Formation Of Layered Structure Research Articles

Development of gel-like, high encapsulation efficiency and antibacterial cinnamaldehyde-loaded Pickering emulsion stabilized by EGCG enhanced whey protein isolate-gum arabic ternary nanocomplex

Pickering emulsions (PEs) loaded with essential oils have proven to be a promising delivery system in food preservation, thus attracting increasing research attention. In this study, epigallocatechin gallate (EGCG) enhanced whey protein isolate(WPI)-gum Arabic(GA) ternary spherical nanocomplex (WGE) was fabricated by thermal and pH double-induced method and used to stabilize antibacterial, antioxidant and sustained release Pickering emulsions loaded with cinnamaldehyde. The WGE nanocomplex exhibited biphasic surface wettability (78.2±2.8°), 1.73 times that of WPI, as well as outstanding interfacial tension (5.60 mN/m), 44.6 % lower than that of WPI-GA, mainly due to the electrostatic interactions between WPI and GA and enhanced surface hydrophobicity causing by EGCG, indicating its superb ability to stabilize Pickering emulsions. Using WGE nanocomplex as the Pickering emulsion stabilizer, PEs template was constructed. Confocal laser scanning microscopy (CLSM) showed the formation of a dense oil-water interface layer and gel-like network structure, which demonstrated good storage stability against creaming and coalescence, benefiting to cinnamaldehyde encapsulation. Finally, cinnamaldehyde was encapsulated effectively using this PEs pattern with high encapsulation efficiency under different conditions. The cinnamaldehyde Pickering emulsions (CPEs) demonstrated superior antioxidant ability against DPPH (>85 %) and ABTS (>78 %), as well as effective antibacterial capability against E. coli (>99.9999 %) and S. aureus (>99.99 %) than pure cinnamaldehyde. Moreover, CPEs showed slow sustained-release ability, which could satisfyingly prolong the biological activity of cinnamaldehyde. Therefore, the WGE stabilized cinnamaldehyde Pickering emulsions fabricated in this work might provide a promising alternative for the delivery of antibacterial and controlled release essential oils in the food industry.

Porous Metal Phosphonate Frameworks: Construction and Physical Properties.

ConspectusPorous metal phosphonate frameworks (PMPFs) as a subclass of metal-organic frameworks (MOFs) have promising applications in the fields of gas adsorption and separation, ion exchange and storage, catalysis, sensing, etc. Compared to the typical carboxylate-based MOFs, PMPFs exhibit higher thermal and water stability due to the strong coordination ability of the phosphonate ligands. Despite their robust frameworks, PMPFs account for less than 0.51% of the porous MOFs reported so far. This is because metal phosphonates are highly susceptible to the formation of dense layered or pillared-layered structures, and they precipitate easily and are difficult to crystallize. There is a tendency to use phosphonate ligands containing multiple phosphonate groups and large organic spacers to prevent the formation of dense structures and generate open frameworks with permanent porosity. Thus, many PMPFs are composed of chains or clusters of inorganic metal phosphonates interconnected by organic spacers. Using this feature, a wide range of metal ions and organic components can be selected, and their physical properties can be modulated. However, limited by the small number of PMPFs, there are still relatively few studies on the physical properties of PMPFs, some of which merely remain in the description of the phenomena and lack in-depth elaboration of the structure-property relationship. In this Account, we review the strategies for constructing PMPFs and their physical properties, primarily based on our own research. The construction strategies are categorized according to the number (n = 1-4) of phosphonate groups in the ligand. The physical properties include proton conduction, electrical conduction, magnetism, and photoluminescence properties. Proton conductivity of PMPFs can be enhanced by increasing the proton carrier concentration and mobility. The former can be achieved by adding acidic groups such as -POH and/or introducing acidic guests in the hydrophilic channels. The latter can be attained by introducing conjugate acid-base pairs or elevating the temperature. Semiconducting PMPFs, on the other hand, can be obtained by constructing highly conjugated networks of coordination bonds or introducing large conjugated organic linkers π-π stacked in the lattice. In the case of magnetic PMPFs, long-range magnetic ordering occurs at very low temperatures due to very weak magnetic exchange couplings propagated via O-P-O and/or O(P) units. However, lanthanide compounds may be interesting candidates for single-molecule magnets because of the strong single-ion magnetic anisotropy arising from the spin-orbit coupling and large magnetic moments of lanthanide ions. The luminescent properties of PMPFs depend on the metal ions and/or organic ligands. Emissive PMPFs containing lanthanides and/or uranyl ions are promising for sensing and photonic applications. We conclude with an outlook on the opportunities and challenges for the future development of this promising field.

Precisely designed 3-stage calcination strategy for lithium-rich manganese-based cathodes with improved cycling performance

The poor cycling performance of Li-rich manganese-based (LMR) cathodes is one of the challenges that need to be urgently overcome. Enhancing the stability of the layered structure responsible for lithium-ion diffusion is an effective way to improve the cycling performance. Layered structures are mainly formed during the high-temperature solid-phase reaction, whereas the prolonged and constant-high-temperature calcination conditions in conventional calcination procedure may pose a threat to the layered structural stability. Thus, in order to optimize the formation environment of layered structures under high-temperature solid-phase reaction, we have designed suitable temperature-controlled strategies for each stage of layered structure formation, gradual maturation, and post-treatment, respectively, referred to as the 3-stage calcination strategy. This calcination strategy contributes to the formation of a more ordered and stable layered structure, which significantly improves the cycling performance of LMR cathodes (capacity retention rate of 85.2 % after 200 cycles at 1C). The shortening of the constant high temperature calcination time helps to further reduce the production cost of the batteries. The design concept of this work is to regulate the formation process of layered structures in stages, which provides inspiration for the efficient and controllable synthesis of electrode materials with excellent structural stability at low production cost.

Effects of implantation of laser produced Ni plasma ions on CR-39 correlated with surface, structural, optical and electrical properties of polymer

Laser produced plasma ions implantation has a great potential to change various characteristics of the polymer after irradiation, such as, surface, structural, optical and electrical properties. For this purpose, polymer CR- 39 is implanted by laser produced Ni plasma ions at various fluences ranging from 75 × 1013 to 95 × 1016 ions/cm2. The ion energy estimated by Thomson parabola technique using CR-39 detectors was 540 KeV. Digital optical microscopic analysis illustrates the formation of granular morphology for all ion fluences. However, at the maximum fluence (95 × 1016 ions/cm2), distinct and well organized grains with sub-granular morphology are observed. Confocal microscopic analysis shows the development of micro/nano sized caters, voids, ion tracks, clusters and bumps for various fluences of Ni ions ranging from 75 × 1013 to 60 × 1015 ions/cm2. Whereas, at the maximum ion fluence (95 × 1016 ions/cm2), hillock like features are observed. Raman spectroscopy analysis shows the formation of carbonaceous structures along with new bonds of Ni–CO in implanted CR-39. Reduction in transmittance value from 92.2% to 60.8% is observed with increase in ion fluence from 75 × 1013 to 95 × 1016 ions/cm2. The electrical conductivity of implanted CR-39 increases by increasing the ion fluence. Formation of conductive layer and carbonaceous structures are considered to be accountable for improvements in electrical conductivity of implanted target polymer. The observed stopping power or Linear Energy Transfer (LET) of 540 KeV Ni ions in CR-39 is 72.88 eV/Ǻ and their corresponding depth is 686 nm.

Self-excited oscillation characteristics and mechanisms of supercritical CO2 flowing in a Helmholtz oscillator for enhancing heat transfer

The drastic variations in thermal properties of supercritical CO2 near its pseudo-critical point induce the formation of complex boundary layer structures within pipelines, rendering it susceptible to heat transfer deterioration under the influence of buoyancy forces. The Helmholtz self-excited cavity can generate self-excited pulsating jets, enhancing the intermixing between fluids inside the heat exchanger tubes, disrupting the thermal boundary layer, and suppressing heat transfer deterioration. In this study, the characteristics and mechanisms of self-excited oscillations of supercritical CO2 flowing vertically upward in the Helmholtz self-excited cavity were investigated using the large eddy simulation (LES) method. A detailed analysis of cavitation and vortex evolution within the cavity was conducted, along with an exploration of the influence of inlet pressure and structural parameters on the frequency characteristics of pulsations. The results indicate a close relationship between cavitation and vortex interactions and the pulsation frequency. An increase in inlet pressure leads to a significant cavitation phenomenon near the jet shear layer and an increase in vortex frequency. Dimensionless cavity length (Lc/d1) enlargement results in an increase in outlet pulsation frequency but a decrease in pulsation amplitude. The critical dimensionless ratio of cavity diameter (Dc/d1) plays a crucial role in maintaining the desired pulsation frequency and amplitude. Within the working range outlined in this paper, practical insights for system design and operation are provided by the optimal parameters of Lc/d1 = 3 and Dc/d1 = 10.

H2O2-sensitized titania with activity under visible light and in the dark

The development of visible-light photoactive materials decomposing pollutants and removing bacteria is a frequent motivation for scientific research. However, the reliance on light to sustain the degradation process restricts the practical application of photocatalysts. In this paper, titania was sensitized with H2O2 to overcome this problemand exhibit photocatalytic and dark activity. Efficiency of degradation of standard pollutant (methylene blue) and antibacterial properties (tested on two strains of bacteria: Enterococcus faecalis and Escherichia coli) were asessed. The comprehensive effect of this material is a result of the peroxide-assisted sol-gel method, without heat treatment, which allows obtaining titanium dioxide with hydroxy and adoxygen groups on the surface and in the volume. The presence of the peroxo and superoxo groups was confirmed using Raman, IR and EPR spectroscopies. The thermal stability of the adoxygen groups was analysed by TG/DSC analysis. X-ray diffraction indicated the formation of an amorphous layered structure. The Tauc plot revealed midgap states which reduced the band gaps towards visible light. The H2O2-sensitized TiO2 was characterized by negative surface potential (pHPZC=3.2) which improved adsorption.The study provides insight for the development of self-cleaning and antibacterial surfaces.

Modified Mg/Fe layered double hydroxide nanosheets as an efficient solar photocatalyst for hydrogen production from ammonium phosphate

Mg/Fe layered double hydroxides (LDHs) modified with Cu and W support were synthesized by a one-pot coprecipitation method. The resulting samples were extensively characterized using TGA, XRD, UV, FTIR, SEM, EDX, TEM, and N2 adsorption-desorption techniques. Finally, the calcined LDHs were evaluated for photocatalytic hydrogen production from triammonium phosphate-water solution under solar light irradiation. The XRD results demonstrated that all as prepared LDH samples had characteristic hydrotalcite phase and validated the formation of a well-crystallized layered structure. After calcination, the LDHs exhibited a sintered, broken-down morphology with 8–40 nm particles. The adsorption-desorption isotherms of the calcined LDHs were categorized as type IV with H3–H2 hysteresis, suggesting condensation capillarity and monolayer formation. The band gap values were 1.5 eV for Mg/Fe, 2.4 eV for Cu/Mg/Fe, and 2.8 eV for W/Mg/Fe calcined LDHs. In hydrogen evolution experiments, the Mg/Fe catalyst showed the highest volume of 45.3 ml, followed by Cu/Mg/Fe (43.7 ml) and W/Mg/Fe (40.1 ml). This was attributed to the higher BET surface area of 172 m2/g for Mg/Fe compared to 38 m2/g for W/Mg/Fe and 14 m2/g for Cu/Mg/Fe, enabling better distribution of active sites.

Crystal structures of four thio-glycosides involving carbamimido-thio-ate groups.

The compounds 2',3',4',6'-tetra-O-acetyl-β-d-gluco-pyranosyl N'-cyano-N-phenyl-carbamimido-thio-ate (C22H25N3O9S, 5a), 2',3',4',6'-tetra-O-acetyl-β-d-galacto-pyranosyl N'-cyano-N-phenyl-carbamimido-thio-ate, (C22H25N3O9S, 5b), 2',3',4',6'-tetra-O-acetyl-β-d-galacto-pyranosyl N'-cyano-N-methyl-carbamimido-thio-ate (C17H23N3O9S, 5c), and 2',3',4',6'-tetra-O-acetyl-β-d-galacto-pyranosyl N'-cyano-N-p-tolyl-carbamimido-thio-ate (C23H27N3O9S, 5d) all crystallize in P212121 with Z = 4. For all four structures, the configuration across the central (formal) C=N(CN) double bond of the carbamimido-thio-ate group is Z. The torsion angles C5-O1-C1-S (standard sugar numbering) are all close to 180°, confirming the β position of the substituent. Compound 5b involves an intra-molecular hydrogen bond N-H⋯O1; in 5c this contact is the weaker branch of a three-centre inter-action, whereas in 5a and 5d the H⋯O distances are much longer and do not represent significant inter-actions. The C-N bond lengths at the central carbon atom of the carbamimido-thio-ate group are almost equal. All C-O-C=O torsion angles of the acetyl groups correspond to a synperiplanar geometry, but otherwise all four mol-ecules display a high degree of conformational flexibility, with many widely differing torsion angles for equivalent groups. In the crystal packing, 5a, 5c and 5d form layer structures involving the classical hydrogen bond N-H⋯Ncyano and a variety of 'weak' hydrogen bonds C-H⋯O or C-H⋯S. The packing of 5b is almost featureless and involves a large number of borderline 'weak' hydrogen bonds. In an appendix, a potted history of wavelength preferences for structure determination is presented and it is recommended that, even for small organic crystals in non-centrosymmetric space groups, the use of Mo radiation should be considered.

Properties regulation and mechanism on ferritin/chitooligosaccharide dual-compartmental emulsions and its application for co-encapsulation of curcumin and quercetin bioactive compounds

Dual-compartmental emulsions, containing multiple chambers, possess great advantages in co-encapsulation of different cargoes. Herein, we reported a stable dual-compartmental emulsion by regulating the ratio of Marsupenaeus japonicus ferritin (MF) and chitooligosaccharide (COS), enabling efficient co-encapsulation of different compounds. The adsorption behavior of MF/COS complex over droplet interface varied at different ratios, thereby exerting an influence on the emulsion properties. Remarkably, emulsions stabilized by MF/COS complex at a ratio of 2:1 exhibited superior stability, as evidenced by no significant creaming or demulsification during storage or heat treatment. The mechanism is that MF/COS2:1 complex can enhance the formation of thicker interfacial layer and dense continuous phase network structure. Additionally, curcumin and quercetin can be co-encapsulated into the emulsions and their retention rates were significantly improved than those in oils, implying the potential of the resulting dual-compartmental emulsions in co-encapsulation and delivery of bioactive compounds.

Morphology and size modulation of Mn2O3 catalysts derived from MnBDC to enhance propane complete oxidation

Three Mn2O3 with different morphologies and particle sizes were synthesized using MnBDC as precursor. Interestingly, the morphology and size of MnBDC can be easily regulated by changing the reaction solvents slightly. The Mn2O3-L catalyst with large layers and small crystal size exhibited the best catalytic activity for complete oxidation of propane, with T50 of 266℃ and T90 of 311℃ at the WHSV of 120 L g−1 h−1. The multi-layered structure and small crystal size of Mn2O3-L allowed it to possess a high surface area and more interfacial oxygen defects that facilitated oxygen mobility, improving the catalytic activity. It seems that the large precursor size of MnBDC-L slowed down the decomposition rate of ligands, promoting the formation of large layered structure and small crystal size of Mn2O3-L. This study offers a simple strategy to control the structure and crystal size of Mn2O3 catalysts.

Anti-bacterial PVA@Ag/PVDF NF membrane made by filtration-coating plus in-situ reduction of NPs for dye removal

In this study, a filtration-coating method was developed to create a PVA layer on a PVDF membrane, and then silver nanoparticles (Ag NPs) were introduced by in-situ reduction to form an antibacterial PVA@Ag/PVDF NF membrane. The relationship between the rejection of dye by the membrane, the morphology of the coated PVA layer and its coating process parameters, such as polymer concentration, crosslinking ratio, vacuum pressure, and time, was investigated. The filtration-coating method facilitated the infiltration of PVA molecules into the porous channel of PVDF membrane, thus improved the stability of coated PVA. Meanwhile, it was observed that high vacuum pressure (1 bar), high polymer concentration (2%), and short filtration time (5 min) have a similar effect to low polymer concentration (1%) and long filtration time (10 min), which results in the formation of a dense layer structure (2–5 μm) on the membrane surface and leads to a high rejection rate but low flux. While filtration at low vacuum pressure (0.1 bar) leads to a thin PVA layer (<0.2μm), and PVA turns to appear on the entrance and surface of pore channel of membrane. The coated membrane showed a stable performance during 72 hrs filtration. Furthermore, Ag NPs were incorporated into PVA layer by the in-situ reduction method, the obtained membrane showed an enhanced dye rejection (92% for methyl blue), and a low salt rejection (NaCl 18%) and moderate flux (17.2 L·m−2·h−1 at 1 bar). Moreover, the composite membrane demonstrated excellent antibacterial properties (Staphylococcus aureus and E. coli). Overall, this work may present a novel approach to prepare new NF membrane.

Ultra-thin layer HTaMoO6 catalyst for the upgrading of carbohydrates into 5-hydroxymethylfurfural

The conversion of carbohydrates into 5-hydroxymethylfurfural (HMF), a vital and valuable platform chemical, is sought after in industrial applications but poses significant challenges. In this research, we engineered an ultra-thin layer HTaMoO6 catalyst using ball-milling/liquid-exfoliation technique, demonstrating its efficiency in catalyzing the transformation of carbohydrates to HMF. In contrast to the conventional method utilizing tetra(n-butylammonium) hydroxide as the intercalation agent, the ball-milling/liquid-exfoliation technique not only reduces catalyst preparation time (within 12 h) but also enhances the efficient intercalation, leading to the formation of an ultra-thin layer structure. The resulting catalyst exhibits high total acidity, a favorable Brønsted/Lewis acid ratio, and improved accessibility of active sites due to the thin layer structure post-exfoliation. Compared with bulk LiTaMoO6, the ultrathin layer HTaMoO6 catalyst enables complete fructose dehydration with an HMF yield reaching 89.1 % under moderate reaction conditions (120 °C, 1 h) and 47.2 % yield of HMF is obtained from sucrose at 130 °C. This work provides a new method to fabricate the solid acid for the transformation of carbohydrates.

Investigation of Layered Structure Formation in MgB2 Wires Produced by the Internal Mg Coating Process under Low and High Isostatic Pressures.

Currently, MgB2 wires made by the powder-in-tube (PIT) method are most often used in the construction and design of superconducting devices. In this work, we investigated the impact of heat treatment under both low and high isostatic pressures on the formation of a layered structure in PIT MgB2 wires manufactured using the Mg coating method. The microstructure, chemical composition, and density of the obtained superconductive wires were investigated using scanning electron microscopy (SEM) with an energy-dispersive X-ray spectroscopy (EDS) analyzer and optical microscopy with Kameram CMOS software (version 2.11.5.6). Transport measurements of critical parameters were made by using the Physical Property Measurement System (PPMS) for 100 mA and 19 Hz in a perpendicular magnetic field. We observed that the Mg coating method can significantly reduce the reactions of B with the Fe sheath. Moreover, the shape, uniformity, and continuity of the layered structure (cracks, gaps) depend on the homogeneity of the B layer before the synthesis reaction. Additionally, the formation of a layered structure depends on the annealing temperature (for Mg in the liquid or solid-state), isostatic pressure, type of boron, and density of layer B before the synthesis reaction.

Numerical simulation and performance optimization of all-inorganic CsGeI3 perovskite solar cells with stacked ETLs/C60 by SCAPS device simulation

Perovskite solar cells, particularly those featuring CsGeI3 as the absorption layer, are distinguished by their non-toxicity and inherent stability. In this work, to optimize the interface contact of the cells, enhance their built-in electric field, and consequently augment the power conversion efficiency, a C60 layer was incorporated into the electronic transport layer. This incorporation led to the formation of a novel dual-electron transport layer structure. Employing SCAPS-1D simulation software, a range of electron and hole transport layer combinations was explored. The optimal configuration was determined to be FTO/SnO2/C60/IDL1/CsGeI3/IDL2/Cu2O/Au. The absorption layer's thickness, doping concentration, defect density, and bandgap were optimized. Furthermore, an investigation was conducted on the performance implications arising from alterations in the dual electron conduction layer SnO2/C60's thickness, bandgap, and doping concentration. Concurrently, adjustments were made to refine the defect density in the interface defect layer, and an investigation was carried out to determine the optimal operational temperature. These endeavors culminated in the achievement of an impressive 30.34% optimal power conversion efficiency, representing a significant 54.25% enhancement over the pre-optimization efficiency of 19.67%. This work stands as a valuable reference for subsequent investigations into the dual electron transport layer structure in Ge-based perovskite solar cells.

Development of a bottom-up coarse-grained model for interactions of lipids with TiO nanoparticles.

Understanding interactions of inorganic nanoparticles with biomolecules is important in many biotechnology, nanomedicine, and toxicological research, however, the size of typical nanoparticles makes their direct modeling by atomistic simulations unfeasible. Here, we present a bottom-up coarse-graining approach for modeling titanium dioxide (TiO ) nanomaterials in contact with phospholipids that uses the inverse Monte Carlo method to optimize the effective interactions from the structural data obtained in small-scale all-atom simulations of TiO surfaces with lipids in aqueous solution. The resulting coarse-grained models are able to accurately reproduce the structural details of lipid adsorption on different titania surfaces without the use of an explicit solvent, enabling significant computational resource savings and favorable scaling. Our coarse-grained simulations show that small spherical TiO nanoparticles ( nm) can only be partially wrapped by a lipid bilayer with phosphoethanolamine headgroups, however, the lipid adsorption increases with the radius of the nanoparticle. The current approach can be used to study the effect of the size and shape of TiO nanoparticles on their interactions with cell membrane lipids, which can be a determining factor in membrane wrapping as well as the recently discovered phenomenon of nanoquarantining, which involves the formation of layered nanomaterial-lipid structures.

Iso- and hetero-polyoxovanadium glycolates [VIV6O6(glyc)6MIII(OH)6]3- (M = V, Cr, Fe, and Al) encapsulating metal hydroxides.

Polyoxovanadium glycolates (NH4)3[V6O6(glyc)6V(μ-OH)6]·10H2O (1-V7) (H2glyc = glycolic acid) and its derivatives added with ammonium sulfates (NH4)3[V6O6(glyc)6M(μ-OH)6][(NH4)2SO4]2·xH2O (M = Cr, x = 6, 2-CrV6; M = Fe, x = 7, 3-FeV6; M = Al, x = 6, 4-AlV6) were obtained through self-assembly and fully characterized. Compounds 1-4 are composed of the same fully reduced cyclic {VIV6O6} unit bridged by six glycolate ligands. The framework encapsulated an octahedral metal(III) hydroxide {M(OH)6} (M = V3+, Cr3+, Fe3+, and Al3+) in the center, forming an iso- or hetero-heptanuclear Anderson-type structure. Moreover, two sulfate anions capped the two sides of cyclic {V6O6} units in compounds 2-4. Each sulfate formed a strong triple hydrogen bond (2.657-2.829 Å) with the μ3-OH group of the hydroxide. The sulfate anions played important roles in the formation of layered structures in 2-4, while the clusters were stacked compactly through strong hydrogen bonds in 1-V7. Because of the different central metals, these heptanuclear clusters exhibited distinct electronic structures as well as redox and magnetic properties. Magnetic studies showed that compounds 1-3 exhibited weak antiferromagnetic interactions in decreasing order with Fe3+, V3+ and Cr3+, while 4-AlV6 displayed weak ferromagnetic interactions. Their relationships with the local environment of the FeV-cofactor in V-nitrogenase are also discussed.

Crystal structures of sixteen phosphane chalcogenide complexes of gold(I) chloride, bromide and iodide.

The structures of 16 phosphane chalcogenide complexes of gold(I) halides, with the general formula R 1 3- nR 2 nPEAuX (R 1 = t-butyl; R 2 = isopropyl; n = 0 to 3; E = S or Se; X = Cl, Br or I), are presented. The eight possible chlorido derivatives are: 1a, n = 3, E = S; 2a, n = 2, E = S; 3a, n = 1, E = S; 4a, n = 0, E = S; 5a, n = 3, E = Se; 6a, n = 2, E = Se; 7a, n = 1, E = Se; and 8a, n = 0, E = Se, and the corresponding bromido derivatives are 1b-8b in the same order. However, 2a and 2b were badly disordered and 8a was not obtained. The iodido derivatives are 2c, 6c and 7c (numbered as for the series a and b). All structures are solvent-free and all have Z' = 1 except for 6b and 6c (Z' = 2). All mol-ecules show the expected linear geometry at gold and approximately tetra-hedral angles P-E-Au. The presence of bulky ligands forces some short intra-molecular contacts, in particular H⋯Au and H⋯E. The Au-E bond lengths have a slight but consistent tendency to be longer when trans to a softer X ligand, and vice versa. The five compounds 1a, 5a, 6a, 1b and 5b form an isotypic set, despite the different alkyl groups in 6a. Compounds 3a/3b, 4b/8b and 6b/6c form isotypic pairs. The crystal packing can be analysed in terms of various types of secondary inter-actions, of which the most frequent are 'weak' hydrogen bonds from methine hydrogen atoms to the halogenido ligands. For the structure type 1a, H⋯X and H⋯E contacts combine to form a layer structure. For 3a/3b, the packing is almost featureless, but can be described in terms of a double-layer structure involving borderline H⋯Cl/Br and H⋯S contacts. In 4a and 4b/8b, which lack methine groups, Cmeth-yl-H⋯X contacts combine to form layer structures. In 7a/7b, short C-H⋯X inter-actions form chains of mol-ecules that are further linked by association of short Au⋯Se contacts to form a layer structure. The packing of compound 6b/6c can conveniently be analysed for each independent mol-ecule separately, because they occupy different regions of the cell. Mol-ecule 1 forms chains in which the mol-ecules are linked by a Cmethine⋯Au contact. The mol-ecules 2 associate via a short Se⋯Se contact and a short H⋯X contact to form a layer structure. The packing of compound 2c can be described in terms of two short Cmethine-H⋯I contacts, which combine to form a corrugated ribbon structure. Compound 7c is the only compound in this paper to feature Au⋯Au contacts, which lead to twofold-symmetric dimers. Apart from this, the packing is almost featureless, consisting of layers with only translation symmetry except for two very borderline Au⋯H contacts.

Influence of different additives on the morphology, defect state and luminescence of ZnO nanoparticles

Zinc oxide (ZnO) is an important multifunctional material with applications in various environmental, drug delivery, sensing, and optoelectronics domains. Binding of different molecules on ZnO enhances the properties and characteristics of nanoparticles through surface modification. In this study, varieties of ZnO nanoparticles (ZnO-NP) are prepared using different additives via simple, low-cost precipitation technique at room temperature. The surface state of ZnO-NP was controlled by three surfactants and two silanes, namely: cetyltrimethyl-ammonium bromide, tween 20, heptaethylene glycol monododecyl ether, 3-aminopropyl triethoxysilane, and tetraethoxysilane. The modified ZnO samples were characterized by various analytical techniques, X-ray diffraction, Raman, FT-IR spectroscopy, surface area analysis and electron paramagnetic resonance. The surface area of the samples significantly increases when silanes are used during the synthesis. Scanning electron microscopy shows the formation of either rounded nanoparticles or layered structures. Depending on the type of additives the zeta potential of colloids increase from 25.92 mV up to 40.36 mV. In this study we show that the chemical nature of additives and the stability of colloids play an important role in the generation of luminescent radiative processes. The green luminescence of ZnO colloids is either enhanced or quenched due to the interaction of additives with the particles surface through covalent, electrostatic, and hydrogen bonds. The ZnO surface becomes more or less permissive toward the movement of surface defects, with formation of oxygen vacancies (VO+ and VO++) responsible for the luminescent response.

Synthesis of LiNi1/3Mn1/3Fe1/3O2 as an Intended Cathode Material for Li-Ion Battery

In the present work, we report the synthesis and characterization of LiNi1/3Mn1/3Fe1/3O2 as cathode material for Li-ion batteries. LiNi1/3Mn1/3Fe1/3O2 was synthesized using a very simple and low-cost sol-gel method and subsequent annealing treatment. The Structural, morphological, and electrochemical performance of the synthesized materials is investigated using X-ray diffraction (XRD), Raman spectroscopy, Field Emission Scanning Electron microscopy (FE-SEM), Cyclic voltammetry (CV), Galvanostatic Charge-Discharge (GCD) and Electrochemical Impedance spectroscopy (EIS), respectively. The XRD results revealed the formation of layer structure with a pure α-NaFeO2 hexagonal phase, space group R3¯m. Moreover, these results show negligible cation mixing, which suggests well order layer structure. Raman spectrum of the synthesized sample shows structural fingerprints at 609 and 503 cm-1, which also confirms the R3¯m space group. Raman results support the XRD results. The non-uniform microsphere-like morphology with an average particle size of around 200-300 nm was revealed using FE-SEM. The electrochemical properties of the synthesized products were evaluated in rechargeable Li-ion half cells using a non-aqueous organic electrolyte (1 M LiPO4). The cyclic voltammetry shows that redox reactions occur at the surface of the electrode, which is attributed to Mn3+/Mn4+ and Fe3+/Fe4+. The EIS of LiNi1/3Mn1/3Fe1/3O2 exhibits a lower charge transfer resistance, which indicates a shorter path to move the ions. Further, the electrochemical performance of the synthesized material will be discussed in detail.

Observation of Catalyst Layer Structure Formation from Electrode Slurry By White Light Confocal Microscopy

Mass transport in the catalyst layers (CLs) is an important factor to improve the cell performance of polymer electrolyte fuel cells (PEFCs). Transport properties in the CLs are determined by their structure and material distributions. The CLs are usually fabricated from electrode slurry in which Pt/C and ionomer are contained through applying and drying processes. Therefore, the structure and material distributions in the CLs are determined in these fabrication processes. However, these fabrication processes have been developed through trial-and-error approaches. A fundamental understanding of the structure formation mechanisms during the fabrication processes is required.The authors have performed impedance measurement and surface displacement measurement of electrode slurry during the drying process at the same time and detected the particle packing process (1, 2). For a further understanding of the fabrication process, observation of the structure formation of electrode slurry during drying by white light confocal microscopy was conducted in this study to break down the structure formation regimes. The observation of flow mode on the surface of the slurry and measurement of surface displacement were performed at the same time.Figure 1 shows confocal images of the electrode slurry during drying. Three different regimes were observed. At the initial state of drying, convection flow was observed. Then, the shrinking of the slurry was observed. After shrinking stopped, the solvent was evaporated from the porous media and finally, the structure of the catalyst layer was formed. Understanding the relationships between the variation of the flow regimes during the drying of electrode slurry and fabrication conditions including materials and process parameters can contribute to revealing the methodology for controlling porous structure and material distributions in the catalyst layers.AcknowledgmentsA part of this work was supported by JST PRESTO JPMJPR22O4.References(1) T. Suzuki et al., ECS Trans., 67(17), 465 (2015).(2) T. Suzuki et al., J. Therm. Sci. Technol., 16(1), 20-00259 (2021). Figure 1