Chemistry-Performance Relationships of Polymer Gel-Electrolytes for Mg−S and Li−S Batteries: Influence of Network Cation Solvation Capacity on Polymer-Polysulfide Interactions

Metal-sulfur batteries are a promising next-generation energy storage technology, offering high theoretical energy densities with low cost and good sustainability. An active area of research is the development of electrolytes that address unwanted migration of sulfur and intermediate species known as polysulfides during operation of metal-sulfur batteries, a phenomenon that leads to low energy efficiency and short life-spans. A particular class of electrolytes, gel polymer electrolytes, are especially attractive for their ability to repel polysulfides on the basis of structure, electrostatics, and other polymer properties. Herein, within the context of magnesium- and lithium-sulfur batteries, we investigate the impact of gel polymer electrolyte cation solvation capacity, a property related to network dielectric constant and chemistry, on sulfur/polysulfide-polymer interactions, an understudied property-performance relationship. Polymers with lower cation solvation capacity are found to permanently absorb less polysulfide active material, which increases sulfur utilization for Li−S batteries and significantly increases charge efficiency and life-span for Li−S and Mg−S batteries.     

Synthesis and Properties of TiO2–SiO2/CaO Biomaterials with Spherical Particles Based on Tokem-200 Cation Exchange Resin

Russian Journal of Applied Chemistry - Biomaterials based on Tokem-200 cation exchanger containing spherical particles were synthesized from solutions using the sol-gel method. The outer frame of...     

A Study on the Effects of Carrier Gases on the Structure and Morphology of Carbon Nanotubes Prepared by Pyrolysis of Ferrocene and C2H2 Mixture

Carbon nanotubes （CNTs） were prepared using different carrier gases, with ferrocene as the catalyst precusor and acetylene as the carbon source. The effects of ammonia and nitrogen as carrier gases on the structure and morphology of CNTs were investigated. Transmission electron microscope （TEM）, high-resolution electron microscope （HRTEM）, scanning electron microscope （SEM） and X-ray diffraction （XRD） were employed to characterize the products and the catalyst. Experiment results show that the CNTs grown in N2 gas exhibited cylindrical and tubular structure, while a bamboo-like structure was observed for the CNTs grown in NH3 gas. Moreover, vertically aligned CNTs were obtained on an A12O3 disk when NH3 was used as the carrier gas. The carrier gas also exerted influence on the shape of the catalyst. Based on the theory of active centers of catalysis and combined with the particle shape of the catalyst, a growth model for the vertically aligned CNTs on the substrate is given.     

New PVC-membrane electrode based on charge-transfer inclusion complex between I2 and 1,4,8,11-tetraazacyclotetracdecane for selective determination of I3 − ions

A new triiodide ion-selective electrode based on charge-transfer complex of iodine with 1,4,8,11-tetraazacyclotetracdecane as membrane carrier was prepared. The best performance of electrode observed with the membrane having the ligand–PVC–NPOE–NaTPB composition 3.0:33:66:0.5 mg which worked well over a wide concentration range 2.8 × 10^?6–1.4 × 10^?1 M with a Nernstian slope of 59.6 ± 0.3 mV per decade and a detection limit of 1.2 × 10^?6 M. This electrode showed a response time of 25 s and was used over a period of 2 months. The electrode exhibits an anti-Hofmeister selectivity sequence with a performance for triiodide at pH 1.5–10.2. The response mechanism of the electrode was investigated by UV–Vis spectroscopic technique. The electrode was successfully applied as an indicator electrode in the potentiometric titration of ascorbic acid and hydroquinone in drugs.     

Structural Modulation on NiCo2S4Nanoarray by N Doping to Enhance 2e-ORR Selectivity for Photothermal AOPs and Zn−O2Batteries**

As a H₂O₂ generator, a 2e⁻ oxygen reduction reaction active electrocatalyst plays an important role in the advanced oxidation process to degrade organic pollutants in sewage. To enhance the tendency of NiCo₂S₄ towards the 2e⁻ reduction reaction, N atoms are doped in its structure and replace S²⁻. The result implies that this weakens the interaction between NiCo₂S₄ and OOH*, suppresses O−O bond breaking and enhances H₂O₂ selectivity. This electrocatalyst also shows photothermal effect. Under photothermal heating, H₂O₂ produced by the oxidation reduction reaction can decompose and releaseOH, which degrades organic pollutants through the advanced oxidation process. Photothermal effect induced by the advance oxidation process shows obvious advantages over the traditional Fenton reaction, such as wide pH adaptation scope and low secondary pollutant due to its Fe²⁺ free character. With Zn as anode and the electrocatalyst as cathode material, a Zn−O₂ battery is assembled. It achieves electricity generation and photothermal effect induced by the advance oxidation process simultaneously.     

Gelatin-Derived 1D Carbon Nanofiber Architecture with Simultaneous Decoration of Single Fe−Nx Sites and Fe/Fe3C Nanoparticles for Efficient Oxygen Reduction

Exploring high-performance non-precious-metal electrocatalysts for the oxygen reduction reaction (ORR) is critical. Herein, a scalable and cost-effective strategy is reported for the construction of one-dimensional carbon nanofiber architectures with simultaneous decoration of single Fe−N_x sites and highly dispersed Fe/Fe₃C nanoparticles for efficient ORR, through the Fe^III-complex-assisted electrospinning of gelatin nanofibers with subsequent pre-oxidation and carbonization. Results show that the presence of a Fe^III complex enables the 1D gelatin nanofibers to be well retained during the pre-oxidation process. Owing to the distinct 1D nanofiber structure and the synergistic effect of Fe/Fe₃C and Fe−N_x sites, the resulting electrocatalyst is highly active for ORR with a half-wave potential of 0.885 V (outperforming commercial Pt/C) and a superior electrochemical stability in alkaline electrolytes. Similarly, it also shows a high power density (144.7 mW cm⁻²) and a superior stability in Zn-air batteries. This work opens a path for the design and synthesis of 1D carbon electrocatalyst for efficient ORR catalysis.     

Concentration Effect,Structural Properties,and Driving Force on Aβ28 Dimerization with and without Zn2+ Cooperation: Learning from Replica Exchange Sampling**

Zn²⁺ is a very important factor in promoting the formation of amyloid beta (Aβ) aggregates and amyloid plaques. The Zn²⁺-bound Aβ species generate amorphous or low molecular-weight oligomers. However, it is a lack of studies to approach the starting structural features (dimerization) in Aβ nucleation processes with and without Zn²⁺, which is the key point in understanding Zn²⁺-induced nucleation mechanisms. To better understand the effect of concentration, structural properties, and the driving force, 14 independent replica exchange molecular dynamics simulations were performed in Aβ₂₈ dimerization with and without Zn²⁺ (zAβ₂₈) cooperation. Our scanning results show that the aggregation propensity is easier in Aβ₂₈-Aβ₂₈ and Aβ₂₈-zAβ₂₈ systems than zAβ₂₈-zAβ₂₈ system. In binding property, the Aβ₂₈-Aβ₂₈ model (−61.5 kcal mol⁻¹) is stronger than zAβ₂₈-zAβ₂₈ (−26.6 kcal mol⁻¹) and Aβ₂₈-zAβ₂₈ (−7.24 kcal mol⁻¹) models. Further analysis confirmed that H13 and H14 residues play specific roles in the three systems. The key point is the orientation of N atom of the imidazole ring in histidine residues. Furthermore, we discovered different driving forces for each system. Our current study contributes to the understanding of how the Aβ₂₈ dimer interacts with Zn²⁺, which could lead to new insights into Zn²⁺-induced nucleation mechanisms.     

A microporous metal-organic framework with FeS(2) topology based on [Zn6(μ6-O)] cluster for reversible sensing of small molecules

The first luminescent metal-organic framework (MOF) with [Zn(6)(μ(6)-O)] cluster has been synthesized and realized for reversible sensing of small molecules.     

A multichannel thiacalix[4]arene-based fluorescent chemosensor for Zn2+, F− ions and imaging of living cells

Abstract

The fluorescent sensor (3) based on the 1,3-alternate conformation of the thiacalix[4]arene bearing the coumarin fluorophore, appended via an imino group, has been synthesised. Sensing properties were evaluated in terms of a colorimetric and fluorescence sensor for Zn²⁺ and F^?. High selectivity and excellent sensitivity were exhibited, and ‘off-on’ optical behaviour in different media was observed. All changes were visible to the naked eye, whilst the presence of the Zn²⁺ and F^? induces fluorescence enhancement and the formation of a 1:1 complex with 3. In addition, 3 exhibits low cytotoxicity and good cell permeability and can readily be employed for assessing the change of intracellular levels of Zn²⁺ and F^?.     

A C−N Coupling Polymerization on Ice-Surface towards Decimeter-Sized 2D Covalent Materials with High Catalytic Activity for Water-Splitting

Compared to other solid templates (metal, ceramic, carbon, etc.), polymerization on ice-surface has many advantages. However, the popularity of this method has been impeded by the lack of appropriate polymerization reactions. To date, only few oxidation polymerizations have been reported to occur on ice-surface, and unfortunately they can only produce supramolecular films rather than fully covalent films. Herein for the first time, 2D covalent materials have been created on ice-surface even at −16 °C through a C−N coupling polymerization, and two free-standing 2D polyarylamines ( 2DPA )s were synthesized. Both 2DPA s have decimeter-size and nanometer thickness. This study provides the first polymerization reaction to synthesize 2D covalent materials on ice-surface, which can be used to fabricate materials/tools/robots with specific 2D structure by copying ice morphologies. Furthermore, both 2DPA s exhibit higher hydrogen evolution reaction activity than many metal-free catalysts and even some metal-based catalysts, so this study also provides further insight for the development of metal-free catalysts for water-splitting.     

A multi-functional fluorescent sensor for Zn2+ and HSO4− based on a new diarylethene derivative

A new photochromic diarylethene derivative with a hydralazine unit was designed and synthesized. It was not only acted as a Zn²⁺ sensor with the fluorescent color change from dark blue to bright orange, but also acted as a fluorescent sensor for HSO₄^? with the fluorescent color change from dark blue to bright blue. Furthermore, the derivative also exhibits multi-addressable switching properties by the stimulations of lights and chemical reagents. Based on these characteristics, two combinational logic circuits were constructed with the emission intensity as the output signals, and the UV/vis lights, chemical species as the input signals.     

A Luminescent Zinc(II) Coordination Polymer for Selective Detection of Fe3+ and Cr2O72− in Water and Catalytic CO2 Fixation

Fluorescence-based detection technique using coordination polymer has been considered an attractive alternative over conventional approaches. Herein, a new luminescent zinc(II) coordination polymer, [Zn(4-ABPT)(NIPA)(H₂O)], SSICG-5 , is synthesized by using a Lewis acidic Zn(II) ion, aromatic nitro group containing ligand 5-nitroisophthalic acid (H₂NIPA), and basic −NH₂ rich ligand 3,5-di(pyridine-4-yl)-4H-1,2,4-triazol-4-amine (4-ABPT). SSICG-5 can detect Fe³⁺ and Cr₂O₇²⁻ selectively with a LOD of 0.16 μM and 1.94 μM, respectively. Additionally, carbon dioxide (CO₂) fixation via one-pot CO₂ cycloaddition reaction has significant importance for reduced waste formation, minimizing reaction time and lowering chemical usage. Zn metal centre of SSICG-5 possesses a replaceable coordinated water molecule. The active metal sites combined with the Lewis acidic and basic sites of the ligands make SSICG-5 an ideal bifunctional heterogeneous catalyst for efficient CO₂ cycloaddition reaction under room temperature (RT), solvent-free conditions. Notably, SSICG-5 exhibits near quantitative conversion (turnover number (TON) of 198) of propylene oxide to its carbonate compound under mild reaction conditions.     

Ratiometric and selective two-photon fluorescent probe based on PET-ICT for imaging Zn2+in living cells and tissues简

A two-photon fluorescent probe TPZn was developed for specific ratiometric imaging Zn2＋ in living cells and tissues. Significant ratiometric fluorescence change was based on photoinduced electron transfer and intramolecular charge transfer. The synthetic method of TPZn was simple. It was successfully used to selectively image Zn2＋ based on the higher binding affinity for Zn2＋ than for Cd2＋. TPZn was easily loaded into the living cell and tissues with high membrane permeability in a complex biological environment. TPZn could clearly visualize endogenous Zn2＋ by TP ratiometric imaging in hippocampal slices at a depth of 120 μm. Thus, TPZn is a useful tool to image of Zn2＋ in living cells and tissues without interference from Cd2＋.     

MOF-derived Cu_2O/Cu NPs on N-doped Porous Carbon as a Multifunctional Sensor for Mercury(Ⅱ) and Glucose with Wide Detection Range

Cu_2O/Cu nanoparticles(NPs) in the nanoporous carbon matrix(designated as Cu_2O/Cu@NPC) has been synthesized by in-situ calcination of a cupper-based metal-organic framework(Cu-MOF), and its morphology and composition were characterized by PXRD, SEM and Raman. Furthermore, elemental mapping and XPS analysis not only show Cu NPs is generated along with nitrogen(N)-doped carbon, but also indicate Cu_2O NPs locates in the external layer of Cu@NPC. In addition, the adsorption of dye studies implies that Cu_2O/Cu@NPC exhibits obvious interaction with Rhodamine B(Rh B) due to the feature of porous and N-doped structure. Cu_2O/Cu@NPC has highly electrocatalytic performance for glucose and mercury(Ⅱ) with wide detection range and good stability, which can be used as a novel multifunctional sensor for glucose and mercury(Ⅱ).     

A review of recent researches on Bunsen reaction for hydrogen production via S–I water and H_2S splitting cycles

The Bunsen reaction is the center reaction for both the sulfur–iodine water splitting cycle for hydrogen production and the novel hydrogen sulfide splitting cycle for hydrogen and sulfuric acid production from the sulfur-containing gases.This paper reviews the research progress of the Bunsen reaction in recent 10–15 years.Researches were initially focused on the optimization of the operating conditions of the conventional Bunsen reaction requiring excessive water and iodine to improve the products separation efficiency and to avoid the side reactions and iodine vapor deposition.Alternative methods including electrochemical methods,precipitation methods,and non-aqueous solvent methods had their respective advantages,but still faced challenges.In development of the technology of H_2S splitting cycle,dissolving iodine in toluene solvent could render the Bunsen reaction to occur with the flowable I_2 stream at ambient temperature such that the side reactions and iodine vaporization can be avoided and the corrosion hazard lessened.It also prevented the Bunsen reaction from using excessive iodine and water.The products from the Bunsen reaction including HI,H_2SO_4,H_2O,and toluene could be directly electrolyzed.     

Micellization and relaxation kinetics of diblock copolymers in dilute solution based on A–W theory: I. Description of a model for core–corona type micelles

On the basis of the Aniansson–Wall (A–W) theory, a calculation method for the time evolution of association-number distribution during micelle formation of diblock copolymer in solution is presented. The rate constant for the elemental process of a chain expulsion from a micelle is evaluated as a function of the association number by application of Halperin's treatment based on the Kramers rate theory. Numerical calculations are carried out for both cases of micellization from unimer state and micellar relaxation under a temperature jump from one micellar state to another. In the micelle relaxation, the micelle size changes stepwise with two steps, clearly showing the characteristic feature of the A–W mechanism, where there exist two processes, the fast process undergoing by consuming/releasing free unimers and the slow process accompanied with almost no change of unimer concentration. On the contrary, in the micellization from unimer state, the very fast process is observed, where the free chains get together quickly to form temporal micelles, and is followed by an ordinary micellar relaxation.     

A new family of magnetic 2D coordination polymers based on [MV(CN)8]3− (M=Mo,W) and pre-programmed Cu2+ centres

The self-assembly of [M(CN)₈]³⁻ (M=Mo, W) anion and polyamine complexes of Cu^II[Cu(tetren)]²⁺ and [Cu(dien)(H₂O)₂]²⁺ (tetren=tetraethylenepentamine, dien=diethylenetriamine) in acidic aqueous solution gives (tetrenH₅)_0.8{Cu^II ₄[W^V(CN)₈]₄}·7.2H₂O 1, (tetrenH₅)_0.8{Cu^II ₄[Mo^V(CN)₈]₄}·7.2H₂O 2, (dienH₃){Cu^II ₃[W^V(CN)₈]₃}·4H₂O 3 and (dienH₃){Cu^II ₃[Mo^V(CN)₈]₃}·4H₂O 4 2D coordination polymers. All compounds are structure-related: the crystal structures of isomorphous 1–2 and 3–4, respectively, consist of double-layered cyano-bridged {Cu^II[W^V(CN)₈]⁻}_n square grid backbones and non-coordinated fully protonated polyamine countercations as well as H₂O molecules located between the sheets. The magnetic measurements reveal long range ferromagnetic ordering with sharp phase transitions at T_C in range 28–37 K and coercivity in range 30–225 Oe at liquid helium temperature, T=4.3 K.     

A rapid selective colorimetric and ‘On–Off’ fluorimetric sensor for detecting Cu2+ ions in aqueous media based on a simple bis-schiff-base derivative

A simple colorimetric and fluorimetric ‘On–Off’ sensor L (3,3′-dimethyl -[1,1′-biphenyl]-4,4′-diyl)bis(azanylylidene)bis(methanylylidene)bis(naphthalen-2-ol) for Cu²⁺ ions bearing o-tolidine substituents has been designed and synthesised, and exhibits significant fluorimetric and colorimetric response for Cu²⁺ in DMSO/H₂O (8:2, v/v) HEPES buffer (pH 7.2) solution. The detection limit of the sensor towards Cu²⁺ is 7.25 × 10^? 8 M and the association constant K_a of 9.86 × 10⁴ M^? 1 was determined. Furthermore, other anions, including Fe³⁺, Hg²⁺, Ag⁺, Ca²⁺, Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Cr³⁺ and Mg²⁺ have almost no influence on the probe's behaviour. Test strips based on the sensor L were fabricated, which could act as convenient and efficient Cu²⁺ test kits.     

Surface Acidity／Basicity and Catalytic Reactivity of CeO2／γ—A12O3 Catalysts for the Oxidative Dehydrogenation of Ethane with Carbon Dioxide to Ethylene

Dehydrogenation of ethane to ethylene in CO2 was investigated over CeO2/γ-Al2O3 catalysts at 700℃ in a conventional flow reactor operating at atmospheric pressure. XRD, BET and microcalorimetric adsorption techniques were used to characterize the structure and surface acidity/basicity of the CeO2/γ-Al2O3 catalysts. The results show that the surface acidity decreased while the surface basicity increased after the addition of CeO2 to γ-Al2O3. Accordingly, the activity of the hydrogenation reaction of CO2 increased, which might be responsible for the enhanced conversion in the dehydrogenation of ethane to ethylene. The highest ethane conversion obtained was about 15% for the 25?O2/γ-Al2O3. The selectivity to ethylene was high for all the CeO2, γ-Al2O3 and CeO2/γ-Al2O3 catalysts.