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Concentrated ionic aqueous electrolytes possess a diverse array of applications across various fields, particularly in the field of energy storage. Despite extensive examination, the intricate relationships and numerous physical mechanisms underpinning diverse phenomena remain incompletely understood. Molecular dynamics simulations are employed to probe the attributes of aqueous solutions containing LiCl, NaCl, KCl, MgCl2, and CaCl2, spanning various solute fractions. The primary emphasis of the simulations is on unraveling the intricate interplay between these attributes and the underlying physical mechanisms. The configurations of cation-Cl− and Cl−–Cl− pairs within these solutions are disclosed. As the solute fraction increases, consistent trends manifest regardless of solute type: (i) the number of hydrogen bonds formed by the hydration water surrounding ions decreases, primarily attributed to the growing presence of counter ions in proximity to the hydration water; (ii) the hydration number of ions exhibits varying trends influenced by multiple factor; and (iii) the diffusion of ions slows down, attributed to the enhanced confinement and rebound of cations and Cl− ions from the surrounding atoms, concurrently coupled with the changes in ion vibration modes. In our analysis, we have, for the first time, clarified the reasons behind the slowing down of the diffusion of the ions with increasing solute fraction. Our research contributes to a better understanding and manipulation of the attributes of ionic aqueous solutions and may help designing high-performance electrolytes. [ABSTRACT FROM AUTHOR]

A flexible tripodal pyrrole-imine ligand (H3L) has been used to facilitate the controlled and sequential single-electron reductions of the uranyl dication from the U(VI) oxidation state to U(V) and further to U(IV), processes that are important to understanding the reduction of uranyl and its environmental remediation. The uranyl(VI) complexes UO2(HL)(sol) (sol = THF, py) were straightforwardly accessed by the transamination reaction of H3L with UO2{N(SiMe3)2}2(THF)2 and adopt 'hangman' structures in which one of the pyrrole-imine arms is pendant. While deprotonation of this arm by LiN(SiMe3)2 causes no change in uranyl oxidation state, single-electron reduction of uranyl(VI) to uranyl(V) occurred on addition of two equivalents of KN(SiMe3)2 to UO2(HL)(sol). The potassium cations of this new [UVO2(K2L)]2 dimer were substituted by transmetalation with the appropriate metal chloride salt, forming the new uranyl(V) tetra-heterometallic complexes, [UVO2Zn(L)(py)2]2 and [UVO2Ln(Cl)(L)(py)2]2 (Ln = Y, Sm, Dy). The dimeric uranyl(V)–yttrium complex underwent further reduction and chloride abstraction to form the tetrametallic U(IV) complex [UIVO2YIII(py)]2, so highlighting the adaptability of this ligand to stabilise a variety of different uranium oxidation states. [ABSTRACT FROM AUTHOR]

The preparation of cationic bis(hydrosilane)–coinage‐metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BArF4] is described. Unlike previously reported hydrosilane‐stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate (ortho‐silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X‐ray diffraction analysis, revealing that both Si−H bonds are activated by the Lewis acidic cationic metal center. The new complexes were found to be effective in catalytic carbonyl hydrosilylation, leading to the corresponding silyl ethers under mild conditions without the addition of an external base. Combined mechanistic control experiments and quantum chemical calculations support an ionic outer‐sphere mechanism, in which a neutral metal alkoxide species instead of a metal hydride is the key intermediate that interacts with the silylcarboxonium ion to generate the silyl ether. [ABSTRACT FROM AUTHOR]

New biodegradable packaging has been developed from renewable sources, mainly of vegetable origin. Arrowroot starch has been recently used to produce high-quality biodegradable films capable of behaving well when incorporating oils, extracts, metal, and metal nanocomposites. The study aimed to verify the impact of incorporating metals in the sulfate and chloride forms in a biopolymeric matrix from arrowroot starch in terms of biodegradability, physicochemical and microbiological parameters. Different arrowroot films were produced to incorporate solutions with a concentration of 1 Mol L-1 of sulfate and chloride metals. The action of biodegradability in soil, UV transmittance, and visible light were observed in UV-Vis spectrophotometry and antimicrobial action on Escherichia coli, Staphylococcus aureus, Salmonella serovar Typhimurium, and Salmonella serovar Enteritidis. Good results were obtained, such as biodegradability time between 81.70 to 100% (30 days), a low transmission rate of UV radiation and visible light between 250 to 890 nm, high capacity for bacterial inhibition between 22.08 to 10.05 mm for E. coli, among 25.59 to 11.10 mm for S. aureus, between 22.14 to 11.66 mm for S. serovar Typhimurium and between 21.11 to 8.26 mm for S. serovar Enteritidis. It is concluded that the biodegradable films of arrowroot starch incorporated with metals showed potential in all the evaluated tests, thus characterizing possible new products for different uses, such as low time available in the environment, preservation of the characteristics of special products, and antimicrobial capacity. [ABSTRACT FROM AUTHOR]

The chlorination of oxides of major concern in cassiterite concentrate with various chlorinating agents is investigated in light of their thermodynamic feasibilities to extract and recover their valuable metal components. Mechanisms responsible for the processes and their Gibbs free energy changes as a function of temperature to selectively separate and/or recover the metal(s) of interest and unwanted ones as their metallic chlorides are identified. Attention is given to gaseous (Cl2 and Cl2 + CO mixture) and solid (CaCl2 and MgCl2) chlorine sources, from which Cl2 + CO shows no reaction selectivity for any of the oxides but a feasible metal chloride formation for all. Chlorine gas (Cl2), on the other hand, could selectively form chlorides with metals of +2 oxidation state in their oxides, leaving those of high oxidation state unreacted. MgCl2, unlike CaCl2, is found capable of producing calcium, ferrous, and stannic chloride from their metallic oxides with enhanced reaction tendencies in the presence of silicon dioxide (SiO2). An overall study of the thermodynamic feasibility of all chlorine sources looked at alongside operational and environmental viabilities suitably suggests MgCl2 for a selective extraction of the valuable metal components in a cassiterite concentrate, in which case, moderate temperatures seem promising. [ABSTRACT FROM AUTHOR]

Stimulus‐responsive materials that exhibit efficient circularly polarized luminescence (CPL) have gained much interest for application in advanced smart photonics. Herein, the CPL‐active enantiomorphic 0D Sb3+‐doped (R/S)2InCl7 (R/S = R/S‐2‐methylpiperazine) are synthesized via a solution method. They show efficient broadband yellow emission with a near‐unity photoluminescence quantum yield and a CPL asymmetry factor of 1.7 × 10−3. Their fascinating chiroptical activity should be attributed to the chirality transfer and self‐trapped exciton emission caused by strong electron–phonon interaction. Particularly, H2O‐induced structural transformation is demonstrated to obtain non‐emission of Sb3+‐doped (R/S)2InCl7·H2O after exposure to a humid environment. Importantly, Sb3+‐doped (R/S)2InCl7 exhibits unique nonlinear optical responses, and the rotation angle between the quarter‐wave plate and linearly polarized plate can regulate the reversible switching of Sb3+‐doped (R/S)2InCl7 between yellow emission and negligible luminescence. Moreover, a circularly polarized white light‐emitting diode is fabricated by combining blue phosphors BaMgAl10O17:Eu2+, and the device exhibits tunable switching control of positive and warm white light by regulating the rotation angle of linear polarizer plate. Based on the tunable optical responses of Sb3+‐doped (R/S)2InCl7, a programmable multi‐mode fluorescence encoding system is constructed, and four‐level information encryption and three‐level encrypted 3D color codes are also realized in a further proof‐of‐concept experiment. [ABSTRACT FROM AUTHOR]

The presented research is the seed of a vision for the development of a waste-for-product strategy. Following this concept, various synthetic solutions containing low concentrations of platinum group metals were used to model their recovery and to produce catalysts. This is also the first report that shows the method for synthesis of a pyramid-like structure deposited on activated carbon composed of Pd and Pt. This unique structure was obtained from a mixture of highly diluted aqueous solutions containing both metals and chloride ions. The presence of functional groups on the carbon surface and experimental conditions allowed for: the adsorption of metal complexes, their reduction to metal atoms and enabled further hierarchical growth of the metal layer on the carbon surface. During experiments, spherical palladium and platinum nanoparticles were obtained. The addition of chloride ions to the solution promoted the hierarchical growth and formation of palladium nanopyramids, which were enriched with platinum nanoparticles. The obtained materials were characterized using UV–Vis, Raman, IR spectroscopy, TGA, SEM/EDS, and XRD techniques. Moreover, Pd@ROY, Pt@ROY, and Pd-Pt@ROY were tested as possible electrocatalysts for hydrogen evolution reactions. [ABSTRACT FROM AUTHOR]

In the synthesis of metal–organic frameworks (MOFs), the choice of the metal precursor plays a key role because of the influence that it can exert on the crystallization kinetics. The present work explores the use of metal-carbamato complexes for the synthesis of benchmark MOFs, namely HKUST-1 and UiO-66. Cu2(O2CNEt2)4·2NHEt2 and Zr(O2CNEt2)4, prepared using straightforward CO2 fixation reactions starting from the corresponding metal chlorides and diethylamine, were employed as metal precursors for MOF formation. The synthesis conditions, including the solvent, temperature, and ligand protonation degree, were systematically investigated, revealing metal carbamates as highly reactive precursors due to their prompt release of CO2 and amine upon reaction with protic species, i.e., the polycarboxylic linkers. This property of metal carbamates allowed us to identify room temperature protocols to achieve MOFs with comparable properties to those obtained using traditional metal precursors. Subsequent optimization of the reaction conditions led to the design of a one-pot synthetic strategy for HKUST-1, starting directly from copper(II) chloride and diethylamine under a CO2 atmosphere. The MOFs were characterized using various techniques, including powder X-ray diffraction, N2 sorption analysis, 1H nuclear magnetic resonance spectroscopy, and CHN elemental analysis, and compared to reference samples prepared according to literature procedures. [ABSTRACT FROM AUTHOR]

It is fundamentally challenging to achieve stable and efficient all‐inorganic perovskite solar cells (PSCs) in ambient air conditions for low‐cost commercial manufacturing, as the crystallinity, surface morphology, and optical activity of all‐inorganic perovskites exhibit high sensitivity to environmental factors such as moisture and illumination. Herein, a dual‐doping strategy is presented to prepare high‐quality dual‐doping CsPbI2Br films under ambient air with relative humidity of 70% (70% RH) by introducing CaCl2 and InCl3 additives into precursor solution. The results from the experiments and calculations reveal that the CaCl2 additive can isolate moisture by forming hydrates at the surface and grain boundary of perovskites. Meanwhile, the addition of InCl3 can significantly improve the optoelectronic properties via the heterovalent substitution of Pb2+ by a small amount of In3+. Moreover, the phase segregation can be significantly suppressed in the dual‐doping CsPbI2Br films owing to decreasing the electron–phonon coupling strength and increasing the activation energy of ion migration. The unencapsulated dual‐doping CsPbI2Br PSC with the power conversion efficiency (PCE) of 15.51% (70% RH) demonstrates high humidity storage and long‐term optical stability, remaining 90% of the original PCE after aging 2400 h under ambient air (50% RH) and 1500 h under continuous illumination, respectively. [ABSTRACT FROM AUTHOR]

The interaction of proteins with salt ions plays an important role in life activities. We used butyramide as a model molecule to investigate the interaction of protein backbones with cations. The experiment was performed in an aqueous solution of metal chloride using UV Raman spectroscopy. It was found that well-hydrated metal cations (Ca2+, Mg2+) tend to bind to C=O in the amide bond, resulting in redistribution of the amide I band peaks. Specifically, the peak intensity ratio of 1655 cm-1 to 1610 cm-1 increases significantly with increasing concentrations. However, this phenomenon is not obviously observed in NaCl solution. Furthermore, we studied the effect of salt ions on the water structures. The addition of Ca2+ and Mg2+ is beneficial to the enhancement of the water signal at the 3400 cm−1 position, while the Na+ at the same concentration is not obvious. The results have shown that the interaction between cations and amides satisfies the following order: Ca2+>Mg2+>Na+, which conforms to the Hofmeister series. [ABSTRACT FROM AUTHOR]

The cost‐effective synthesis of high‐performance hard carbons (HCs) is a key step of sodium‐ion batteries toward practical applications. Considering the rich resource of low‐value aromatic hydrocarbons (e.g., pitch), there is tremendous interesting in its conversion into value‐added HCs. Unfortunately, it still lacks an efficient way for the synthesis, in addition to the time‐consuming oxygen contamination of the carbon framework. Herein, a universal strategy is reported that enables the efficient synthesis of HCs from pitch by modulating hydrogen transfer using metal chlorides. CuCl2 is selected as the model modulator and the effect of different metal chlorides (FeCl3, AlCl3, ZnCl2, and MgCl2) are further explored. Based on material characterizations and density functional theory calculation employing 1‐methylnaphthalene as the model molecule, it shows that the hydrogen capture and chlorination reactions mediated by CuCl2 and FeCl3 are thermodynamically favored, which promote the crosslinking of pitch to form HCs. After optimization, the derived HC exhibits superior performance of reversible capacity of 304.8 mAh g−1 and a high initial Columbic efficiency of 88.4%. These discoveries provide new insights into the synthesis of HCs from aromatic hydrocarbons, facilitating their utilization in electrochemical energy storage. [ABSTRACT FROM AUTHOR]

Converting any desired C−H bond to the intended C−Z bond in a given organic molecule could be the final peak of the C−H functionalization methodology. Among the three types of C−H bonds, the functionalization of the ubiquitous C(sp3)−H bond has gained particular attention, especially in the last two decades. There are different ways to transform C(sp3)−H bonds into desired C−Z bonds. The use of chlorine radicals is one of these methods with a promising future. The literature review shows that different sources have been used for chlorine, including chloride ions (HCl or chloride salts), coordinated chlorides (transition metal complexes), and organic chlorides (organochlorine compounds). However, HCl and FeCl3 have gained the most attention among these sources. There are three major ways to convert chlorine from these sources to chlorine radicals: 1) oxidation of hydrogen chloride or chloride salts, 2) photolysis of metal chloride, and 3) transition metal insertion into C−Cl bonds. This review summarizes published research papers on the use of chlorine radicals for C(sp3)−H bonds functionalization. Therefore, chlorination reactions of C(sp3)−H bonds and reactions in which chlorine radicals do not play a direct role in C(sp3)−H bond cleavage are not within the scope of this review. [ABSTRACT FROM AUTHOR]

Based on a literature review, the relevance and necessity of processing e‑waste are shown. Pyro-, hydro- and biometallurgical methods for processing e‑waste are briefly described, and the advantages and disadvantages of existing technologies are compared. The efficiency and the environmental and health impacts of various technologies are analyzed. The low-temperature chlorination technology applied to e‑waste processing is given a thermodynamic interpretation to obtain additional information necessary for better understanding of the behavior of gold and other non-ferrous metals with low metal content. The mechanism of the interaction between e‑waste elements and gaseous chlorine during low-temperature roasting was studied. The behavior of metals at low temperatures of chlorination of e‑waste (below 673 K) was assessed from the changes in the thermodynamic quantities of the system. Thermodynamic calculations were conducted to determine the Gibbs free energy (Δ G T 0 ) of the reactions between e‑waste elements and gaseous chlorine at various temperatures. Based on the thermodynamic calculations of the reactions of precious (gold, silver, platinum, palladium) and other non-ferrous metals (Cu, Pb, Zn) with gaseous chlorine at low chlorination temperatures of 323–673 K, it was established that it is possible to selectively recover gold as sublimates Au2Cl6(g) and to produce a solid-phase cinder containing solid chlorides of precious and non-ferrous metals. The low-temperature chlorination roasting of e‑waste is a good prerequisite for the integrated recovery of gold and other precious and non-ferrous metals with high efficiency. The obtained results will be used for the selection, justification, and science-based design of innovative technology for processing e‑waste, using not only gaseous chlorine, but also solid chlorine-containing reagents (CaCl2, NaCl). [ABSTRACT FROM AUTHOR]

Conventional farming practices have negatively impacted micronutrient fertility and overall soil health. Metal lactates are an organic micronutrient amendment that provide both a labile carbon substrate as well as mineral nutrition for plant and microbial growth. To determine the ability of metal lactates to provide readily available micronutrients, Zn, Cu, Mn, Ni, and Co in lactate and chloride salt form were amended to soils and incubated for 28 days. Operationally defined speciation was determined using sequential extraction on samples incubated for 1, 5, or 28 days. The results show a comparable distribution of metals in chloride and lactate form; however, differences were detected in water‐soluble and exchangeable Ni and Zn at each timepoint. For example, in the water exchangeable fraction, there was 2.6%–2.9% less Ni and 0.2%–0.3% less Zn in the metal lactate‐treated soil compared to soil treated with metal chlorides. Furthermore, carbonate‐bound Ni averaged 4.1% and 4% less in metal lactate‐treated soils as compared to metal chloride‐treated soils on days 1 and 5, and Cu decreased 2.9%–3.3% during the treatment period for the lactate‐bound form. Additionally, microbial phospholipid fatty acid (PLFA) was performed and found a stimulatory effect of metal lactates on bacterial biomass with an increase of 12%–18% relative to the metal chloride treatment. Results from this study support the use of metal lactates as a sustainable alternative to conventional fertilizers by providing bioavailable micronutrients for plant nutrition in addition to a labile carbon source to support the growth of microbial populations. Core Ideas: Zn, Cu, Ni, and Co in lactate and chloride salt form have similar distribution in silt loam soil.Zn, Cu, and Ni supplied in chloride form were significantly more available than lactate forms.Metal lactates led to significantly greater bacterial and protozoan biomass compared to metal chlorides. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are now enjoying an increased scientific interest due to their interesting properties and growing range of possible applications. Computational methods are at the forefront of deciphering their structure and dynamics. Type IV DESs, composed of metal chloride and a hydrogen bond donor, are among the less studied systems when it comes to their understanding at a molecular level. An important example of such systems is the zinc chloride–urea DES, already used in chemical synthesis, among others. In this paper, the ZnCl2(urea)2 crystal is studied from the point of view of its structure, infrared spectrum, and intermolecular interactions using periodic density functional theory and non-covalent interactions analysis. The two main structural motifs found in the crystal are a strongly hydrogen-bonded urea dimer assisted by chloride anions and a tetrahedral Zn(II) coordination complex. The crystal is composed of two interlocking parallel planes connected via the zinc cations. The infrared spectrum and bond lengths suggest a partially covalent character of the Zn−Cl bonds. The present analysis has far-reaching implications for the liquid ZnCl2–urea DES, explaining its fluidity, expected microstructure, and low conductivity, among others. [ABSTRACT FROM AUTHOR]

This study was focused on the activation of the C＝P bond via reactions of Ph2C＝P-PtBu2 (1) with 1,6-hexanediol and selected dithiols (1,4-butanedithiol, 1,4-benzenedithiol and 1,4-benzenedimethanethiol). These reactions proceed according to a 1,2-addition mechanism, providing new compounds with formulas {(Ph)2(H)C-P-PtBu2}{μ2-(O-(CH2)6-O)}{tBu2P-P-C(H)(Ph)2} (2), {(Ph)2(H)C-P-PtBu2}{μ2-(S-(CH2)4-S)}{tBu2P-P-C(H)(Ph)2} (3a), {(Ph)2(H)C-P-PtBu2}{μ2-(S-C6H4-S)}{tBu2P-P-C(H)(Ph)2} (3b), and {(Ph)2(H)C-P-PtBu2}{μ2-(S-CH2-C6H4-CH2-S)}{tBu2P-P-C(H)(Ph)2} (3c). Next, the reactions of 3a and 3c with metal chlorides led to the growth of desired coordination polymers of copper(I) and silver(I). All the obtained compounds remained stable under atmospheric conditions. [ABSTRACT FROM AUTHOR]

The chemical etching method has the advantages of high precision and low cost for the preparation of steel surface microchannel, but the composition of the etching solution and the etching process have a great influence on the precision of the microstructure. In this article, the influence of etching solution composition and the etching time on the etching precision of stainless steel using a mixture of HCl and H2O2 as an etching solution is studied. The reactions and passivation processes that occur during the etching process are analyzed. The etching mechanism is revealed. The sample prepared with HCl:H2O2 = 1:2 can obtain better etching precision and high-dimensional stability. The amount of lateral erosion and the depth of etching increases with the increase of etching time, resulting in a decrease in the etching factor and precision. Pitting and intergranular corrosion mainly occur during the etching process, and the loss of metal chloride formed in the process forms holes, which become rapid diffusion channels for corrosive Cl and O elements, and promotes the etching process. The etching reaction forms a passivation film on the surface of the substrate, which reduces the rate of the etching reaction. [ABSTRACT FROM AUTHOR]

Although MXenes have been synthesized by liquid phase and molten salt etching approaches, it still suffers from sluggish reaction kinetics of removing A species from MAX phases associated with an overlong production time (5–48 h). Here, a minute‐level production approach is developed to produce MXenes (Ti2CClx) by selectively etching MAX phases (Ti2AlC) under metal chloride (ZnCl2) vapor. In this synthetic protocol, metal chloride vapor possesses a very high chemical activity to the interlaminar A metal layers of MAX phases owing to negative Gibbs free energies, accompanied with the fast removal of gaseous A‐containing chlorides in the reaction system. Moreover, some M species can be controllably etched off from the lattice of MX slabs to generate metal vacancies, which have a high reducing ability to implant single‐atom Zn from ZnCl2 vapor. Finally, vacancy‐enriched MXenes are produced after the volatilization of Zn. In this manner, the etching time is less than one‐sixtieth those of liquid phase and molten salt etching approaches. The resultant MXenes can be employed as an efficient platform for implanting single‐atom Pt, showing a low overpotential of 41 mV at a current density of 10 mA cm−2 and a good long‐term stability up to 5000 cycles. [ABSTRACT FROM AUTHOR]

Transition metal oxides (such as Co3O4 and Mn3O4) have become a focal point of battery material research due to their high specific capacity. Previous studies have shown that transition metal chlorides can be used to prepare metal oxides (TMOs) through electroconversion in aqueous solutions. However, in industry, TMOs are typically prepared by thermally decomposing metal hydroxides or carbonates (TMCs) precursors. TMCs, in particular, are lithium-ion batteries (LIBs) anode materials with high specific capacity and initial Coulombic efficiency. In this paper, we aim to further investigate the electroconversion process by introducing CO2 directly into the catholyte. Our goal is to determine whether CO2 can be converted into TMCs without the need for a surfactant. Through our research, we successfully obtained monodisperse cubic particles of MnCO3 with regular shapes and edges measuring approximately 300 nm. As an anode material for LIBs, MnCO3 exhibits a higher capacity than graphite and demonstrates good capacity retention. Additionally, the use of submicron MnCO3 as an anode material could potentially replace other more toxic and expensive options currently utilized in commercial LIBs products. [ABSTRACT FROM AUTHOR]

Broadband ferromagnetic resonance (BFMR) spectroscopy analysis can be achieved with different setups involving the frequency-sweep and field-sweep setups. To evaluate and compare the two former regimes, a frequency-sweep and a field-sweep shortcut BFMR regimes were conducted on Co–Ni ferrite nanoparticles that were synthesized by the co-precipitation method of metal chlorides. The nanoparticles were structurally and magnetically characterized, with an average particle size of around 23 nm and a spinel structure. The saturation magnetization was about 59 emu/g, and the coercivity was about 30 Oe. The BFMR analyses were achieved through a frequency range of (2–26) GHz and a field range of (0-104 )Oe. The two regimes, frequency sweep and field sweep, showed linear behavior between the resonance field and resonance frequency. The frequency–sweep regime displayed more complicated curves involving small multi-peaks within the multi-FMR absorption band that were not found in the field sweep regime. The intercepts of the linear dispersion relationship between the two regimes are nearly equivalent to each other. The field-sweep g-factor was higher and more reasonable than the frequency-sweep one, whereas its damping factor was lower. The fluctuation in the frequency linewidth vs. resonance field in the frequency-sweep method is higher than that for the field-sweep. [ABSTRACT FROM AUTHOR]

CO2 hydrate technology can be applied to seawater desalination. However, the kinetics of CO2 hydrate formation were inhibited in the aqueous solution with inorganic salts, and the kinetic mechanism of CO2 hydrate formation for inorganic salts with different metal cations and anions was still unclear. In this work, CO2 hydrate nucleation and growth were studied in aqueous solutions of metal chlorides. Instead of Na+ and K+ ions, CO2 hydrate nucleation was promoted in the presence of Ni2+, Mn2+, Zn2+ and Fe3+ ions due to the co‐ordination bonds between transition metal ions and water molecules to enhance the formation of the critical crystal nuclei. The induction time was increased by 61.1% in aqueous solution with 0.32 mol/L NaCl, while it was shortened by 55.6% in FeCl3 aqueous solution at the same concentration of Cl− anions. In the process of CO2 hydrate growth, Cl− ions played a more important role than the metal ions in affecting the stability of CO2 hydrate cages. The gas storage capacity was reduced by 10.3% in the presence of NaCl, and was lower than that of other metal chlorides. Cl− anions were absorbed on the hydrate surface and involved in hydrate cages to inhibit the hydrate growth due to the hydrogen bonds between the Cl− ions and water molecules of the hydrate cages. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

In this paper, palmitic acid and sodium N-methyl taurine were used as raw materials to directly synthesize sodium palmitic methyl taurine. The structure of the product was characterized by Fourier-transform infrared spectrometer and liquid chromatograph-mass spectrometer. Series of metal oxides (zinc oxide and magnesium oxide), metal chlorides (magnesium chloride and stannous chloride) and boronic acids (methylboronic acid, phenylboronic acid and 2-chlorophenylboronic acid) were screened for their ability to catalyze the reaction. The effect of catalysts on the yield and selectivity of sodium palmitic methyl taurine was studied systematically. The results showed that the yield of sodium palmitic methyl taurine increased significantly during the early stage of the reaction, and remained barely changed after 4 h. Boronic acids performed better than the other catalysts tested. The reaction kinetics was studied in detail using 2-chlorophenylboronic acid as the catalyst with a loading amount of 4% relative to palmitic acid. The concentration of N-methyl taurine was determined at different time points with different temperatures. According to the experimental data, the reaction rate constant, reaction order, reaction activation energy and pre-exponential factor were calculated to obtain an expression of the reaction rate. Under the optimal condition, a yield of sodium palmitic methyl taurine of 97.5%, and a selectivity of 98.4% were obtained. With an excess of palmitic acid, an activation energy of 68.0 kJ/mol and a pre-exponential factor of 1.6 x 1010 h-1 were obtained. [ABSTRACT FROM AUTHOR]

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This work presents a generic strategy to create a series of metal mercaptides complexes via coordination selfassembly between transition metals (Mn, Cu, Co, Fe, and Ni) and cysteine (Cys) by forming the sulfur-metal bridges. This strategy involves dissolving metal chlorides and Cys into deep eutectic solvents (DES), followed by the precipitation of metal mercaptides complexes (such as Cys-Mn) by adding water as an antisolvent, where DES serves as the solvent, shape directing, and capping agent, thereby preventing the formation of other metal impurities. Interestingly, the prepared complexes possess both laccase and peroxidase-like properties, allowing the design of a technique for the detection of L-3,4-dihydroxyphenylalanine (L-DOPA) and uric acid, respectively. The prepared Cys-Mn can linearly oxidize L-DOPA with its concentrations from 0.1 to 130 µM and the detection limit was calculated to be 75.5 nM. Additionally, the Cys-Mn can mimic the activity of peroxidase towards oxidization of o-phenylenediamine at neutral pH, allowing single-step and one-pot cascade reactions for visual and fluorometric measurements of uric acid (UA) that could work in the range of 0.2-500 µM UA with a detection limit of 0.06 µM and 0.054 µM, respectively. The assay was successful in detecting UA in serum and urine samples with relative standard deviation (RSD) ranging from 7.3% to 10.2% and 3.0%-8.5% respectively, suggesting that it may prove useful in medical diagnostic testing. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) are green solvents involved in chemical reaction and separation processes. In this paper, four ILs-based metal catalysts were prepared by dissolving four transition metal chlorides into 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). Their catalytic performance was measured, and the catalytic mechanism was studied via density functional theory (DFT) based on the analysis of the Mayer bonding order, Mulliken charge, molecular electrostatic potential (ESP), electron localization function (ELF), and partial density of states (PDOS). The results show that the catalytic activity follows the order [Bmim]Cl-RuCl3 > [Bmim]Cl-AgCl > [Bmim]Cl-CuCl2 > [Bmim]Cl-CuCl. [Bmim]Cl helps to dissolve and activate HCl, and the metal chlorides can greatly reduce the activation energy of the reaction. This study provides new insights into the catalytic mechanism of IL, transition metals, and their synergistic effect from a microscopic point of view and sheds light on the development of new catalysts for acetylene hydrochlorination. [ABSTRACT FROM AUTHOR]

The conversion of biomass energy sources is a crucial direction in the transformation of energy resources, such as cellulose to high-value chemicals. As an important platform compound, 5-hydroxymethylfurfural (HMF) is one of the worthwhile products from biomass. Previously, the use of Hf/ZSM-5 catalyst demonstrated excellent catalytic performance, with the yield of HMF reaching 67.50% under optimal reaction conditions (120 min, 190 °C, H2O(NaCl)/THF). Based on the previous work, the effect of a series of metal salts on the preparation of HMF from cellulose catalyzed by Hf/ZSM-5 catalyst was investigated in this paper. This result demonstrates the addition of AlCl3 promoted the production of HMF yield and AlCl3 completed with excellent performance among five metal salts. Moreover, the yield of HMF was improved to 70.95% by adjusting the optimal reaction conditions. [ABSTRACT FROM AUTHOR]

Spent automobile exhaust catalysts are a typical platinum group metal secondary resource. In the traditional hydrometallurgical process, the extraction of platinum group metals by oxidative acid leaching will lead to the problem of a low palladium leaching ratio. In this paper, the E-pH diagram of platinum group metals and chloride ions is drawn. The existing forms of platinum group metals under different pH and potential conditions are analyzed, and the reason for this phenomenon is explained. It is proposed to use ferric chloride as oxidant to efficiently leach palladium in a hydrochloric acid system. The leaching ratio of palladium reached 97.67%, which is 6.77% higher than that of hydrogen peroxide as oxidant. The leaching residue is then oxidized by hydrogen peroxide. The comprehensive leaching ratios of platinum, palladium, and rhodium can reach 97.72%, 98.92%, and 99.53%, respectively. [ABSTRACT FROM AUTHOR]

The separation and enrichment of precious metal gold in chloride system with synergistic extraction system composed of DIBK(HA) and TBP(B) was stuied. The effects of extraction system and composition, extraction time, extraction temperature, aqueous chloride ion concentration, and extraction ratio(VO/VA) on the separation performance of gold extraction was investigated, and the extraction mechanism was preliminarily explored by slope method. The results indicate that under the conditions of synergistic extraction system of TBP-D1BK, total extractant concentration of 1. 5 mol/L, n(TBP) = n(DIBK) = 1 : 4, extraction time of 20 min, extraction temperature of 20 °C, VO/VA = 2/1, aqueous chloride ion concentration of 6 mol/L, the extraction rate of gold can reach 98. 82%. The maximum gold/copper extraction separation coefficient is 1 189. 05. Gradient method suggests that the composition of the extract may be [AuCl6 ⋅ 3A ⋅ B]. The extraction chemical reaction formula can be rewritten as: Au3+ +6Cl1- + 3HA + B → [AuCl6 ⋅ 3A ⋅ B]+3H+. [ABSTRACT FROM AUTHOR]

The oxyhydrogen flame (OHF) can generate temperatures as high as 2800 K and a jet flow of highly reactive free radicals including H, OH, HO 2 and O. Therefore, it could serve as an effective means for treating various chemical wastes, particularly organic wastes. Building upon our previous research on metal chlorides, we present here a study on the degradation mechanism of aqueous methyl orange (MO) solution under OHF. Although the decolorization of MO solution is rapid, complete degradation is a slow and intricate process. Initially, MO solution undergoes decolorization by breaking the azo bond followed by oxidation processes that convert aminobenzene compounds to benzoquinone and break down the benzene ring until ultimately being fully converted into CO 2 and H 2 O. [Display omitted] • Oxyhydrogen flame (OHF) produces only water and highly reactive radicals. • MO eventually degraded to simplest stable molecules such as CO 2 , H 2 O and N 2 by OHF. • OHF is promising for treatment of organic wastewater without any more waste. [ABSTRACT FROM AUTHOR]

Dansyl chloride has been widely used in metal ion recognition as a fluorescent sensing molecule. The interaction between fluorescent probes and metal ions is summarized, and the research progress in the structural design of dansyl group receptors in the field of metal ion fluorescent probes since 2010 is discussed. Its sensing mechanism involves intramolecular induced photoelectron transfer, charge transfer, dimethylamino deprotonation/protonation, formation of monomer-excitation complex, chelate-enhanced fluorescence transfer, complexation reaction, fluorescence resonance energy transfer, and other ones. The rules of the fluorescent responses of dansyl group under various mechanisms are also discussed, such as fluorescence quenching induced by intramolecular charge transfer and chelation triggered fluorescence enhancement. The future application trends of dansyl group in the field of fluorescent probe design are proposed as well. [ABSTRACT FROM AUTHOR]

Single nano high-entropy pyrochlore-type compound (A2B2O7) with 7 different rareearth cations at site A and 3 different metal cations at site B with equiatomic amounts (7A1/7)2(3B1/3)2O7 is successfully obtained. The powder with nominal composition (La1/7Sm1/7Nd1/7Pr1/7Y1/7Gd1/7Yb1/7)2(Sn1/3Hf1/3Zr1/3)2O7 was fabricated by reacting metal nitrates (site A) and metal chlorides (site B) with glycine during the combustion reaction. The XRD analysis revealed that the powder attained during synthesis is in an amorphous state. To induce crystallization of the obtained pyrochlore structure, the post-calcination process at 600-1500 oC was conducted and studied. Results of this study showed that the monophase pyrochlore (A2B2O7) structure is obtained during the calcination at 900 °C. The high-density ceramic pellet with 97% of theoretical density and free of any additives was obtained through pressureless sintering at 1650 °C for 4 h in the air using the powder calcined at 900 °C. [ABSTRACT FROM AUTHOR]

ZnFe2O4 (ZFO) nanospheres with complex structures have been synthesized by a one-step simple solvothermal method using two different types of precursors—metal chlorides and nitrates —and were fully characterized by XRD, SEM, XPS, and EDS. The ZFO nanospheres synthesized from chloride salts (ZFO_C) were loose with a size range of 100–200 nm, while the ZFO nanospheres synthesized from nitrate salts (ZFO_N) were dense with a size range of 300–500 nm but consisted of smaller nanoplates. The different morphologies may be caused by the different hydrolysis rates and different stabilizing effects of chloride and nitrate ions interacting with the facets of forming nanoparticles. Electrochemical tests of nitrate-based ZFO nanospheres as anode materials for lithium-ion batteries demonstrated their higher cyclic stability. The ZFO_C and ZFO_N samples have initial specific discharge/charge capacities of 1354/1020 and 1357/954 mAh∙g−1, respectively, with coulombic efficiencies of 75% and 71%. By the 100th cycle, ZFO_N has a capacity of 276 mAh∙g−1, and for ZFO_C, only 210 mAh∙g−1 remains after 100 cycles. [ABSTRACT FROM AUTHOR]

Magnesium has been regarded as an intriguing anode material for chloride ion batteries (CIB) because of its abundant resources, multi-electron reaction feature, and high volumetric capacity. However, the passivation of magnesium in the electrolyte and formation of insulating MgCl2 discharge product lead to poor reaction activity of magnesium anode in CIBs. Herein, the Mg2Sn alloy prepared by mechanical alloying of magnesium and tin powders is first developed as the anode material with enhanced interfacial activity in the CIB using a metal chloride cathode. The cathode exhibits a significant increase in the discharge capacity from 82 to 175 mAh g−1 when an Mg/carbon anode was replaced by the Mg2Sn alloy anode. The discharge capacity can be further increased to more than 200 mAh g−1 when the graphene nanoplatelet is incorporated in the Mg2Sn alloy by mechanical milling, thus demonstrating the highly active alloy anode for chloride ion storage. This strategy also benefits the improvement in the cycling performance of the magnesium anode. [ABSTRACT FROM AUTHOR]

Corrosion behaviours of Fe–25Cr, Fe–25Cr–2Mn–1Si, Fe–25Cr–20Ni, 310SS, Ni–25Cr, and Ni–25Cr–2Mn–1Si (all in wt%) with and without NaCl–KCl deposits in Ar–60%CO2–20%H2O gas at 750 °C were studied. Without salt deposits, Fe–25Cr performed protectively, while Fe–25Cr–20Ni and Ni–25Cr underwent breakaway oxidation with multilayered scales formed. Adding alloy elements Si + Mn increased the corrosion resistance of all alloys by forming additional Mn-rich oxides and silica. Surface deposits of NaCl–KCl accelerated corrosion, forming porous Fe-rich oxide nodules for Fe–25Cr and thick, porous scales and internal oxidation zones for all other alloys. The protective effect of Si + Mn alloying disappeared in the presence of chlorides. Limited intergranular carbides were observed for all alloys in the gas-only condition. The extent of carburisation increased with the presence of chloride deposits for all Fe-based alloys, but remained unchanged for Ni-based alloys. Corrosion of these alloys at 750 °C is compared with that at 650 °C. The effect of chlorides in volatilising metals at 750 °C is discussed. [ABSTRACT FROM AUTHOR]

The experimental and calculated Raman spectrum of PuCl3 has been reported for the first time. PuCl3 is a primary species found in plutonium metal refinement, specifically in pyrochemical salt processes including multicycle direct oxide reduction, metal chlorination, and electrorefining. As such, Raman signatures of PuCl3 could serve as potential forensic indicators of material process history. A novel technique for synthesizing PuCl3 from the in situ chlorination of plutonium metal with HCl was developed to establish these signatures. Cerium metal surrogates were utilized to ensure optimization of the plutonium experiments and to minimize personnel exposure, and all experiments were carried out in a Raman reaction chamber designed for air‐tight, high vacuum environments. In situ Raman spectroscopy was employed in conjunction with density functional theory (DFT) to investigate the vibrational modes of PuCl3. Associated mixed oxy and hydroxyl phases are also reported. The combined Raman and DFT results have eliminated inconsistencies in Raman mode assignments for the MX3 family of metal chlorides having P63/m symmetry, and IR modes derived from the DFT calculations are additionally presented. The data observed in this study are of potential interest to nuclear forensic analyses, nuclear sample aging, nuclear energy, plutonium processing, and stockpile stewardship. [ABSTRACT FROM AUTHOR]

Metal chloride salt pretreatment was performed to isolate and convert cellulose to glucose from poplar. A glucose yield of 82.0% ± 0.7 was achieved after 0.05 mol/L AlCl3 pretreatment conducted at 180 °C for 20 min, ascribing to the removal of hemicellulose, the alteration of crystallinity, surface morphology, and the retention of the majority of cellulose. Then, the influence of different additives on glucose yield was assessed, generating the highest glucose yield of 88.5 ± 0.06 with the addition of PEG 8000. Meanwhile, a similar glucose yield of 82.8% ± 0.3 could be obtained with PEG 8000 when hydrolysis time was reduced by a quarter and enzyme dosage by three-quarters. It can be seen that AlCl3 pretreatment is a viable and efficient pretreatment method for poplar, while the addition of PEG 8000 can enhance the enzymatic efficiency and reduce cellulase loading, ascribing to the reservation of free enzyme and enzyme activity in the supernatant and the reduction in surface tension, which provide an idea to improve the economics of the enzymatic conversion of poplar. [ABSTRACT FROM AUTHOR]

In recent years, metabolomics has become a valuable new resource in environmental monitoring programs based on the use of bio-indicators such as Mytilus galloprovincialis. The reproductive system is extremely susceptible to the effects of environmental pollutants, and in a previous paper, we showed metabolomic alterations in mussel spermatozoa exposed to metal chlorides of copper, nickel, and cadmium, and the mixture with these metals. In order to obtain a better overview, in the present work, we evaluated the metabolic changes in the male gonad under the same experimental conditions used in the previous work, using a metabolomic approach based on GC-MS analysis. A total of 248 endogenous metabolites were identified in the male gonads of mussels. Statistical analyses of the data, including partial least squares discriminant analysis, enabled the identification of key metabolites through the use of variable importance in projection scores. Furthermore, a metabolite enrichment analysis revealed complex and significant interactions within different metabolic pathways and between different metabolites. Particularly significant were the results on pyruvate metabolism, glycolysis, and gluconeogenesis, and glyoxylate and dicarboxylate metabolism, which highlighted the complex and interconnected nature of these biochemical processes in mussel gonads. Overall, these results add new information to the understanding of how certain pollutants may affect specific physiological functions of mussel gonads. [ABSTRACT FROM AUTHOR]

Parkinson's disease (PD) is a neurodegenerative condition marked by loss of motor coordination and cognitive impairment. According to global estimates, the worldwide prevalence of PD will likely exceed 12 million cases by 2040. PD is primarily associated with genetic factors, while clinically, cases are attributed to idiopathic factors such as environmental or occupational exposure. The heavy metals linked to PD and other neurodegenerative disorders include copper, manganese, and zinc. Chronic exposure to metals induces elevated oxidative stress and disrupts homeostasis, resulting in neuronal death. These metals are suggested to induce idiopathic PD in the literature. This study measures the effects of lethal concentration at 10% cell death (LC10) and lethal concentration at 50% cell death (LC50) concentrations of copper, manganese, and zinc chlorides on SH-SY5Y cells via markers for dopamine, reactive oxygen species (ROS) generation, DNA damage, and mitochondrial dysfunction after a 24 h exposure. These measurements were compared to a known neurotoxin to induce PD, 100 µM 6-hydroxydopamine (6-ODHA). Between the three metal chlorides, zinc was statistically different in all parameters from all other treatments and induced significant dopaminergic loss, DNA damage, and mitochondrial dysfunction. The LC50 of manganese and copper had the most similar response to 6-ODHA in all parameters, while LC10 of manganese and copper responded most like untreated cells. This study suggests that these metal chlorides respond differently from 6-ODHA and each other, suggesting that idiopathic PD utilizes a different mechanism from the classic PD model. [ABSTRACT FROM AUTHOR]

The amorphous aerogel precursor with a BET-specific surface area of 203.58 m2/g was synthesized by sol-gel and CO 2 supercritical drying using metal chlorides as cation source. It was then calcined at 950 °C to obtain a monolithic defective fluorite (Zr 0.25 Ce 0.25 Hf 0.25 Y 0.25)O 2-δ ceramic aerogel with a grain size of 20 nm and an ultra-low thermal conductivity of 0.054 W m−1 K−1 at room temperature. Bulk (Zr 0.25 Ce 0.25 Hf 0.25 Y 0.25)O 2-δ with porosity of 62.24–66.11% and flexural strength of 2.359–4.487 MPa were synthesized by pressing and sintering. The sintered porous (Zr 0.25 Ce 0.25 Hf 0.25 Y 0.25)O 2-δ ceramic has a low thermal diffusivity of 0.152–0.207 mm2/s and a thermal conductivity of 0.138–0.201 W m−1 K−1 with a thermal transfer behavior distinct from that of micro-grain ceramics, which is caused by the severe lattice distortion, porous structure, and nanoscale phonon boundary scattering. [ABSTRACT FROM AUTHOR]

With the aim of constructing hydrogen‐bonding networks in synthetic complexes, two new ligands derived from cis,cis‐1,3,5‐triaminocyclohexane (TACH) have been prepared that feature pendant pyrrole or indole rings as outer‐sphere H‐bond donors. The TACH framework offers a facial arrangement of three N‐donors, thereby mimicking common coordination motifs in the active sites of nonheme Fe and Cu enzymes. X‐ray structural characterization of a series of CuI‐X complexes (X=F, Cl, Br, NCS) revealed that these neutral ligands (H3LR, R=pyrrole or indole) coordinate in the intended facial N3 manner, yielding four‐coordinate complexes with idealized C3 symmetry. The N−H units of the outer‐sphere heterocycles form a hydrogen‐bonding cavity around the axial (pseudo)halide ligand, as verified by crystallographic, spectroscopic, and computational analyses. Treatment of H3Lpyrrole and H3Lindole with divalent transition metal chlorides (MIICl2, M=Fe, Cu, Zn) causes one heterocycle to deprotonate and coordinate to the M(II) center, giving rise to tetradentate ligands with two remaining outer‐sphere H‐bond donors. Further ligand deprotonation is observed upon reaction with Ni(II) and Cu(II) salts with weakly coordinating counteranions. The reported complexes highlight the versatility of TACH‐based ligands with pendant H‐bond donors, as the resulting scaffolds can support multiple protonation states, coordination geometries, and H‐bonding interactions. [ABSTRACT FROM AUTHOR]

Metal phosphates are important catalysts and materials in synthesis chemistry. Herein, we describe the synthesis and characterization of phosphate‐catecholate chelated Nd(III), Zr(IV) and Al(III) chlorides (2–5). These species are achieved via ethyl chloride elimination reaction of oxophosphoranes with corresponding metal chlorides. The product 2–5 represent a new serial of monometallic and bimetallic phosphate‐catecholate chelated metal complexes stabilized by both P−O and catecholate‐O donors. These findings pave the way for future explorations of such species in catalysis. [ABSTRACT FROM AUTHOR]

We found that bis(neopentylglycolato)diboron (B2nep2) served as a bidentate ligand and a one-electron reducing agent for early transition metal chlorides to afford MCl4(B2nep2). Treatment of B2nep2 with MCl5 (M = Nb and Mo) produced MCl4(B2nep2) via two successive reactions, coordination of B2nep2 to the metal center and one-electron reduction from M(V) to M(IV), while coordination of B2nep2 to MCl4 (M = Zr, Ti) was observed without reduction of the central metals. DFT studies for the reduction of NbCl5 by B2nep2 clarified the initial formation of seven-coordinated and B2nep2-ligated Nb(V) species, NbCl5(B2nep2), and one chloride on niobium(V) moves to the Lewis acidic boron center to generate NbCl4[(B2nep2)Cl]. The chloride on the boron atom of NbCl4[(B2nep2)Cl] is trapped by the second B2nep2 to give [NbCl4(B2nep2)][ClB2nep2]. After the formation of [ClB2nep2]– as an anionic sp2–sp3 diboron adduct, one-electron reduction of the niobium(V) center produces NbCl4(B2nep2) along with [ClB2nep2]˙ as a plausible diboron species, whose decomposition affords ClBnep and B2nep2. The reduction of metal halides in the presence of B2nep2 was exemplified by green LED irradiation of TiCl4(B2nep2), producing chloride-bridged titanium(III) species, (B2nep2)TiCl2(μ-Cl)2TiCl2(B2nep2). [ABSTRACT FROM AUTHOR]

A facile strategy that directly reduces alkynyl‐silver precursors and copper salts for the synthesis of bimetallic nanoclusters using the weak reducing agent Ph2SiH2 is demonstrated. Two alkynyl‐protected concentric‐shell nanoclusters, (Ph4P)2[Ag22Cu12(C≡CR)28] and (Ph4P)3[Ag42Cu12Cl(C≡CR)36] (Ag22Cu12 and Ag42Cu12Cl, R=bis(trifluoromethyl)phenyl), were successfully obtained and characterized by single‐crystal X‐ray diffraction and electro‐spray ionization mass spectrometry. For the first time, a hybrid 55‐atom two‐shell Mackay icosahedron was found in Ag42Cu12Cl, which is icosahedral M54Cl instead of M55. The incorporation of a chloride in the metal icosahedron contributes to the stability of the cluster from both electronic and geometric aspects. Alkynyl ligands show various binding‐modes including linear "RC≡C−Cu−C≡CR" staple motifs. [ABSTRACT FROM AUTHOR]

Given the paramount importance of information security and confidentiality, various optical information encryption (OIE) strategies are developed based on luminescence. However, the protected information usually can be decrypted, and there is a lack of high‐level security because only one protection key can be applied. Herein, a double‐key OIE strategy is developed based on multi‐state excitation–emission of Mn‐doped metal chlorides (MMCs). The information delivered by different MMCs can be encrypted based on the similar orange luminescence of Mn d–d transition. The distinguishable excitation conditions, switchable luminescence, and unique afterglow in MMCs enable new encryption mechanisms with a great potential for high confidentiality multi‐key encryption. It is demonstrated that four information channels can be encrypted into a single luminescent pattern, concealing the true information by three interference messages, which greatly increases the security. As a demo, an encrypted quick response (QR) code is created, which can only be decrypted with both the "excitation wavelength key" and "capture time key." The double‐key mechanism enhances the level of security and confidentiality without using expensive equipment or external stimuli. [ABSTRACT FROM AUTHOR]

Experimental analysis and density functional theory (DFT) calculation were performed on methanol gasification catalyzed by transition metal chlorides (CdCl 2 , CuCl 2 , FeCl 3 , and NiCl 2) in supercritical water. The reaction temperatures (550–625 °C), residence times (6–60 s), and catalyst concentrations (0.00025–0.001 mol L−1) were experimentally investigated using a continuous reactor. Non-catalytic gasification of methanol produced the H 2 yield of 0.64 mol mol−1 and gasification efficiency (GE) of 28.42 wt%, while the addition of 0.0005 mol L−1 transition metal chlorides contributed to significantly improved H 2 yield and GE of 1.17–1.16 mol mol−1 and 61.13–106.16 wt% at 575 °C, respectively. The water molecules decrease the overall energy barrier of methanol decomposition pathways to promote methanol hydrogenation by forming intermolecular hydrogen bonds. Different transition metal cations form coordinate bond force with the O atom of the hydroxy group, causing a 20.5–41.1% reduction in the energy barrier of methanol oxidation and promoting methanol decomposition. • Effects of four transition metal chlorides on gas yield and composition were studied. • The gasification efficiency increased 37% after adding 0.0005 mol L−1 CdCl 2. • The reaction pathways of methanol decomposition were investigated. • Water molecule can act as a catalyst to facilitate the decomposition of methanol. • Fe3+, Cu2+, Cd2+ and Ni2+ decreases energy barrier of methanol oxidation. [ABSTRACT FROM AUTHOR]

A N-aryloxide-amidine ligand (H3L), integrating phenoxide (PhO−) and amidine ligands through methylene linkers, has been synthesized from 2-(aminomethyl)-6-(tert-butyl)phenol in two steps. Upon reacting the deprotonated H3L ligand with group 4 metal chloride MIVCl4, a corresponding (LMIV–Cl)2 dimer could be obtained. The coordination modes exhibit variation depending on the radius of the metal ions. In the case of (LTiIV–Cl)2, the two ArO− arms from the same ligand bond to two different Ti(IV) centers, while in the case of (LZrIV/HfIV–Cl)2, both ArO− arms coordinate with the same metal center. Moreover, the two C–N bonds in the amidinate moiety are localized in (LTiIV–Cl)2, whereas they delocalize in (LZrIV–Cl)2. Notably, (LHfIV–Cl)2 could further react with one equivalent of HfCl4, yielding the binuclear metal azide in the presence of KN3 and LiCl, where the coordination mode of the amidinate moiety changed from the bidentate chelating type to the bimetallic bridging coordination. [ABSTRACT FROM AUTHOR]