Removal of methyl orange from aqueous solutions through adsorption by calcium aluminate hydrates

Methyl orange (MO) is a kind of anionic dye and widely used in industry. In this study, tricalcium aluminate hydrates (Ca-Al-LDHs) are used as an adsorbent to remove methyl orange (MO) from aqueous solutions. The resulting products were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), thermal analysis (TG-DTA) and scanning electron microscope (SEM). The XRD results indicated that the MO molecules were successfully intercalated into the tricalcium aluminate hydrates, with the basal spacing of Ca-Al-LDH expanding to 2.48 nm. The MIR spectrum for CaAl-MO-LDH shows obvious bands assigned to the N@N, N@H stretching vibrations and S@O, SO_ 3 group respectively, which are considered as marks to assess MO_ ion intercalation into the interlayers of LDH. The overall morphology of CaAl-MOLDH displayed a ‘‘honey-comb’’ like structure, with the adjacent layers expanded.

Enhanced coloration efficiency for electrochromic devices based on anodized N2O5 / Electrodeposited MoO3 Binary Systems

There is a continuous quest for developing electrochromic (EC)transition metal oxides (TMOs) with increased coloration efficiency. As emerging TMOs, Nb2O5 films, even those of ordered anodized nanochannels, have failed to produce the required EC performance for practical applications. This is attributed to limitations presented by its relatively wide bandgap and low capacity for accommodating ions. To overcome such issues, MoO3 was electrodeposited onto Nb2O5 nanochannelled films as homogeneously conformal and stratified α-MoO3 coatings of different thickness. The EC performance of the resultant MoO3 coated Nb2O5 binary system was evaluated. The system exhibited a coloration efficiency of 149.0 cm2 C−1, exceeding that of any previous reports on MoO3 and Nb2O5 individually or their compounds. The enhancement was ascribed to a combination of the reduced effective bandgap of the binary system, the increased intercalation probability from the layered α-MoO3 coating, and a high surface-tovolume ratio, while the Nb2O5 nanochannelled templates provided stability and low impurity pathways for charge transfer to occur.

Insight into the thermal decomposition of kaolinite intercalated with potassium acetate : an evolved gas analysis

The thermal decomposition process of kaolinite–potassium acetate intercalation complex has been studied using simultaneous thermogravimetry coupled with Fourier-transform infrared spectroscopy and mass spectrometry (TG-FTIR-MS). The results showed that the thermal decomposition of the complex took place in four temperature ranges, namely 50–100, 260–320, 320–550, and 650–780 °C. The maximal mass losses rate for the thermal decomposition of the kaolinite–potassium acetate intercalation complex was observed at 81, 296, 378, 411, 486, and 733 °C, which was attributed to (a) loss of the adsorbed water, (b) thermal decomposition of surface-adsorbed potassium acetate (KAc), (c) the loss of the water coordinated to potassium acetate in the intercalated kaolinite, (d) the thermal decomposition of intercalated KAc in the interlayer of kaolinite and the removal of inner surface hydroxyls, (e) the loss of the inner hydroxyls, and (f) the thermal decomposition of carbonate derived from the decomposition of KAc. The thermal decomposition of intercalated potassium acetate started in the range 320–550 °C accompanied by the release of water, acetone, carbon dioxide, and acetic acid. The identification of pyrolysis fragment ions provided insight into the thermal decomposition mechanism. The results showed that the main decomposition fragment ions of the kaolinite–KAc intercalation complex were water, acetone, carbon dioxide, and acetic acid. TG-FTIR-MS was demonstrated to be a powerful tool for the investigation of kaolinite intercalation complexes. It delivers a detailed insight into the thermal decomposition processes of the kaolinite intercalation complexes characterized by mass loss and the evolved gases.

DNA adduction by the potent carcinogen aflatoxin B1 : mechanistic studies

Aflatoxin B1, a potently carcinogenic fungal metabolite, is converted to the biologically active form by chemical oxidation using dimethyldioxirane and enzymatically by cytochrome P450 mixed-function oxidases. Both processes give rise to mixtures of the exo- and endo-8,9-epoxides. Methanolysis studies reveal exclusive trans opening of both epoxides under neutral conditions in CH3OH and CH3OH/H2O mixtures; an SN2 mechanism is postulated. Under acidic conditions, the exo isomer gives mixtures of trans and cis solvolysis products, suggesting that the reaction is, at least in part, SN1; the endo isomer gives only the trans product. The exo isomer reacts with DNA by attack of the nitrogen atom at the 7 position of guanine on C8 of the epoxide to give the trans adduct; the endo epoxide fails to form an adduct at this or any other site in DNA. The exo isomer is strongly mutagenic in a base-pair reversion assay employing Salmonella typhimurium; the endo isomer is essentially nonmutagenic. Aflatoxin B1 and its derivatives intercalate in DNA. These results are consistent with a mechanism in which intercalation of the exo epoxide optimally orients the epoxide for an SN2 reaction with guanine but intercalation of the endo isomer places the epoxide in an orientation which precludes reaction. Thus, while the exo epoxide is a potent mutagen, the endo epoxide fails to react with DNA.

Optical gas sensing properties of nanoporous Nb2O5 films

Nanoporous Nb2O5 has been previously demonstrated to be a viable electrochromic material with strong intercalation characteristics. Despite showing such promising properties, its potential for optical gas sensing applications, which involves the production of ionic species such as H+, has yet to be explored. Nanoporous Nb2O5 can accommodate a large amount of H+ ions in a process that results in an energy bandgap change of the material, which induces an optical response. Here, we demonstrate the optical hydrogen gas (H¬2) sensing capability of nanoporous anodic Nb2O5 with a large surface-to-volume ratio prepared via a high temperature anodization method. The large active surface area of the film provides enhanced pathways for efficient hydrogen adsorption and dissociation, which are facilitated by a thin layer of Pt catalyst. We show that the process of H2 sensing causes optical modulations that are investigated in terms of response magnitudes and dynamics. The optical modulations induced by the intercalation process and sensing properties of nanoporous anodic Nb2O5 shown in this work can potentially be used for future optical gas sensing systems.

Synthesis of organoclays: A critical review and some unresolved issues

The synthesis of organoclays (OC) by intercalation of quaternary ammonium cation (QAC) into expanding clay minerals, notably montmorillonite (Mt), has attracted a great deal of attention during the past two decades. The OC have also found applications in the manufacture of clay polymer nanocomposites (CPN) and environmental remediation. Despite the wealth of information that exists on the formation and properties of OC, some problems remain to be resolved. The present contribution is an attempt at clarifying two outstanding issues, based on the literature and experimental data obtained by the authors over the past years. The first issue concerns the relationship between the cation exchange capacity (CEC) of the Mt and the basal spacing of the OC which, in turn, is dependent on the concentration and the nature of the added QAC. At a concentration less than 1 CEC, organo-Mt (OMt) formed using the QAC with a short alkyl chain length with nc < 16 (e.g., dodecyl trimethylammonium) gives basal spacings of 1.4–1.6 nm that are essentially independent of the CEC. However, for long-chain QAC with nc ≥ 16 (e.g., hexadecyl trimethylammonium), the basal spacing varies with the QAC concentration. For Mt with a CEC of 80–90 meq/100 g, the basal spacing of the OC increases gradually with the CEC and shows a sudden (stepwise) increase to 3.2–3.8 nm at a QAC concentration of 1.5 CEC and to 3.5–4.0 nm at a concentration of 2.0 CEC. The second issue pertains to the “locking” effect in QAC- and silane-modified pillared interlayered clays (PILC) and Mt. For silylated Mt, the “locking” effect results from the covalent bonding of silane to two adjacent layers within a single clay mineral particle. The same mechanism can operate in silane-grafted PILC but in this case, the “locking” effect may primarily be ascribed to the pillaring of adjacent basal surfaces by metal hydr(oxides).

Tailoring surface properties and structure of layered double hydroxides using silanes with different number of functional groups

Four silanes, trimethylchlorosilane (TMCS), dimethyldiethoxylsilane (DMDES), 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS), were adopted to graft layered double hydroxides (LDH) via an induced hydrolysis silylation method (IHS). Fourier transform infrared spectra (FTIR) and 29Si MAS nuclear magnetic resonance spectra (29Si MAS NMR) indicated that APTES and TEOS can be grafted onto LDH surfaces via condensation with hydroxyl groups of LDH, while TMCS and DMDES could only be adsorbed on the LDH surface with a small quantity. A combination of X-ray diffraction patterns (XRD) and 29Si MAS NMR spectra showed that silanes were exclusively present in the external surface and had little influence on the long range order of LDH. The surfactant intercalation experiment indicated that the adsorbed and/or grafted silane could not fix the interlamellar spacing of the LDH. However, they will form crosslink between the particles and affect the further surfactant intercalation in the silylated samples. The replacement of water by ethanol in the tactoids and/or aggregations and the polysiloxane oligomers formed during silylation procedure can dramatically increase the value of BET surface area (SBET) and total pore volumes (Vp) of the products.

Conformational Dynamics in Alkyl Chains of an Anchored Bilayer: A Molecular Dynamics Study

Molecular dynamics (MD) simulations are reported for an anchored bilayer formed by the intercalation of cetyl trimethyl ammonium (CTA) and CH3(CH2)15N+(CH3) ions in a layered solid, CdPS3. The intercalated CTA ions are organized with the cationic headgroups tethered to the inorganic sheet and the hydrocarbon tails arranged as bilayers. Simulations were performed at three temperatures, 65, 180, and 298 K, using an isothermal−isobaric ensemble that was subsequently switched once macroscopic parameters had converged to a canonical isothermal−isochoric ensemble. The simulations are able to reproduce the experimental features of this system, including the formation of the bilayer and layer-to-layer separation distance. An analysis of the conformation of the chains showed that at all three temperatures a fraction of the alkyl chains retained a planar all-trans conformation, and that gauche bonds occurred as part of a “kink” (gauche+−trans−gauche−) sequence and not as isolated gauche bonds. Trans−gauche isomerization rates for the alkyl chains in the anchored bilayer are slower than those in lipid bilayers at the same temperature and show a progressive increase as the torsion numbers approach the tail. A two-dimensional periodic Voronoi tessellation analysis was performed to obtain the single-molecular area of an alkyl chain in the bilayer. The single-molecular area relaxation times are an order of magnitude longer than the trans−gauche isomerization times. The results indicate that the trans−gauche isomerization is associated with the creation and annihilation of a kink defect sequence. The results of the present MD simulation explain the apparent conflicting estimates of the gauche disorder in this system as obtained from infrared and 13C nuclear magnetic resonance measurements.

Biophysical Characterization of Oxidized Phospholipids : Implications for Altered Membrane Structure and Function

The present study aims to elucidate the modifications in the structure and functionality of the phospholipid matrix of biological membranes brought about by free radical-mediated oxidative damage of its molecular constituents. To this end, the surface properties of two oxidatively modified phospholipids bearing an aldehyde or carboxyl function at the end of truncated sn-2 acyl chain were studied using a Langmuir balance. The results obtained reveal both oxidized species to have a significant impact on the structural dynamics of phospholipid monolayers, as illustrated by the progressive changes in force-area isotherms with increasing mole fraction of the oxidized lipid component. Moreover, surface potential measurements revealed considerable modifications in the electric properties of oxidized phospholipid containing monolayers during film compression, suggesting a packing state-controlled reorientation of the intramolecular electric dipoles of the lipid headgroups and acyl chains. Based on the above findings, a model describing the conformational state of oxidized phospholipid molecules in biological membranes is proposed, involving the protrusion of the acyl chains bearing the polar functional groups out from the hydrocarbon phase to the surrounding aqueous medium. Oxidative modifications alter profoundly the physicochemical properties of unsaturated phospholipids and are therefore readily anticipated to have important implications for their interactions with membrane-associating molecules. Along these lines, the carboxyl group bearing lipid was observed to bind avidly the peripheral membrane protein cytochrome c. The binding was reversed following increase in ionic strength or addition of polyanionic ATP, thus suggesting it to be driven by electrostatic interactions between cationic residues of the protein and the deprotonated lipid carboxyl exposed to the aqueous phase. The presence of aldehyde function bearing oxidized phospholipid was observed to enhance the intercalation of four antimicrobial peptides into phospholipid monolayers and liposomal bilayers. Partitioning of the peptides to monolayers was markedly attenuated by the aldehyde scavenger methoxyamine, revealing it to be mediated by the carbonyl moiety possibly through efficient hydrogen bonding or, alternatively, formation of covalent adduct in form of a Schiff base between the lipid aldehydes and primary amine groups of the peptide molecules. Lastly, both oxidized phospholipid species were observed to bind with high affinity three small membrane-partitioning therapeutic agents, viz. chlorpromazine, haloperidol, and doxorubicin. In conclusion, the results of studies conducted using biomimetic model systems support the notion that oxidative damage influences the molecular architecture as well as the bulk physicochemical properties of phospholipid membranes. Further, common polar functional groups carried by phospholipids subjected to oxidation were observed to act as molecular binding sites at the lipid-water interface. It is thus plausible that oxidized phospholipid species may elicit cellular level effects by modulating integration of various membrane-embedded and surface-associated proteins and peptides, whose conformational state, oligomerization, and functionality is known to be controlled by highly specific lipid-protein interactions and proper physical state of the membrane environment.

Rate capability of graphite materials as negative electrodes in lithium-ion capacitors

The lithium-ion exchange rate capability of various commercial graphite materials are evaluated using galvanostatic charge/discharge cycling in a half-cell configuration over a wide range of C-rates (0.1 similar to 60C). The results confirm that graphite is capable of de-intercalating stored charge at high rates, but has a poor intercalating rate capability. Decreasing the graphite coating thickness leads to a limited rate performance improvement of the electrode. Reducing the graphite particle size shows enhanced C-rate capability but with increased irreversible capacity loss (ICL). It is demonstrated that the rate of intercalation of lithium-ions into the graphite is significantly limited compared with the corresponding rate of de-intercalation at high C-rates. For the successful utilisation of commercially available conventional graphite as a negative electrode in a lithium-ion capacitor (LIC), its intercalation rate capability needs to be improved or oversized to accommodate high charge rates.

Structural and thermal properties of inorganic–organic montmorillonite: Implications for their potential environmental applications

Inorganic–organic clays (IOCs), clays intercalated with both organic cations such as cationic surfactants and inorganic cations such as metal hydroxy polycations have the properties of both organic and pillared clays, and thereby the ability to remove both inorganic and organic contaminants from water simultaneously. In this study, IOCs were synthesised using three different methods with different surfactant concentrations. Octadecyltrimethylammonium bromide (ODTMA) and hydroxy aluminium ([Al13O4 (OH)24(H2O)12]7+ or Al13) are used as the organic and inorganic modifiers (intercalation agents). According to the results, the interlayer distance, the surfactant loading amount and the Al/Si ratio of IOCs strictly depend on the intercalation method and the intercalation agent ratio. Interlayers of IOCs synthesised by intercalating ODTMA before Al13 and IOCs synthesised by simultaneous intercalation of ODTMA and Al13 were increased with increasing the ODTMA concentration used in the synthesis procedure and comparatively high loading amounts could be observed in them. In contrast, Al/Si decreased with increasing ODTMA concentration in these two types of IOCs. The results suggest that Al-pillars can be fixed within the interlayers by calcination and any increment in the amount of ODTMA used in the synthesis procedure did not affect the interlayer distance of the IOCs. Overall the study provides valuable insights into the structure and properties of the IOCs and their potential environmental applications.

Environmental applications of inorganic-organic clays for recalcitrant organic pollutants removal: Bisphenol A

Bisphenol-A (BPA) adsorption onto inorganic-organic clays (IOCs) was investigated. For this purpose, IOCs synthesised using octadecyltrimethylammonium bromide (ODTMA, organic modifier) and hydroxy aluminium (Al13, inorganic modifier) were used. Three intercalation methods were employed with varying ODTMA concentration in the synthesis of IOCs. Molecular interactions of clay surfaces with ODTMA and Al13 and their arrangements within the interlayers were determined using Fourier transform infrared spectroscopy (FTIR). Surface area and porous structure of IOCs were determined by applying Brunauer, Emmett, and Teller (BET) method to N2 adsorption-desorption isotherms. Surface area decreased upon ODTMA intercalation while it increased with Al13 pillaring. As a result, BET specific surface area of IOCs was considerably higher than those of organoclays. Initial concentration of BPA, contact time and adsorbent dose significantly affected BPA adsorption into IOCs. Pseudo-second order kinetics model is the best fit for BPA adsorption into IOCs. Both Langmuir and Freundlich adsorption isotherms were applicable for BPA adsorption (R2 > 0.91) for IOCs. Langmuir maximum adsorption capacity for IOCs was as high as 109.89 mg g‒1 and it was closely related to the loaded ODTMA amount into the clay. Hydrophobic interactions between long alkyl chains of ODTMA and BPA are responsible for BPA adsorption into IOCs.

Bismuth sulfide: A high-capacity anode for sodium-ion batteries

Exploring high-performance anode materials is currently one of the most urgent issues towards practical sodium-ion batteries (SIBs). In this work, Bi2S3 is demonstrated to be a high-capacity anode for SIBs for the first time. The specific capacity of Bi2S3 nanorods achieves up to 658 and 264 mAh g-1 at a current density of 100 and 2000 mA g-1, respectively. A full cell with Na3V2(PO4)3-based cathode is also assembled as a proof of concept and delivers 340 mAh g-1 at 100 mA g-1. The sodium storage mechanism of Bi2S3 is investigated by ex-situ XRD coupled with high-resolution TEM (HRTEM), and it is found that sodium storage is achieved by a combined conversion-intercalation mechanism.

Effect of Crystallographic Structure of MnO2 on Its Electrochemical Capacitance Properties

MnO2 is currently under extensive investigations for its capacitance properties. MnO2 crystallizes into several crystallographic structures, namely, α, β, γ, δ, and λ structures. Because these structures differ in the way MnO6 octahedra are interlinked, they possess tunnels or interlayers with gaps of different magnitudes. Because capacitance properties are due to tercalation/deintercalation of protons or cations in MnO2, only some crystallographic structures, which possess sufficient gaps to accommodate these ions, are expected to be useful for capacitance studies. In order to examine the dependence of capacitance on crystal structure, the present study involves preparation of these various crystal phases of MnO2 in nanodimensions and to evaluate their capacitance properties. Results of α-MnO2 prepared by a microemulsion route (α-MnO2(m)) are also used for comparison. Spherical particles of about 50 nm, nanorods of 30−50 nm in diameter, or interlocked fibers of 10−20 nm in diameters are formed, which depend on the crystal structure and the method of preparation. The specific capacitance (SC) measured for MnO2 is found to depend strongly on the crystallographic structure, and it decreases in the following order: α(m) > α δ > γ > λ > β. A SC value of 297 F g-1 is obtained for α-MnO2(m), whereas it is 9 F g-1 for β-MnO2. A wide (4.6 Å) tunnel size and large surface area of α-MnO2(m) are ascribed as favorable factors for its high SC. A large interlayer separation (7 Å) also facilitates insertion of cations in δ-MnO2 resulting in a SC close to 236 F g-1. A narrow tunnel size (1.89 Å) does not allow intercalation of cations into β-MnO2. As a result, it provides a very small SC.

High Rate Capability of a Dual-Porosity LiFePO4/C Composite

Mesoporous intercalation compounds consisting of two differentdistributions of pores represent a potentially attractive material for high-rate cathodes. A mesoporous LiFePO4/C composite with two sizes of pores is prepared for the first time via a solution-based polymer templating technique. The precursor of the LiFePO4/C composite is heated at different temperatures in the range from 600 to 800 degrees C to study the effect of crystallinity, porosity, and morphology on the electrochemical performance. The composite is found to attain reduction in the surface area, carbon content, and porosity upon increasing temperature. Nonetheless, the composite prepared at 700 degrees C with pore-size distributions of around 4 and 50 nm exhibits a high rate capability and stable capacity retention upon cycling.