An examination of isotherm generation : impact of bottle-point method upon potassium ion exchange with strong acid cation resin

This paper relates to the importance of impact of the chosen bottle-point method when conducting ion exchange equilibria experiments. As an illustration, potassium ion exchange with strong acid cation resin was investigated due to its relevance to the treatment of various industrial effluents and groundwater. The “constant mass” bottle-point method was shown to be problematic in that depending upon the resin mass used the equilibrium isotherm profiles were different. Indeed, application of common equilibrium isotherm models revealed that the optimal fit could be with either the Freundlich or Temkin equations, depending upon the conditions employed. It could be inferred that the resin surface was heterogeneous in character, but precise conclusions regarding the variation in the heat of sorption were not possible. Estimation of the maximum potassium loading was also inconsistent when employing the “constant mass” method. The “constant concentration” bottle-point method illustrated that the Freundlich model was a good representation of the exchange process. The isotherms recorded were relatively consistent when compared to the “constant mass” approach. Unification of all the equilibrium isotherm data acquired was achieved by use of the Langmuir Vageler expression. The maximum loading of potassium ions was predicted to be at least 116.5 g/kg resin.

Suppression of cluster ions during rapidly increasing particle number concentration events in the environment

We show that the cluster ion concentration (CIC) in the atmosphere is significantly suppressed during events that involve rapid increases in particle number concentration (PNC). Using a neutral cluster and air ion spectrometer, we investigated changes in CIC during three types of particle enhancement processes – new particle formation, a bushfire episode and an intense pyrotechnic display. In all three cases, the total CIC decreased with increasing PNC, with the rate of decrease being greater for negative CIC than positive. We attribute this to the greater mobility, and hence the higher attachment coefficient, of negative ions over positive ions in the air. During the pyrotechnic display, the rapid increase in PNC was sufficient to reduce the CIC of both polarities to zero. At the height of the display, the negative CIC stayed at zero for a full 10 min. Although the PNCs were not significantly different, the CIC during new particle formation did not decrease as much as during the bushfire episode and the pyrotechnic display. We suggest that the rate of increase of PNC, together with particle size, also play important roles in suppressing CIC in the atmosphere.

Fabrication of Nb2O5 nanosheets for high-rate lithium ion storage applications

Nb2O5 nanosheets are successfully synthesized through a facile hydrothermal reaction and followed heating treatment in air. The structural characterization reveals that the thickness of these sheets is around 50 nm and the length of sheets is 500~800 nm. Such a unique two dimensional structure enables the nanosheet electrode with superior performance during the charge-discharge process, such as high specific capacity (~184 mAh.g-1) and rate capability. Even at a current density of 1 A.g-1, the nanosheet electrode still exhibits a specific capacity of ~90 mAh.g-1. These results suggest the Nb2O5 nanosheet is a promising candidate for high-rate lithium ion storage applications.

Removal of herbicides from aqueous solutions by modified forms of montmorillonite

This investigation for the removal of agricultural pollutants, imazaquin and atrazine was conducted using montmorillonite (MMT) exchanged with organic cations through ion exchange. The study found that the adsorption of the herbicides was affected by the degree of organic cation saturations, the size of organic cations and the different natures of the herbicides. The modified clays intercalated with the larger surfactant molecules at the higher concentrations tended to enhance the adsorption of imazaquin and atrazine. In particular, the organoclays were highly efficient for the removal of imazaquin while the adsorption of atrazine was minimal due to the different hydrophobicities. Both imazaquin and atrazine were influenced by the changes of pH. The amphoteric imazaquin exists as an anion at the pH 5–7 and the anionic imazaquin was protonated to a neutral and further a cationic form when the pH is lower. The weak base, atrazine was also protonated at lower pH values. The anionic imazaquin had a strong affinity to the organoclays on the external surface as well as in the interlayer space of the MMT through electrostatic and hydrophobic interactions. In this study, the electrostatic interaction can be the primary mechanism involved during the adsorption process. This study also investigated a comparative adsorption for the imazaquin and atrazine and the lower adsorption of atrazine was enhanced and this phenomenon was due to the synergetic effect. This work highlights a potential mechanism for the removal of specific persistence herbicides from the environment.

The molecular structure of kaolinite–potassium acetate intercalation complexes: A combined experimental and molecular dynamic simulation study

The kaolinite (Kaol) intercalated with potassium acetate (Ac) was prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry. Molecular dynamic simulation was performed to investigate the structure of Kaol–Ac intercalation complex and the hydrogen bonds between Kaol and intercalated Ac andwater using INTERFACE forcefield. The acetate anions andwater arranged in a bilayer structure in the interlayer space of Kaol. The potassium cations distributed in the interlayer space and strongly coordinated with acetate anions aswell aswater rather than keyed into the ditrigonal holes of tetrahedral surface of Kaol. Strong hydrogen bonds formed between the hydrogen atoms of hydroxyl on the octahedral surface and oxygen atoms of both acetate anions and water. The acetate anions andwater also weakly bonded hydrogen to the silica tetrahedral surface through their hydrogen atoms with the oxygen atoms of silica tetrahedral surface.

New insights into the molecular structure of kaolinite–methanol intercalation complexes

A series of kaolinite–methanol complexes with different basal spacings were synthesized using guest displacement reactions of the intercalation precursors kaolinite–N-methyformamide (Kaol–NMF), kaolinite–urea (Kaol–U), or kaolinite–dimethylsulfoxide (Kaol–DMSO), with methanol (Me). The interaction of methanol with kaolinite was examined using X-ray diffraction (XRD), infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Kaolinite (Kaol) initially intercalated with N-methyformamide (NMF), urea (U), or dimethylsulfoxide (DMSO) before subsequent reaction with Me formed final kaolinite–methanol (Kaol–Me) complexes characterized by basal spacing ranging between 8.6 Å and 9.6 Å, depending on the pre-intercalated reagent. Based on a comparative analysis of the three Kaol–Me displacement intercalation complexes, three types of Me intercalation products were suggested to have been present in the interlayer space of Kaol: (1) molecules grafted onto a kaolinite octahedral sheet in the form of a methoxy group (Al-O-C bond); (2) mobile Me and/or water molecules kept in the interlayer space via hydrogen bonds that could be partially removed during drying; and (3) a mixture of types 1 and 2, with the methoxy group (Al-O-C bond) grafted onto the Kaol sheet and mobile Me and/or water molecules coexisted in the system after the displacement reaction by Me. Various structural models that reflected four possible complexes of Kaol–Me were constructed for use in a complimentary computational study. Results from the calculation of the methanol kaolinite interaction indicate that the hydroxyl oxygen atom of methanol plays the dominant role in the stabilization and localization of the molecule intercalated in the interlayer space, and that water existing in the intercalated Kaol layer is inevitable.

Multifunctional SA-PProDOT binder for lithium ion batteries

An environmentally benign, highly conductive, and mechanically strong binder system can overcome the dilemma of low conductivity and insufficient mechanical stability of the electrodes to achieve high performance lithium ion batteries (LIBs) at a low cost and in a sustainable way. In this work, the naturally occurring binder sodium alginate (SA) is functionalized with 3,4-propylenedioxythiophene-2,5-dicarboxylic acid (ProDOT) via a one-step esterification reaction in a cyclohexane/dodecyl benzenesulfonic acid (DBSA)/water microemulsion system, resulting in a multifunctional polymer binder, that is, SA-PProDOT. With the synergetic effects of the functional groups (e.g., carboxyl, hydroxyl, and ester groups), the resultant SA-PProDOT polymer not only maintains the outstanding binding capabilities of sodium alginate but also enhances the mechanical integrity and lithium ion diffusion coefficient in the LiFePO4 (LFP) electrode during the operation of the batteries. Because of the conjugated network of the PProDOT and the lithium doping under the battery environment, the SA-PProDOT becomes conductive and matches the conductivity needed for LiFePO4 LIBs. Without the need of conductive additives such as carbon black, the resultant batteries have achieved the theoretical specific capacity of LiFePO4 cathode (ca. 170 mAh/g) at C/10 and ca. 120 mAh/g at 1C for more than 400 cycles.

Effects of metal ion concentration on electrodeposited CuZnSn film and its application in kesterite Cu2ZnSnS4solar cells

In this study, effects of concentrations of Cu(II), Zn(II) and Sn(II) ions in the electrolytic bath solution on the properties of electrochemically deposited CuZnSn (CZT) films were investigated. Study of the composition of a CZT film has shown that the metallic content (relative atomic ratio) in the film increased linearly with increase in the metal ion concentration. It is the first time that the relationship of the compositions of the alloy phases in the co-electrodeposited CZT film with the concentration of metal ions has been revealed. The results have confirmed that the formation and content of Cu6Sn5 and Cu5Zn8 alloy phases in the film were directly controlled by the concentration of Cu(II). SEM measurements have shown that Sn(II) has significant impact on film morphology, which became more porous as a result of the larger nucleation size of tin. The changes in the surface properties of the films was also confirmed by chronoamperometry characteristic (i–t) deposition curves. By optimization of metal ion concentrations in the electrolyte solution, a copper-poor and zinc-rich kesterite Cu2ZnSnS4 (CZTS) film was synthesized by the sulfurization of the deposited CZT film. The solar cell with the CZTS film showed an energy conversion efficiency of 2.15% under the illumination intensity of 100 mW cm 2.

Ion exchange treatment of saline solutions using lanxess S108H strong acid cation resin

Common to many types of water and wastewater is the presence of sodium ions which can be removed by desalination technologies, such as reverse osmosis and ion exchange. The focus of this investigation was ion exchange as it potentially offered several advantages compared to competing methods. The equilibrium and column behaviour of a strong acid cation (SAC) resin was examined for the removal of sodium ions from aqueous sodium chloride solutions of varying normality as well as a coal seam gas water sample. The influence of the bottle-point method to generate the sorption isotherms was evaluated and data interpreted with the Langmuir Vageler, Competitive Langmuir, Freundlich, and Dubinin-Astakhov models. With the constant concentration bottle point method, the predicted maximum exchange levels of sodium ions on the resin ranged from 61.7 to 67.5 g Na/kg resin. The general trend was that the lower the initial concentration of sodium ions in the solution, the lower the maximum capacity of the resin for sodium ions. In contrast, the constant mass bottle point method was found to be problematic in that the isotherm profiles may not be complete, if experimental parameters were not chosen carefully. Column studies supported the observations of the equilibrium studies, with maximum sodium loading of ca. 62.9 g Na/kg resin measured, which was in excellent agreement with the predictions of the data from the constant concentration bottle point method. Equilibria involving coal seam gas water were more complex due to the presence of sodium bicarbonate in solution, albeit the maximum loading capacity for sodium ions was in agreement with the results from the more simple sodium chloride solutions.

Clinoenstatite coatings have high bonding strength, bioactive ion release, and osteoimmunomodulatory effects that enhance in vivo osseointegration

A number of coating materials have been developed over past two decades seeking to improve the osseointegration of orthopedic metal implants. Despite the many candidate materials trialed, their low rate of translation into clinical applications suggests there is room for improving the current strategies for their development. We therefore propose that the ideal coating material(s) should possess the following three properties: (i) high bonding strength, (ii) release of functional ions, and (iii) favourable osteoimmunomodulatory effects. To test this proposal, we developed clinoenstatite (CLT, MgSiO3), which as a coating material has high bonding strength, cytocompability and immunomodulatory effects that are favourable for in vivo osteogenesis. The bonding strength of CLT coatings was 50.1 ± 3.2 MPa, more than twice that of hydroxyapatite (HA) coatings, at 23.5 ± 3.5 MPa. CLT coatings released Mg and Si ions, and compared to HA coatings, induced an immunomodulation more conducive for osseointegration, demonstrated by downregurelation of pro-inflammatory cytokines, enhancement of osteogenesis, and inhibition of osteoclastogenesis. In vivo studies demonstrated that CLT coatings improved osseointegration with host bone, as shown by the enhanced biomechanical strength and increased de novo bone formation, when compared with HA coatings. These results support the notion that coating materials with the proposed properties can induce an in vivo environment better suited for osseointegration. These properties could, therefore, be fundamental when developing high-performance coating materials.

Delay tolerant routing protocols for energy-neutral animal tracking

This paper investigates communication protocols for relaying sensor data from animal tracking applications back to base stations. While Delay Tolerant Networks (DTNs) are well suited to such challenging environments, most existing protocols do not consider the available energy that is particularly important when tracking devices can harvest energy. This limits both the network lifetime and delivery probability in energy-constrained applications to the point when routing performance becomes worse than using no routing at all. Our work shows that substantial improvement in data yields can be achieved through simple yet efficient energy-aware strategies. Conceptually, there is need for balancing the energy spent on sensing, data mulling, and delivery of direct packets to destination. We use empirical traces collected in a flying fox (fruit bat) tracking project and show that simple threshold-based energy-aware strategies yield up to 20% higher delivery rates. Furthermore, these results generalize well for a wide range of operating conditions.

Directional synthesis of tin oxide@graphene nanocomposites via a one-step up-scalable wet-mechanochemical route for lithium ion batteries

Directional synthesis of SnO2@graphene nanocomposites via a one-step, low-cost, and up-scalable wetmechanochemical method is achieved using graphene oxide and SnCl2 as precursors. The graphene oxides are reduced to graphene while the SnCl2 is oxidized to SnO2 nanoparticles that are in situ anchored onto the graphene sheets evenly and densely, resulting in uniform SnO2@graphene nanocomposites. The prepared nanocomposites possess excellent electrochemical performance and outstanding cycling in Li-ion batteries.

Pre-lithiation of onion-like carbon/MoS2 nano-urchin anodes for high-performance rechargeable lithium ion batteries

Hybrid urchin-like nanostructures composed of a spherical onion-like carbon (OLC) core and MoS2 nanoleaves were synthesized by a simple solvothermal method followed by thermal annealing treatment. Compared to commercial MoS2 powder, MoS2/OLC nanocomposites exhibit enhanced electrochemical performance as anode materials of lithium-ion batteries (LIBs) with a specific capacity of 853 mA h g−1 at a current density of 50 mA g−1 after 60 cycles, and a moderate initial coulombic efficiency of 71.1%. Furthermore, a simple pre-lithiation method based on direct contact of lithium foil with MoS2/OLC nano-urchins was used to achieve a very high coulombic efficiency of 97.6% in the first discharge/charge cycle, which is at least 26% higher compared to that of pristine MoS2/OLC nano-urchins. This pre-lithiation method can be generalized to develop other carbon-metal sulfide nanohybrids for LIB anode materials. These results may open up a new avenue for the development of the next-generation high-performance LIBs.

Long, vertically aligned single-walled carbon nanotubes from plasmas: Morpho-kinetic and alignment controls

The enhanced large-scale model and numerical simulations are used to clarify the growth mechanism and the differences between the plasma- and neutral gas-grown carbon nanotubes, and to reveal the underlying physics and the key growth parameters. The results show that the nanotubes grown by plasma can be longer due to the effects of hydrocarbon ions with velocities aligned with the nanotubes. We show that the low-temperature growth is possible when the hydrocarbon ion flux dominates over fluxes of other species. We have also analysed the dependencies of the nanotube growth rates on nanotube and process parameters. The results are verified by a direct comparison with the experimental data. The model is generic and can be used for other types of carbon nanostructures such as carbon nanowalls, vertical graphenes, etc.

SnO2 decorated graphene nanocomposite anode materials prepared via an up-scalable wet-mechanochemical process for sodium ion batteries

A facile and up-scalable wet-mechanochemical process is designed for fabricating ultra-fine SnO2 nanoparticles anchored on graphene networks for use as anode materials for sodium ion batteries. A hierarchical structure of the SnO2@graphene composite is obtained from the process. The resultant rechargeable SIBs achieved high rate capability and good cycling stability.