CeO_2 as the Oxygen Carrier for Partial Oxidation of Methane to Synthesis Gas in Molten Salts: Thermodynamic Analysis and Experimental Investigation

A new technique -- the direct partial oxidation of methane to synthesis gas using lattice oxygen in molten salts medium has been introduced. Using CeO2 as the oxygen carrier, thermodynamic data were calculated in the reaction process, and the results indicated that direct partial oxidation of methane to synthesis gas using lattice oxygen of cerium oxide is feasible in theory. In a stainless steel reactor, the effects of temperature and varying amounts of γ-Al2O3 supported CeO2 on cn4 conversion, H2 and CO selectivity, were investigated, respectively. The results show that 10% CeO2/γ-Al2O3 has the maximal reaction activity at a temperature of 865 ℃ and above, the H2/CO ratio in the gas that has been produced reaches 2 and the CH4 conversion, H2 and CO selectivity reached the following percentages： i.e. 61%, 89%, and 91% at 870 ℃, respectively. In addition, increase of reaction temperature is favorable for the partial oxidation of methane.

Electrochemical synthesis of ammonia in molten salts

Ammonia is important feedstock for both fertilizer production and carbon-free liquid fuel.Many techniques for ammonia formation have been developed,hoping to replace the industrial energy-intensive Haber-Bosch route.Electrochemical synthesis of ammonia in molten salts is one promising alternative method due to the strong solubility of N3- ions,a wide potential window of molten salt electrolytes and tunable electrode reactions.Generally,electrochemical synthesis of ammonia in molten salts begins with the electro-cleavage of N2/hydrogen sources on electrode surfaces,followed by diffusion of N3^-/H^+-containing ions towards each other for NH3 formation.Therefore,the hydrogen sources and molten salt composition will greatly affect the reactions on electrodes and ions diffusion in electrolytes,being critical factors determining the faradaic efficiency and formation rate for ammonia synthesis.This report summarizes the selection criteria for hydrogen sources,the reaction characteristics in various molten salt systems,and the preliminary explorations on the scaling-up synthesis of ammonia in molten salt.The formation rate and faradaic efficiency for ammonia synthesis are discussed in detail based on different hydrogen sources,various molten salt systems,changed electrolysis conditions as well as diverse catalysts.Electrochemical synthesis of ammonia might be further enhanced by optimizing the molten salt composition,using electrocatalysts with well-defined composition and microstructure,and innovation of novel reaction mechanism.

Molten salt synthesis of porous carbon and its application in supercapacitors: A review

Carbon materials have taken an important role in supercapacitor applications due to their outstanding features of large surface area,low price,and stable physicochemical properties.Considerable research efforts have been devoted to the development of novel synthesis strategy for the preparation of porous carbon materials in recent years.In particular,molten salt strategy represents an emerging and promising method,whereby it has shown great potential in achieving tailored production of porous carbon.It has been proved that the molten salt-assisted production of carbon via the direct carbonization of carbonaceous precursors is an effective approach.Furthermore,with the incorporation of electrochemical technology,molten salt synthesis of porous carbon has become flexible and diversiform.Here,this review focuses on the mainstream molten salt synthesis strategies for the production of porous carbon materials,which includes direct molten salt carbonization process,capture and electrochemical conversion of CO_(2)to value-added carbon,electrochemical exfoliation of graphite to graphene-based materials,and electrochemical etching of carbides to new-type carbide-derived carbon materials.The reaction mechanisms and recent advances for these strategies are reviewed and discussed systematically.The morphological and structural properties and capacitive performances of the obtained carbon materials are summarized to reveal their appealing points for supercapacitor applications.Moreover,the opportunities and challenges of the molten salt synthesis strategy for the preparation of carbon materials are also discussed in this review to provide inspiration to the future researches.

Molten salt synthesis and supercapacitor properties of oxygen-vacancy LaMnO3-δ

Due to the unique structure of perovskite materials,their capacitance can be improved by introducing oxygen vacancy.In this paper,the LaMnO3-δ material containing oxygen vacancy was synthesized by molten salt method in KNO3-NaNO3-NaNO2 melt.The La-Mn-O crystal grows gradually in molten salt with the increase of temperature.It was confirmed that LaMnO3-δ with perovskite structure and incomplete oxygen content were synthesized by molten salt method and presented a three-dimensional shape.LaMnO3-δ stores energy by redox reaction and adsorption of OH-in electrolyte simultaneously.In comparison with the stoichiometric LaMnO3 prepared by the sol-gel method,LaMnO3-δ prepared by molten salt method proffered higher capacitance and better performance.The galvanostatic charge-discharge curve showed specific capacitance of 973.5 F/g under current density of 1 A/g in 6 M KOH.The capacitance of LaMn03-δ was 82.7%under condition of 5 A/g compared with the capacitance at the current of 1A/g,and the specific capacitances of 648.0 and 310.0 F/g were obtained after 2000 and 5000 cycles of galvanostatic charging-discharging,respectively.Molten salt synthesis method is relatively simple and suitable for industrial scale,presenting a promising prospect in the synthesis of perovskite oxide materials.

Molten salt synthesis of α-MnO_(2)/Mn_(2)O_(3) nanocomposite as a high-performance cathode material for aqueous zinc-ion batteries

Thanks to low cost,high safety,and large energy density,aqueous zinc-ion batteries have attracted tremendous interest worldwide.However,it remains a challenge to develop high-performance cathode materials with an appropriate method that is easy to realize massive production.Herein,we use a molten salt method to synthesize nanostructured manganese oxides.The crystalline phases of the manganese oxides can be tuned by changing the amount of reduced graphene oxide added to the reactant mixture.It is found that the α-MnO_(2)/Mn_(2)O_(3) nanocomposite with the largest mass ratio of Mn_(2)O_(3) delivers the best electrochemical performances among all the products.And its rate capability and cyclability can be significantly improved by modifying the Zn anode with carbon black coating and nanocellulose binder.In this situation,the nanocomposite can deliver high discharging capacities of 322.1 and 213.6 mAh g^(-1) at 0.2 and 3 Ag^(-1),respectively.After 1000 cycles,it can retain 86.2% of the capacity at the 2 nd cycle.Thus,this nanocomposite holds great promise for practical applications.

Molten Salt Synthesis of Ba(Mg_(1/3)Nb_(2/3))O_3 Powder

The single-phase Ba(Mg_(1/3)Nb_(2/3))O_3(BMN) powder was successfully prepared by the KCl molten salt synthesis(MSS) method.The temperature for single-phase BMN powders by MSS was about 400℃ lower than that by the solid-phase method.The average particle size(APS) was about 0.91μm at 900℃ and increased with increasing synthesis temperature.Based on the APS,the activation energy for particle growth in the MSS,whose value was 64.1kJmol^(-1),was attained.The sinterability of the powder prepared by MSS method was better than that prepared by solid-phase method.

Molten Salt-Shielded Synthesis(MS^(3))of MXenes in Air

MXenes are two-dimensional transition metal carbides and/or nitrides with unique physiochemical properties and have attracted extensive interest in numerous fields.However,current MXene synthesis methods are limited by hazardous synthesis conditions,high production costs,or difficulty in largescale production.Therefore,a general,safe,cost-effective,and scalable synthesis method for MXenes is crucial.Here,we report the fast synthesis of MXenes in the open air using a molten salt-shielded synthesis(MS^(3))method,which uses Lewis-acid salts as etchants and a low-melting-point eutectic salt mixture as the reaction medium and shield to prevent MXene oxidation at high temperatures.Carbide and nitride MXenes,including Ti_(3)C_(2)T_(x),Ti_(2)CT_(x),Ti_(3)CNT_(x),and Ti_(4)N_(3)T_(x),were successfully synthesized using the MS^(3) method.We also present the flexibility of the MS^(3) method by scaling the etching process to large batches of 20 and 60 g of Ti_(3)AlC_(2) MAX precursor in one pot.When used as negative electrodes,the prepared MS^(3)-MXenes delivered excellent electrochemical properties for high-rate Li-ion storage.

Advances in Molten Salt Synthesis of Non-oxide Materials

The properties of non-oxide materials are continuously revealed,and their applications in the fields of ceramics,energy,and catalysis are increasingly extensive.Regardless of the traditional binary materials or the MAX phases,the preparation methods,which are environmentally friendly,efficient,economical,and easy to scale-up,have always been the focus of attention.Molten salt synthesis has demonstrated unparalleled advantages in achieving non-oxide materials.In addition,with the development of the process in molten salt synthesis,it also shows great potential in scale-up production.In this review,the recent progress of molten salt synthesis in the preparation of binary non-oxide and MAX phase is reviewed,as well as some novel processes.The reaction mechanisms and the influence of synthetic conditions for certain materials are discussed in detail.The paper is finalized with the discussion of the application prospect and future research trends of molten salt synthesis in non-oxide materials.

Electrochemical Synthesis of Chromium Silicides from Molten Salts

Electrochemical synthesis of chromium silicides from NaCl-KCl-K2SiF6-CrF3 system has been investigated by cyclic voltammetry and DC （direct current） electrolysis at 850℃. The process of Cr and Si joint electroreduction in chloride-fluoride melt proceeds in one stage in a kinetic mode. The cathode product was analyzed using XRD （X-ray diffraction） method. XRD data have confirmed that CraSi is the dominant phase. SEM （scanning electron microscopy） results have shown that Cr3Si powder samples consist of 50-150 lain particles and that tungsten silicide was formed at the surface of tungsten cathode after chrome-free system electrolysis.

Molten salt-assisted synthesis of bulk CoOOH as a water oxidation catalyst

Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing temperature,and its size can reach dozens of microns.X-ray absorption near edge structure and XPS studies demonstrate that the Co valence state of CoOOH-750 is trivalent,and X-ray Absorption Fine Structure shows that it had a higher symmetry and lower disorder degree,indicating that CoOOH-750 has higher crystallinity and Co3+.The results of electrochemical tests show that CoOOH-750 exhibited the best oxygen-evolution-reaction(OER)catalytic activity.

Structures and magnetic anisotropy of β-Mn_2V_2O_7 crystals synthesized by the molten salt method

β-Mn2V2O7 crystals with strip shape are successfully prepared by the molten salt method in a closed crucible, and are characterized by x-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, selected area of electron diffraction （SAED） and high-resolution transmission electron microscopy （HRTEM）. The results indicate that the sample is of the β-Mn2V2O7 crystal with monoclinic symmetry, level natural cleavage facets and directional growth. Magnetic properties are measured by vibration sample magnetometry （VSM） at room temperature, and the magnetic hysteresis loop indicates that the β-Mn2V2O7 has anti-ferromagnetic properties with low coercive force and remnant magnetization. The magnetic measurement results in different directions exhibit that the β-Mn2V2O7 has magnetic anisotropy, which is due to the fact that the magnetic interaction energy of the β-Mn2V2O7 is lowest only when the electron configuration is in a certain direction.

Preparation and Magnetic Property of La_(0.7)Sr_(0.3)MnO_3 Nanorod by Combination Sol-Gel with Molten Salt

La0.7Sr0.3MnO3（LSMO） nanorods were synthesized by a method combining sol-gel with molten salts at 950 ℃ for 10 h, which employed KCl＋NaCl（mass ratio 4：1） as eutectic molten salts. The morphologies and magnetic properties of the resulting LSMO nanorods were investigated by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, and vibrating sample magnetometer（VSM） measurements. It was found that the obtained perovskite manganite LSMO was a uniform nanorod with a diameter of about 50 nm and a length of longer than 500 rim. The Curie temperature（To） of the LSMO nanorod used here was 262 K, much lower than that of bulky single crystal LSMO（360 K）. The low Curie temperature might be a result of the great disorder near the grain boundary, which could be observed clearly from the TEM picture.

Synthesis and Microstructure of Partly-oriented Bismuth Layer Structure Ferroelectrics Ceramics SrBi_4Ti_4O_(15)

SrBi4Ti4O15 powder was synthesized by conventional solid state synthesis （ CS ） and molten salt synthesis （ MSS ） . MSS method can synthesize plate-like SrBi4Ti4O15 at lower temperature （900℃） than CS method. Plate-like form becomes more distinct when the synthesis temperature increases. This would help cause the grain orientation of the ceramics after sintering. The sintered samples of MSS had grain orientation at （0,0, 10） plane. The degree of （0,0,10） grain orientation F was 62.1% . Hot pressing made （0,0,10） grain orientation more distinct （ F = 85.7% ）. The microstructures of the sintered samples were detected by SEM. Due to the grain orientation the density of samples fabricated by MSS was lower than that of prepared by CS.

In-situ Synthesis of Cr_(3)C_(2) Nanosheets by Carbon Reduction Route from Cr_(2)AlC

Carbon black and Cr_(2)AlC were used as raw materials to obtain a large number of Cr_(3)C_(2)nanosheets by means of the molten salt heat treatment at 1100℃for 1.5 hours.Results showed that carbon black can promote the decomposition of a large number of Cr_(2)AlC to form Cr_(3)C_(2)and Cr_(7)C_(3)nanoparticles at 1100℃in the absence of molten salt.Under a molten salt environment,carbon black can promote the complete decomposition of Cr_(2)AlC to form Cr_(3)C_(2)and Cr_(7)C_(3)nanosheets.The thickness of chromium carbide nanosheets is approximately 10-20 nm,and the length is approximately 100-200 nm.The addition of excess carbon black can promote the complete decomposition of Cr_(2)AlC into a material with Cr_(3)C_(2)as the main phase.

Synthesis of LiSm_(0.01)Mn_(1.99)O_4 by molten salt technique

Samarium substituted lithium manganese oxide powders were successfully prepared by molten-salt synthesis(MSS) using eutectic mixture of LiCl,SmCl3.6H2O and MnO2 salt at 700 °C.The synthesis was carried out in open atmosphere.The crystalline powders were characterized for their phase identification using X-ray diffraction(XRD) analysis.The physico-chemical properties of the samarium substituted lithium manganese oxide powders were investigated by thermal analysis(TGA/DTA),FT-IR spectroscopy,EDAX,electron par...

Molten salt synthesis, formation mechanism, and oxidation behavior of nanocrystalline HfB2 powders

Nanocrystalline Hf B2 powders were successfully synthesized by molten salt synthesis technique at 1373 K using B and Hf O2 as precursors within KCl/Na Cl molten salts.The results showed that the as-synthesized powders exhibited an irregular polyhedral morphology with the average particle size of 155 nm and possessed a single-crystalline structure.From a fundamental aspect,we demonstrated the molten-salt assisted formation mechanism that the molten salts could accelerate the diffusion rate of the reactants and improve the chemical reaction rate of the reactants in the system to induce the synthesis of the high-purity nanocrystalline powders.Thermogravimetric analysis showed that the oxidation of the as-synthesized Hf B2 powders at 773–1073 K in air was the weight gain process and the corresponding oxidation behavior followed parabolic kinetics governed by the diffusion of oxygen in the oxide layer.

Recent progress in molten salt synthesis of low-dimensional perovskite oxide nanostructures, structural characterization,properties, and functional applications: A review

Molten salt synthesis （MSS） method has advantages of the simplicity in the process equipment, versatile and large-scale synthesis, and friendly environment, which provides an excellent approach to synthesize high pure oxide powders with controllable compositions and morphologies. Among these oxides, perovskite oxides with a composition of ABO3 exhibit a broad spectrum of physical properties and functions （e.g. ferroelectric, piezoelectric, magnetic, photovoltaic and photocatalytic properties）. The downscaling of the spatial geometry of perovskite oxides into nanometers result in novel properties that are different from the bulk and film counterparts. Recent interest in nanoscience and nanotechnology has led to great efforts focusing on the synthesis of low-dimensional perovskite oxide nanostructures （PONs） to better understand their novel physical properties at nanoscale. Therefore, the low-dimensional PONs such as perovskite nanoparticles, nanowires, nanorods, nanotubes, nanofibers, nanobelts, and two dimensional oxide nanostructures, play an important role in developing the next generation of oxide electronics. In the past few years, much effort has been made on the synthesis of PONs by MSS method and their structural characterizations. The functional applications of PONs are also explored in the fields of storage memory, energy harvesting, and solar energy conversion. This review summarizes the recent progress in the synthesis of low-dimensional PONs by MSS method and its modified ways. Their structural char- acterization and physical properties are also scrutinized. The potential applications of low-dimensional PONs in different fields such as data memory and storage, energy harvesting, solar energy conversion, are highlighted. Perspectives concerning the future research trends and challenges of low-dimensional PONs are also outlined. ~ 2017 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science ＆ Technology.

Molten salt synthesis of neodynium oxyfluoride in various fluoride media with different fluoride ion activities

Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)and O_(2)^(-)anions.In this work,neodynium oxyfluoride was synthesized by the reaction between neodymium oxide and four fluoride media with different fluoride ion activities.The synthesis processes in molten LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),NaF-CaF_(2)-NdF_(3)and NaF-KF-NdF_(3)are observed in situ by a confocal scanning laser microscope.The expansion of neodymium oxide particle is observed in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts,and the growth of needle crystals on neodymium oxide particle is clearly observed in molten NaF-CaF_(2)-NdF_(3).Based on scanning electron microscopy(SEM)-energy dispersive X-ray spectroscopy(EDS)and X-ray diffraction(XRD)analyses of products,neodynium oxyfluoride was successfully synthesized in the four fluoride media.The neodynium oxyfluoride generated in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts is a tetragonal structure.However,in molten NaF-CaF_(2)-NdF_(3),neodynium oxyfluoride with a rhombohedral structure is formed.It is suggested that the substitution of Na(Ⅰ)and Ca(Ⅱ)for Nd(Ⅲ)can transform NdOF from tetragonal structure to rhombohedral structure.The growth rate of needle crystals generated in molten NaF-CaF_(2)-NdF_(3)was calculated based on the result of a confocal scanning laser microscope,and it is found that the reaction kinetics of crystal formation is zero-order reaction.The effect of fluoride media on the structure and morphology of formed NdOF were evaluated by XRD,X-ray photoelectron spectroscopy(XPS)and SEM.The neodymium oxyfluoride prepared in the fluoride media with high fluoride ion activity has low binding energy of F 1 s.The ratio of adsorbed oxygen to lattice oxygen for neodymium oxyfluoride prepared in molten LiF-NdF_(3)is larger than those in the other three fluoride media,so it can have better catalytic performance.

Facile synthesis of hollow Ti_(3)AlC_(2)microrods in molten salts via Kirkendall effect

The microstructure and morphology of Ti_(3)AlC_(2)powders not only affect the preparation of Ti_(3)C_(2) MXene but also have a great influence on their potential applications,such as microwave absorbers,alloy additives,or catalytic supports.However,the synthesis of Ti_(3)AlC_(2)powders with desired microstructure and morphology remains a challenge.Herein,hollow Ti_(3)AlC_(2)microrods were prepared for the first time in NaCl/KCl molten salts by using titanium,aluminum,and short carbon fibers as starting materials.It was found that the short carbon fibers not only performed as carbon source but also acted as sacrificial template.Furthermore,it was revealed that TiC and Ti2AlC were initially formed on the surface of carbon fibers.The subsequent reactions between the outer Ti,Al and the inner carbon were dominated by the Kirkendall effect which gave rise to the formation of a hollow structure.Based on this mechanism,hollow Ti_(3)AlC_(2)microspheres and a series of hollow TiC,Ti_(2)AlC,and V_(2)AlC powders were also successfully fabricated.This work provides a facile route to synthesize hollow MAX phases and may give enlightenment on preparing other hollow carbide powders via the Kirkendall effect in the molten salts.

Molten salt synthesis of Z-scheme CeO_(2)/C_(3)N_(4) photocatalysts with excellent properties for removal of organic pollutants:Characterization,kinetics and mechanisms

In this work,we firstly synthesized a CeO_(2)/C_(3)N_(4) photocatalyst with Z-scheme heterojunction by a facile LiC-KCI molten salt method.The synthesized catalyst has an excellent quality for removing organic pollution of dyes and antibiotics in wastewater.As an example,the CeCN-1:5 prepared with a mass ratio of Ce_(2)(CO_(3))_(3)·xH_(2)O:C_(3)H_(3)N_(6)=1:5 exhibits a methylene blue(MB)removal capacity of 100%within 90 min and tetracycline(TC)removal capacity of 94.6%.After 4 cycles,the CeCN-1:5 keeps a removal efficiency of nearly 100%in 150 min for MB and 85.7%for TC.The kinetics study reveals that the MB removal process with the CeCN-1:5 fits the modified Elovich model with strong adsorption while TC removal fits the first-order model.The large surface area(238 m^(2)/g)and negative zeta potential(-39.3 mV)of CeCN-1:5 contribute to superior adsorption capacity to MB.However,the adsorption of TC is restricted due to the positive surface/pore potential in acidic solution.CeCN-1:5has combined Z-scheme heterojunction and exhibits a low recombination rate of electrons(e^(-))/holes(h^(+))and the photo-generated active radicals of·OH/·O_(2)^(-)that promotes the photocatalytic performance.This novel CeO_(2)/C_(3)N_(4) photocatalyst with an excellent photocatalysis removal activity has an enormous potential for photocatalytic applications.