures applied to graphene sheets in out-of-plane direction, generated by metal cation-π interactions, reach magnitudes on the order of gigapascals (GPa). More importantly, the electronic and mechanical properties of graphene sheets are modified by the adsorption of various metal cations, resulting in opened bandgaps and enhanced rigidity characterized by a higher elastic modulus. These findings show great potential for applications for producing ripples at the nanoscale in graphene through the regulation of metal cation adsorption.

Alkali metal cation adsorption–induced surface polarization in polymeric carbon nitride for enhanced photocatalytic hydrogen peroxide production

Photocatalytic hydrogen peroxide (H2O2) generation on the catalyst surface from oxygen is an electron-demanding process, making the construction of an electron-rich surface highly advantageous. In this study, a localized electric field was observed on the surface of polymeric carbon nitride (g-C3N4) when alkali metal cations were adsorbed onto it. These fields effectively inhibited surface carrier recombination and extended their lifespan, thereby enhancing H2O2 production. As a result, g-C3N4 achieved a superior H2O2 yield of 2.25 mM after 1 h in a 0.25 M K+ solution, which was 2.06 times greater than that (1.09 mM) achieved in a pure solvent. Notably, the increase in photocatalytic efficiency showed a remarkable dependence on ion species. At low concentrations, H2O2 generation efficiency was in the order of Li+ < Na+ < K+ < Rb+ < Cs+. However, after optimizing the ion concentration, the highest H2O2 production was achieved in a solution containing K+ instead of Cs+. Molecular dynamics simulations and temperature-dependent photocatalysis experiments revealed that the synergistic interaction between adsorption energy and adsorption distance was crucial in governing the extent to which alkali metal cation adsorption enhanced g-C3N4 photocatalytic H2O2 production. This study provides theoretical insights for the design of materials for electron-demanding photocatalysis and aids in understanding variations in photocatalytic behavior in natural waters.

Utilization of waste PET-derived metal–organic framework grafted polyaniline composite for heavy metal adsorption from aqueous solution

In this research, we used waste polyethylene terephthalate (PET) bottles as a source to develop an iron-based MOF-supported polyaniline (Fe-MOF@PANI) composite, which was then applied for the adsorptive removal of cadmium (Cd(II)) and lead (Pb(II)) ions from aqueous environment. A comprehensive characterization of the Fe-MOF@PANI composite was conducted using several analytical techniques including FTIR, PXRD, SEM, EDX with mapping, and XPS analysis, which provided significant insights into its functionality, crystalline structure, surface morphology, and elemental composition. The synthesized Fe-MOF exhibited a spindle-shaped morphology that was evenly distributed over the surface of the PANI composite, as confirmed by SEM analysis. Additionally, the porous characteristics of the Fe-MOF@PANI composite were proven through BET analysis. The Fe-MOF@PANI composite exhibited remarkable adsorption efficiencies for selected metal cations, achieving adsorption capacities of 143.36 mg/g and 258.59 mg/g for Cd(II) and Pb(II) ions, respectively. The findings of the isotherm and kinetic studies demonstrated that the adsorption process fitted well with Langmuir and pseudo-second-order kinetics, indicating that adsorption of both metal cations occurs in a monolayer formation and includes chemisorption mechanisms, respectively. This research paves the way for further development and application of post-functionalized PET-derived MOF adsorbents to remove Cd(II) and Pb(II) ions from water efficiently.

Variation in Cation Adsorption Mechanism Controlled by Chemical and Structural Heterogeneities at the Quartz (101)–Water Interface

Variation in Cation Adsorption Mechanism Controlled by Chemical and Structural Heterogeneities at the Quartz (101)–Water Interface