Adsorption Of Ca Research Articles

Mitigation of Fluoride Contamination in Drinking Water Supply Sources by Adsorption Using Bone Char: Effects of Mineral and Organic Matrix

This study focused on fluoride (F−) contamination of water sources in Bahimi village, Cameroon. After the first investigation, results revealed that all water samples collected had elevated concentrations of fluoride ions (2.3 ± 0.1) mg/L to (4.5 ± 0.2) mg/L above the WHO guidelines (less than 1.5 mg/L). To mitigate the F− levels, the use of bone char (BC) as an adsorbent material was proposed and its performance was tested. BC was prepared from bovine bones at different calcination temperatures (350 °C, 450 °C, 550 °C and 650 °C) and residence times (1 h and 2 h). The prepared materials were characterized in detail by SEM/EDS, BET, FTIR, and XRD. The BET findings indicated that the surface area of BC samples decreased with increasing calcination temperature and residence time. At a lower heating temperature and holding time (350 °C, 1 h), the prepared BC exhibited a higher specific surface area (112.3 ± 0.3) m2/g and adsorption capacity for F− in the sampled water. Also, the batch adsorption experiments showed that the optimized adsorbent dose of 8 g/L facilitates the reduction in the F− level of the sampled water below the acceptable limit level (1.5 mg/L) within 5 min of treatment. The presence of Ca2+ and Mg2+ in natural water has a positive effect on the removal of F− in BC resulting in a high adsorption performance range of (72.5 ± 1.4)% to (80.3 ± 0.6)%. It was found that the adsorption of Ca2+ on the BC surface occurs via cation exchange with Na+. However, an increase in dissolved organic carbon (DOC) in the treated water limited the application of BC. Overall, the study presented a cost-effective adsorbent for the removal of this recalcitrant ion in the water source.

Flotation of Li Pegmatite with a Soybean Oil-Based Collector: Fundamental Studies

ABSTRACT In this work, the effect of a soybean oil-based collector on the surface properties of spodumene, feldspar, quartz, and muscovite was characterized and evaluated. By means of gas chromatography, it was determined that the reagent was composed of a mixture of carboxylic acids: linoleic (48%), oleic (28%), palmitic (13.3%), stearic (3.6%), α-linolenic (3.4%), and elaidic (3.2%). The reagent contained ~14 ppm Ca (determined by inductively coupled plasma optical emission spectroscopy – ICP-OES) and a critical micellar concentration (CMC) of 100 mg/L. At pH 6, the spodumene recovery was 50–60% higher than the other mineral recoveries, ascribed to chemical adsorption of the collector ionic-molecular species, which has high hydrophobicity power, on Al3+ sites on the spodumene surface. For pH values >10, the recoveries of feldspar and quartz were higher than spodumene, due to their activation by hydroxyl and hydroxide of Ca and subsequent adsorption of ionic specimen of the collector. The electrokinetic potential curves of spodumene, feldspar, and muscovite with collector were shifted toward more negative values compared to their electrokinetic potential curves without reagent. Fourier transform infrared spectroscopy (FT-IR) showed chemical adsorption of the anionic species of the collector at pH 6 with the Al3+, Fe3+, and Ca sites on the surface of aluminosilicates and Ca for quartz.

Effects of kaolinite and montmorillonite calcined clays on the sulfate balance, early hydration, and artificial pore solution of limestone calcined clay cements (LC3)

This study investigated the physicochemical effects of kaolinite (CK) and montmorillonite (CM) calcined clays on the sulfate balance, early hydration, and artificial pore solution of limestone calcined clay cement (LC3). The effects of fineness, clay dissolution, and ion-adsorption capacity were evaluated by isothermal calorimetry, compressive strength, ICP-OES, and zeta potential within 72 h, respectively. Increasing the fineness of both calcined clays did not significantly affect the sulfate depletion kinetics or the compressive strength and the adsorption of Ca2+ ions onto the calcined clay’s surface is not the main factor responsible for differences in sulfate demand. The higher dissolution of ions Al in CK provided an intensified and accelerated formation of ettringite that competes for the available sulfate. We demonstrate that the chemical effects have a significant impact on the sulfate balance of LC3, revealing the lesser impact of alternative clays like montmorillonite compared to metakaolin (MK) which can minimize the problem of accelerated sulfate depletion of LC3 mixes with MK.

Effect of dissolved metal ions from mineral surfaces on the surface wettability of phosphate ore by flotation

The dissolved metal ions have a significant effect on the wettability of mineral surface in flotation slurry. In this work, the composition and characteristic of phosphate ore raw (R), flotation concentrate (FC), and flotation tailing (FT), the dissolution of metal ions from mineral surface and its effect on mineral surface wettability were investigated. The results of the dissolution test indicated that the concentrations of Ca2+ and Mg2+ are high (FT > R > FC), while Fe3+ and Al3+ were low in the slurry. H3PO4, as the slurry pH regulator, has the weakest dissolved ability of metal ions from mineral surface compared with HCl, HNO3 and H2SO4. The surface tension tests revealed that metal ions will combine with NaOL in the slurry, causing the consumption of NaOL. The contact Angle tests performed that some of NaOL adsorption sites on the FC and FT surface were covered the hydrolysates of Fe3+ and Al3+, which inhibited the hydrophobicity of the FC and FT surfaces. Ca2+ and Mg2+ consumed part of NaOL in the slurry, inhibiting the hydrophobicity of the FT surface. However, the adsorption of Ca2+ and Mg2+ on the FC surface increased the adsorption of NaOL, which enhanced the hydrophobicity of the FC surface.

Adsorption and electronic structure of submonolayer Ca on Ag(111)

Adsorption and electronic structure of submonolayer Ca on Ag(111)

Theoretical study on the effect of shear deformation on WSe2 as a cathode material for calcium ion batteries

AbstractIn this paper, the first‐principles method is used to calculate the electronic structure of the intrinsic WSe2 system and the Ca adsorbed WSe2 system under shear deformation, and the diffusion barrier of Ca on WSe2 is studied in depth. The results show that shear deformation can effectively reduce the band gap of WSe2 system, and shear deformation can easily lead to the transition from semiconductor properties to metal properties. The adsorption of Ca leads to the change of the band structure of WSe2. The contribution of Ca‐d electrons leads to an increase in the peak in the range of 3–6 eV. The shear deformation reduces the diffusion barrier of Ca on the WSe2 surface. This paper provides an improvement method for the application of WSe2 in the field of battery.

The electronic, magnetic, and optical behaviors of graphyne modulated by metal atoms adsorption: a first-principles study

The electronic, magnetic, and optical behaviors of graphyne modulated by various adsorbed metal atoms (Li, Na, K, Mg, Ca, Al, and Zn) from typical metal-ion batteries are studied by first-principles calculation. Notably, Mg and Zn adsorption systems are deemed unstable. In contrast, Li, Na, K, Ca, and Al systems exhibit two preferential adsorption sites, with the optimal position being the hollow center site within the large acetylenic ring. Upon the adsorption of these metal atoms, except for Ca adsorption systems exhibit semi-metallic behavior, while the other metal adsorption systems induced a transition from p-type to n-type semiconductors with decreased band gaps. Intriguingly, the inherent magnetism of the metal atoms vanished, resulting in a total magnetic moment of 0 μ B for the adsorption systems. Furthermore, the optical absorption and reflectivity peak positions for Ca adsorption systems show a significant redshift from violet to green and blue light regions. Conversely, other adsorption systems exhibit new absorption and reflection peaks in the infrared range, accompanied by an increase in both absorption coefficient and reflectivity across various spectral regions. These findings are conducive to the application in the field of novel optoelectronics and optical films.

Co/Ni/Cu-NH2BDC MOF@natural Egyptian zeolite ore nanocomposite for calcium ion removal in water softening applications.

Water softening is a treatment process required to remove calcium (Ca(II)) and magnesium (Mg(II)) cations from water streams. Nanocomposites can provide solutions for such multiple challenges and have high performance and low application costs. In this work, a multimetallic cobalt, nickel, and copper 2-aminoterephthalic acid metal-organic framework ((Co/Ni/Cu-NH2BDC) MOF) was synthesized by a simple solvothermal technique. This MOF was supported on an Egyptian natural zeolite ore and was used for the adsorption of Ca(II) ions for water-softening applications. The adsorbent was characterized using Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), N2 adsorption-desorption isotherms, and zeta potential measurements. The adsorption isotherm data for the prepared adsorbent toward Ca(II) were best fit using the Redlich-Peterson model and showed a maximum adsorption capacity of 88.1 mg/g. The adsorption kinetics revealed an equilibrium time of 10 min, which was best fit using the Avrami model. The intermolecular interactions of Ca(II) ions with zeolite and MOF were investigated by Monte Carlo simulations, molecular dynamics simulations, and FTIR and XRD analyses. The adsorption sites in the zeolite structure were oxygen atoms, while those in the MOF structure were amine nitrogen atoms. The Ca(II) ions are coordinated with the solvent molecules in both structures. Finally, the in vitro cytotoxicity of this nanocomposite was assessed, revealing viability levels of 74.57 ± 2.1% and 21 ± 2.79% for Vero and African green monkey kidney and human liver (HepG2) cells, respectively. Cytotoxicity assays help assess the environmental impact of these materials, ensuring that they do not harm aquatic organisms or disrupt ecosystems. Thus, this study demonstrated the valorization of MOF/zeolite as a valuable and industry-ready adsorbent that can appropriate Ca(II) contaminants from aqueous streams.

Potentiometric titration study of CaCO3 scaling control with non-water soluble polyetherimide and sulfonated polyetherimide films

Automatic potentiometric titration (APT) is a chemical analysis method to study the crystallization of CaCO3 in solution. We demonstrate how APT is also valuable for studying CaCO3 crystallization using water-insoluble polymer films, ideal for studying surfaces exposed to Ca2+ and CO32− ions with the capacity to remove Ca2+ and/or susceptible to scale formation, equipment surfaces, ion exchange surfaces or desalination membranes, etc. Polyetherimide (PEI) and sulfonated polyetherimide (SPEI) films were prepared by solvent casting technique, and their surface studied using FESEM, XPS, Z potential, and contact angle. APT assays were performed with polymer films, using a carbonate buffer (pH 9), dosed with CaCl2, and monitoring free Ca2+. The APT curves with PEI showed no significant difference compared to the control, while the presence of SPEI film affected the kinetics of CaCO3 formation. This was evidenced by changes in the slope and peak maximum of the APT curves. FTIR, XRD, and FESEM of the polymeric films and the CaCO3 after the APT assays showed control over the types of CaCO3 polymorphs. We show that the SPEI film is a good candidate to delay the formation of CaCO3 in water, through the adsorption of Ca2+ ions and the adsorption of pre-nucleation clusters of CaCO3.

Water Quality Characteristics and Water-Rock Interaction Mechanisms of Coal Mine Underground Reservoirs.

Constructing underground reservoirs in coal mines can effectively improve the recycling of mine water. Water-rock interactions within underground reservoirs have been demonstrated to improve water quality; however, the mechanisms underlying these water-rock interactions remain unclear, hindering the widespread applications of underground reservoirs. Thus, this study focused on the underground reservoir of the Shendong Daliuta coal mine. Through on-site sampling tests and single-mineral leaching experiments, combined with X-ray diffraction, X-ray fluorescence spectrometry, and scanning electron microscopy, the water quality characteristics of the inlet and outlet water samples from the coal mine underground reservoir were analyzed. Moreover, the physical and chemical properties of the collapsed rocks in the reservoir were investigated, with the aim of clarifying the mechanism underlying the water-rock interactions in coal mine underground reservoirs. The results revealed a significant self-purification effect of the coal mine underground reservoir. Compared with the inlet water sample, the outlet water sample featured substantially reduced amounts of solid-suspended substances, turbidity, total dissolved solids, and electrical conductivity, with the average removal rates of Fe and Mn approaching 98.73 and 92.12%, respectively. Along the flow direction of the inlet and outlet water of the coal mine underground reservoir, the concentrations of Na+ and Cl- presented an increasing trend, whereas the concentrations of Ca2+, Mg2+, and HCO3 - presented a decreasing trend. The concentration of K+ changed insignificantly, while the concentration of SO4 2- fluctuated unstably. The collapsed rocks in the Daliuta coal mine underground reservoir primarily comprised mudstone and sandstone with mineral components including quartz, orthoclase, albite, illite, kaolinite, glauconite, calcite, and pyrite. Among these, kaolinite exhibited the strongest adsorption capacity for Na+, Ca2+, and Mg2+ present in the mine water, while glauconite demonstrated the strongest dissolution capacity for Mg2+. Illite presented the strongest dissolution capacity for K+, while albite presented the strongest dissolution capacity for Na+. The water-rock interactions within the coal mine underground reservoir primarily included dissolution and adsorption processes, wherein mudstone and fine sandstone both played dominant roles in the adsorption of Ca2+, as well as in the dissolution of K+, Na+, and Mg2+. In particular, mudstone exhibited a stronger adsorption capacity than fine sandstone, whereas fine sandstone presented a stronger dissolution capacity than mudstone. Thus, our results offer theoretical guidance for understanding water quality purification mechanisms in coal mine underground reservoirs.

First-principles study on the effect of torsional deformation on WSe2 as an anode material for calcium ion batteries.

In this paper, the effects of torsional deformation on the electronic properties of intrinsic WSe2 system and Ca-adsorbed WSe2 system were systematically studied by first-principles method. The results show that Ca can be stably adsorbed on the vacancy (H site) of WSe2 surface in all deformation systems, and the adsorption energy of the system without deformation is the highest. Intrinsic WSe2 is a semiconductor with a direct band gap of 1.53 eV. The torsional deformation makes WSe2 change from a direct band gap semiconductor to an indirect band gap semiconductor and finally to a metal property. The adsorption of Ca makes the conduction band of WSe2 move down and increases the number of peaks in the conduction band region. The new density of state peaks are mainly derived from the contribution of W-d, Se-p, and d orbitals of adsorbed atoms in each adsorption system. Mulliken charge analysis shows that Ca transfers most of the valence electrons to the substrate, and the torsional deformation changes the amount of transferred charge. The twist deformation reduces the diffusion barrier of Ca on WSe2 surface from 0.20 to 0.14 eV. The above results provide a basis for the improved application of WSe2 in ion batteries. In this study, all the first-principles calculations are based on Materials Studio 8.0 software package. The generalized gradient approximation (GGA) functional Perdew-Burke-Ernzerhof (PBE) is used for the electron exchange correlation interactions in all systems. The optimization algorithm uses Broyden-Fletcher-Goldfarb-Shanno (BFGS) to optimize the model structure and calculate the energy. The measured cutoff energy is optimized to 450 eV, and the radius of the vacuum layer in the Z-axis direction is 20 Å. The K-point of 7 × 7 × 1 is selected by Monkhorst-Pack method. The structural optimization criterion is selected, the convergence radius of the force is 0.01 eV/Å, and the displacement radius between atoms is within 0.001 Å distance. The energy convergence radius of each atom is less than 1.0 × 10-6 eV/atom.

Effect of the type of ion-exchange resin on Mn<sup>2+</sup> adsorption in the presence of competing cations

Present in soils, ground and surface waters, manganese is among the most common metals in Earth crust. It is also an essential trace element to the functioning of several enzymes in the human body. However, exposure to high manganese concentrations can also be harmful to humans with psychiatric and motor effects and therefore, manganese concentrations in drinking water and also industrial effluents are regulated. In the current work, the adsorption of Ca<sup>2+</sup>, Mg<sup>2+</sup> and Mn<sup>2+</sup> on three different ion-exchange resins: (i) aminophosphonic acid - chelating (Purolite S950), (ii) polyacrylic weak acid cation (Purolite C104E) and (iii) polystyrene strong acid cation (Purolite C100) was investigated. The results revealed that Purolite S950 had the highest Mn2+ uptake (37.9 mg/mL-resin or 0.69 mmol/mL-resin) as compared to Ca<sup>2+</sup> (3.2 mg/mL-resin or 0.08 mmol/mL-resin) and Mg<sup>2+</sup> (~0 mg/mL-resin) and was selected for further kinetics and equilibrium studies. The results indicated Purolite S950 as particularly suited to be applied in the treatment of neutral mine waters with high Mg/Mn ratios. Additionally, Purolite S950 showed a small affinity for Ca<sup>2+</sup> and therefore an efficient Mn<sup>2+</sup> removal will depend on the Ca/Mn ratio of the mine water under treatment. According to the kinetic analysis, manganese sorption on Purolite S950 was described by the pseudo-second order model (r<sup>2</sup> > 0.98) with an activation energy of 10.40 kJ/mol and thus pore-difussion was the rate controlling step of the process. In terms of equilibrium studies, manganese sorption on Purolite S950 followed the Langmuir model with maximum loadings of up to 41.5 mg/mL-resin. The thermodynamic modelling indicated an exothermic process (-85.0 kJ/mol, as standard enthalpy) with a standard entropy of -274 J/mol.K, which was ascribed to the release of two adsorbed H<sup>+</sup> ions for each Mn<sup>2+</sup> ion taken up from solution

Effects of the hydrologic process and geochemistry on dissolved carbon in shallow groundwater surrounding Qinghai Lake

A high concentration of dissolved carbon in groundwater increases drinking water health risks and carbon transport. Understanding the comprehensive impact of hydrologic processes and geochemistry on dissolved carbon in shallow groundwater also is a fundamental prerequisite for estimating the carbon budget of lakes in the Tibetan Plateau. This study investigated the spatial–temporal characteristics of the hydrologic process, geochemistry and dissolved carbon in shallow groundwater by the stable isotope tracer method, Piper diagram and Boomerang envelope model. The driving factors of dissolved carbon in shallow groundwater were explored by correlation analysis and redundancy analysis. The results showed low dissolved inorganic carbon (DIC) concentrations and high dissolved organic carbon (DOC) concentrations during the thawing period and rainy season and high DIC concentrations and low DOC concentrations during the freezing period. The seepage velocity, soil carbon dioxide dissolution and gypsum dissolution were the main factors influencing DIC concentrations during the thawing period. The mineralization and decomposition of DOC and dissolution of carbonate rocks were the main factors influencing DIC concentrations during the freezing period. The concentrations of DOC were mainly controlled by the adsorption of Ca2+ and Mg2+, microbial activity and pollutants produced by human activities. Our results are useful for ecological sustainable development, human health, and research on the carbon transport in groundwater in the Tibetan Plateau.

Theoretical study on the effect of shear deformation on MoTe2 as cathode material for calcium ion batteries.

In this study, the electronic structure and diffusion barrier of Ca adsorbed MoTe2 system under different degrees of shear deformation were calculated based on the first-principles method. The results show that both the pure MoTe2 system and Ca-adsorbed MoTe2 system are affected by shear deformation. The pure MoTe2 undergoes a transition from direct to indirect band gap under shear deformation. The adsorption of Ca makes MoTe2 changes from semiconductor to quasi-metal. The results of the density of states show that Ca insertion makes the conduction band part of the adsorption system significantly enhanced. The diffusion barrier of Ca through MoTe2 indicates that the shear deformation promotes the diffusion of Ca on the surface of MoTe2. Shear deformation can effectively modulate the electronic properties of the MoTe2 system, which provides a theoretical basis for the application of MoTe2 materials in the field of ion batteries. In this study, Materials Studio 8.0 software was used to construct the MoTe2 model and Ca adsorbed MoTe2 model, and the CASTEP module was used for first-principles calculation.

Adsorption of Ca (II), Mn (II), Fe (III), Mg (II), and Pb (II) Ions from New Valley Groundwater Using Illite and Nanoparticles

Heavy metal pollution is a significant environmental concern due to its potential hazards. In this study, the adsorption of Ca (II), Mn (II), Fe (III), Mg (II), and Pb (II) ions from diluted aqueous solutions was investigated using both illite and nano-illite particles. The integration of illite as a natural and cost-effective material in water treatment for areas facing water pollution challenges offers a holistic solution with positive implications for the environment, economy, and public health. The multifaceted benefits of illite underscore its potential as a valuable tool in addressing water-related issues in remote and economically constrained regions. The synthesis and characterization of nano-illite were conducted through SEM, TEM, and FTIR spectroscopy. Notably, the TEM analysis revealed that the particle size of nano-illite (ranging from 2 to 4 nm) was smaller than that of illite (ranging from 20 to 30 nm). For the adsorption experiments, batch tests were performed, and the optimal conditions were determined. It was found that the highest adsorption efficiency for the studied metal ions was achieved at a pH of 7, a contact time of 60 minutes, an illite dosage of 0.4 g, and a nano-illite dosage of 0.3 g. Furthermore, the adsorption kinetics were analyzed using the pseudo-second-order kinetic model, while the adsorption isotherms were evaluated using the Langmuir model. This investigation provides valuable insights into the effective removal of heavy metal ions from aqueous solutions using illite and nano-illite particles. The results highlight the potential applicability of these adsorbents in addressing heavy metal pollution, thereby contributing to the mitigation of environmental risks associated with such contaminants.

Occurrence Modes of AAEMs (Na+ and Ca2+) and the Effect on the Molecular Structures of Zhundong Coal via Quantum Chemistry.

Zhundong coal is known for its high content of alkali and alkaline earth metals (AAEMs), which greatly influences coal processing and utilization. To reveal the occurrence modes and the effect of AAEM ions on the molecular structures of Zhundong coal, the previously constructed molecular structure models of vitrinite-rich and inertinite-rich Zhundong coal (ZD-V and ZD-I) were selected to simulate using quantum chemical methods. By focusing on Na+ and Ca2+, the adsorption capacity at different adsorption sites was investigated based on the density functional theory (DFT), and the effects of adsorption of Na+ and Ca2+ on nearby atomic charges, chemical bonds, and molecular orbitals were investigated. Results show that compared with ZD-I, ZD-V contains a more negative electrostatic potential (ESP) distribution and lower bond order, indicating that vitrinite contains more adsorption sites for AAEM ions and exhibits stronger chemical reactivity. Na+ and Ca2+ are easily adsorbed to the most negative ESP with the optimal adsorption site near the carbonyl group (C=O). Compared with adsorbed Na+, Ca2+ has a smaller adsorption distance from the molecule and a higher adsorption energy. Ca2+ can transfer more charge than Na+ and has more affinity with the coal molecule. Ca2+ at all adsorption sites is bound to organic molecules by chemisorption, which also reveals the reason for the low water-soluble Ca content in coal at the molecular level. Adsorption of AAEM ions has a more significant effect on the chemical bond of oxygen-containing functional groups near AAEM ions compared to the overall molecular fragments, which makes the nearby chemical bonds (C-O/C=O) decrease in bond order and increase in bond length. Ca2+ makes the nearby chemical bonds more prone to break than Na+. Additionally, Ca2+ has a more significant impact on the energy gaps (ΔEgap) compared to Na+. Adsorption of Ca2+ near the carbonyl and carboxyl groups leads to a significant decrease in ΔEgap, indicating an enhanced chemical reactivity of coal molecular fragments.

Adsorption of Ca on borophene for potential anode for Ca-ion batteries.

Two-dimensional borophene can be used in rechargeable batteries due to its high specific surface area. In this paper, the performance of borophene as an anode material for calcium ion batteries is predicted based on density functional theory calculations. The calculation results show that P doping enhances the calcium storage properties of borophene. The maximum adsorption number of calcium atoms in the P-doped system is 7, with a theoretical capacity of 964 mAh/g. DOS analysis showed that borophene exhibited metallic properties after adsorbing calcium atoms, which improved the electrical conductivity of the electrode material. Calculation of the diffusion energy barrier shows that strain has an effect on calcium diffusion in monolayer borophene, and compressive strain promotes calcium diffusion through borophene. The findings suggest that borophene may be a promising electrode material for calcium-ion batteries. In this paper, the intrinsic model and doping model of borophene are constructed by Material Studio 8.0, and the first-principles calculation is carried out by CASTEP module.

Understanding adsorption of divalent metals ions (Mg, Ca) on Nitrogen-, Boron- doped, and defective graphene in nanofiltration process using van der Waals density functional method

Removal of divalent metal ions (Mg and Ca) by graphene membrane has a great implication for manufacturing chitin and chitosan in filtration process. Despite its importance, influences of the doping and vacancy in graphene on the adsorption of those metal ions remain unclear. Here, we study the adsorption of those metal ions on several graphene surfaces, namely pristine graphene (Gra), graphitic N- and B- doped graphene (N- and B-Gra), monovacancy graphene (MV-Gra), monovacancy graphene functionalized by an epoxy (O-MV-Gra), and monovacancy graphene functionalized by an hydroxyl group (OH-MV-Gra) by van der Waals density functional (vdW-DF) method. It was found all considered graphene surfaces have strong interactions with Ca, whereas Mg only chemisorbs on MV-Gra and B-Gra. Energetically, comparing with Ca adosprtion on pristine graphene, both B doping and vacancy creation strengthen the Ca adsorption, while N doping slight decreases it. The electronic structure analysis uncovers enhancement of the Cagraphene interaction by B doping and vacancy formation. Because of the results that have been observed, the removal of Ca ions from aqueous solution can be enhanced by the creation of nanopore or B doping in graphene, in which Ca atom are strongly captured by graphene.

Calcium isotope fractionation associated with adsorption and desorption on/from δ-MnO2

Small mineral particles present in soils, such as clay minerals and some oxyhydroxides, constitute important nutrient reservoirs. This behavior is due to the negative charges and high specific surface areas of these particles allowing them to adsorb cations such as calcium (Ca), a macronutrient that occupies key physiological and structural functions in plant metabolism. Although the chemical reactivity of clay minerals is rather well-known in the literature, especially toward macronutrients such as Ca, that of oxyhydroxides such as phyllomanganate minerals remains largely unexplored.To enhance our understanding of the mechanisms at the origin of the storage/release of the different isotopes of Ca in a soil solution, the possible fractionation between 40Ca and 44Ca during adsorption and desorption of Ca on a synthetic phyllomanganate, abiotically precipitated in the laboratory [synthetic analog of vernadite (δ-MnO2)], was studied. Experiments were performed in batch (closed system), and several parameters (time, pH of the solution, Ca concentration and nature and concentration of the desorbent) were tested to cover a large range of physicochemical conditions.This study demonstrated that the light 40Ca isotope is preferentially adsorbed on δ-MnO2, with Δ44/40Ca (the apparent fractionation of the aqueous solution at the stationnary state of adsorption compared to the initial one) of the adsorbed Ca that can reach 1.19 ± 0.15‰. The results showed that this isotopic fractionation occurs at chemical equilibrium in a closed system and that the isotopic fractionation measured in this study during Ca adsorption on phyllomanganate is significantly higher than that reported in the literature during Ca adsorption on other soil constituents such as clay minerals. At pH below 4 Ca occupies only the interlayer/basal sites whereas above this pH Ca fills interlayer/basal sites (∼86%) and edges sites (∼14%). By combining the experimental data obtained at different pH values, initial Ca concentrations and interaction times, our results suggest that isotopic signature of the Ca adsorbed on δ-MnO2 is dependent on the nature of the site involved in the adsorption step (i.e., enriched in 40Ca in the interlayer with Δ44/40Ca equal to −0.43‰ and enriched in 44Ca when bound to the edges with Δ44/40Ca equal to +3.5‰). As revealed by surface complexation modeling, such contrasting behavior between the two types of adsorption sites could be due to the bidendate nature of the Ca adsorption occurring on edges and to ion exchange of Ca2+ with H+ in the interlayer sites. Finally, desorption experiments point to total but not instantaneous Ca desorption, probably due to a partial collapse of the interlayer with some ions used to desorb Ca2+ (K+, NH4+, hexaamine-cobalt). This suggests that the amount of bioavailable Ca in soils by simple ion-exchange reactions is highly dependent on the nature of the ions which could desorb Ca present in the soil solution.

Modulation of the magnetic, electronic, and optical behaviors of WS2 after metals adsorption: A first-principles study

The electronic, magnetic, and optical absorption properties of partial metal adsorbed WS2 systems were calculated by using the first-principles approach. The optimal adsorption sites corresponding to each metal adsorption on the WS2 system are diverse. The Pt-, Mg-, and Zn-WS2 systems are non-magnetic semiconductors, and the Ag-, Au-, Cr-, Fe-, Mn-, Mo-, Nb-, Ni-, and Ti-WS2 systems appear magnetic semiconductors. Whereas the Ca-, Li-, and Na-WS2 systems exhibit magnetic metal properties. The Ca- and Nb-WS2 systems have a significant red-shift tendency in the ultraviolet region. In particular, the adsorption of Ca and Nb enhance the absorption of WS2 in the ultraviolet region. The Nb-WS2 system has a strong absorption peak intensity that reached 1.09◊105 cm−1 at 448.3 nm. Therefore, metal adsorbed WS2 systems will be helpful for the studying of nano-spintronics and photovoltaics devices.