Electrical conductivity of NaF-AlF_3-CaF_2-Al_2O_3-ZrO_2 molten salts

The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt system decreases with increase of ZrO2 content in an interval of 0-5%. The increase of 1%ZrO2 results in a corresponding electrical conductivity decrease of 0.02 S/cm, and the equivalent conductivity increases with the increase of molar ratio of NaF to AlF3. When the temperature increases by 1 °C, the electrical conductivity increases by 0.004 S/cm. At last, the regression equations of electrical conductivity relative to temperature and ZrO2 are obtained by quadratic regression analysis.

Etching Mechanism of Ti_(3)C_(2)Cl_(2) MXene Phases by CuCl_(2)-Lewis Molten Salt Method

We described a method for obtaining fluorine-free Ti_(3)C_(2)Cl_(2)MXene phases by melting copper in CuCl_(2)instead of aluminum in Ti_(3)AlC_(2).XRD results show that when molten salt CuCl_(2)etches Ti_(3)AlC_(2),it forms an intermediate product Ti_(3)CuC_(2),and then reacts with Ti_(3)CuC_(2)to obtain Ti_(3)C_(2)Cl_(2).The reaction of Ti_(3)AlC_(2)and CuCl_(2)at a temperature of 800℃for 2 h to obtain Ti_(3)C_(2)Cl_(2)with an optimal lamellar structure is shown in SEM results.The pseudopotential plane-wave(PP-PW)method is used to calculate on the electronic structure.The etching mechanism is investigated by the total energies of each substance.The chemical reaction of Ti_(3)AlC_(2)and CuCl_(2)will first become Ti_(3)CuC_(2)and Cu,and then become Ti_(3)C_(2)Cl_(2)during the Lewis acid etching process,which are consistent with the experimental results.

Preparation of low-oxygen titanium powder by magnesiothermic reduction of TiO2 assisted by MgCl_(2)−HoCl_(3) molten salt

To reduce the production cost of titanium,a new method for direct preparation of low-oxygen titanium powder by the magnesiothermic reduction of TiO_(2) with the assistance of a MgCl_(2)−HoCl_(3) molten salt was proposed.Thermodynamic calculations showed that the magnesiothermic reduction of TiO_(2) was feasible.However,hindrance of the reduction reaction by the reduction by-product of MgO resulted in a considerably high O concentration in the titanium powder.The addition of HoCl_(3) to the system significantly reduces the activity of MgO to produce low-oxygen titanium powder.Thermochemical deoxidation and reduction experiments were conducted with MgCl_(2)−HoCl_(3) molten salt in the temperature range of 1023−1273 K.The results showed that titanium powder with oxygen concentration(mass fraction)below 5.00×10^(-4) can be prepared at the Mg−MgCl_(2)−HoOCl−HoCl_(3) equilibrium.

Molten salt construction of core-shell structured S-scheme CuInS_(2)@CoS_(2) heterojunction to boost charge transfer for efficient photocatalytic CO_(2) reduction

Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.

CaCl_2-CaF_2-CaO-SiO_2熔盐体系基础性质研究

分析了加入不同质量分数的CaO-SiO_2对CaCl_2-CaF_2空白熔盐的电导率、密度以及初晶温度的影响。结果表明,每添加2%的CaO-SiO_2,熔盐体系的初晶温度平均升高17.5℃、密度相应增加0.015 1g/cm^3、电导率增大0.224 13S/cm,侧面论证了CaO-SiO_2在基础体系中以硅酸盐分子形式存在。

CaCl_2-CaF_2熔盐的CaO溶解度及吸水性能研究

采用不同真空脱水工艺制备了CaCl_2-CaF_2熔盐,对CaO在熔盐中的溶解度和熔盐吸水性能进行了研究。结果表明,随着熔盐脱水温度的升高、脱水时间的增加,熔盐中H_2O、CaO的含量逐渐降低,且表现出相同的变化趋势;熔盐中CaO的溶解度随着熔盐温度、溶解时间的增加逐渐增加,CaO在不同脱水工艺制备的熔盐中的溶解度有所差异,随着熔盐中H_2O含量的增加,CaO的溶解度逐渐降低;不同脱水工艺制备的熔盐表现出不同的吸水性能,熔盐中H_2O含量越低,吸水性能越强。

MOLECULAR DYNAMICS STUDY OF STRUCTURE IN MOLTEN SALT SOLUTION NaF-CaF_2

The NaF-CaF_2 system has been studied by molecular dynamics simulation.The pair correlation functions between cations and anions and the bond angle distributions of cation and anion triplets have been obtained.The bridging and complexing in the system are discussed based on the pair correlation functions and bond angle distributions.The results simulated show that the F^- ions around a Ca^(2+)ion do not form tetrahedron coordination,so some of small complexing clusters such as CaF_4^(2-)are hardly found.A possible structure of F^- ions around Ca^(2+)ions is that three Ca^(2+)ions constitute an equilateral triangle through three Ca-F-Ca bridges and two F^- ions are located over and under the center of the right triangle,respectively.Meanwhile,on the outside of the triangle,every Ca^(2+)ion has other two F^- ions as its neighbors.

Low temperature molten salt synthesis of porous La_(1-x)Sr_xMn_(0.8)Fe_(0.2)O_3(0≤x≤0.6) microspheres with high catalytic activity for CO oxidation

A molten salt method was developed to prepare porous La1‐xSrxMn0.8Fe0.2O3 （0≤ x ≤ 0.6） micro‐spheres using hierarchical porous δ‐MnO2 microspheres as a template in eutectic NaNO3‐KNO3. X‐ray diffraction patterns showed that single phase LaMn0.8Fe0.2O3 with good crystallinity was syn‐thesized at 450℃ after 4 h. Transmission electron microscope images exhibited that the LaMn0.8Fe0.2O3 sample obtained at 450？？ after 4 h possessed a porous spherical morphology com‐posed of aggregated nanocrystallites. Field emission scanning electron microscope images indicated that the growth of the porous LaMn0.8Fe0.2O3 microspheres has two stages. SEM pictures showed that a higher calcination temperature than 450？？ had an adverse effect on the formation of a po‐rous spherical structure. The LaMn0.8Fe0.2O3 sample obtained at 450？？ after 4 h displayed a high BET surface area of 55.73 m2/g with a pore size of 9.38 nm. Fourier transform infrared spectra suggested that Sr2＋ions entered the A sites and induced a decrease of the binding energy between Mn and O. The CO conversion with the La1‐xSrxMn0.8Fe0.2O3 （0≤x≤0.6） samples indicated that the La0.4Sr0.6Mn0.8Fe0.2O3 sample had the best catalytic activity and stability. Further analysis by X‐ray photoelectron spectroscopy demonstrated that Sr2＋doping altered the content of Mn4＋ions, oxygen vacancies and adsorbed oxygen species on the surface, which affected the catalytic performance for CO oxidation.

Direct electrolytic preparation of chromium metal in CaCl_2-NaCl eutectic salt

The electro-reduction of chromium oxide（Cr2O3） was investigated in an equimolar mixture of CaCl2-NaCl molten salt at 800℃ for developing a more efficient process for chromium preparation. Cyclic voltammetry and potentiostatic electrolysis were used to study the electro-reduction of the Cr2O3-loaded metallic cavity electrode. In addition, a number of parameters affecting the rate and extent of Cr2O3 electrolysis were considered to better understand the electrolysis process. The results demonstrate that CaCl2-NaCl molten salt is applicable for preparing Cr directly from Cr2O3 and the electrolysis parameters exert great influence on the cathode product. Under optimal experimental conditions, nodular Cr with an oxygen content of 0.5%（mass fraction） was obtained without any chromium carbides detected by XRD. Furthermore, the relatively high solubility of CaO and quite rapid crystal growth result in the formation of large platelet CaCr2O4, and the addition of NaCl to CaCl2 results in several variations on the electrolysis process and the product morphology from pure CaCl2 molten salt.

CaCl_2-CaF_2熔盐的脱水工艺及性能研究

采用真空脱水工艺对CaCl_2-CaF_2熔盐进行处理,研究了脱水温度、脱水时间对CaCl_2-CaF_2熔盐中H_2O、CaO含量的影响,研究了不同粒度对吸水性能的影响以及金属铈溶解度和温度、时间的关系。结果表明,脱水温度500℃、脱水时间5 h时,熔盐中的H_2O、CaO含量最低;温度800℃、保温时间2 h制备的熔盐中的H_2O<0.05%、CaO<0.02%;金属铈在熔盐中的溶解度随着熔盐温度、溶解时间的增加逐渐增加;不同粒度的熔盐表现出不同的吸水性能,熔盐粒度越小,吸水性能越强。

Capture and electro-splitting of CO_2 in molten salts

Due to the serious greenhouse gas effects caused by the increasing concentration of atmospheric CO_2,carbon capture and storage(CCS) has been an important area of research and many technologies are developed within this field. Molten salt CO_2 capture and electrochemical transformation(MSCC-ET) process is a desirable method due to a high CO_2 solubility, a wide potential window of molten salts and easily-controlled electrode reactions. Generally, electro-splitting CO_2 in molten salts begins with CO_2 absorption reactions to form CO_3^(2-), which is then followed by the carbon deposition at the cathode and O_2 evolution at the anode. As a result, CO_2 is electro-converted to O_2 and carbon with different morphologies, compositions, microstructures and functional properties. This report introduces the MSCC-ET process, summarizes the reactions occurring in the molten salts and at the electrode surfaces, as well as the morphological variations of the cathodic products. The inert anode materials, cost estimation and scale-up evaluation of the process are then discussed. It is presumed that with a comprehensive understanding of the electrode reactions during electrolysis and the functional properties of carbon materials obtained during CO_2 electro-splitting can provide a foundation for further developing this environmentally friendly process.

Molten salts-modified MgO-based adsorbents for intermediate-temperature CO_2 capture: A review

Carbon dioxide（CO2） capture using magnesium oxide（MgO）-based adsorbents at intermediate temperatures has been regarded as a very prospective technology for their relatively high adsorption capacity,low cost, and wide availability. During the past few years, great effort has been devoted to the fabrication of molten salts-modified MgO-based adsorbents. The extraordinary progress achieved by coating with molten salts greatly promotes the COcapture capacity of MgO-based adsorbents. Therefore, we feel it necessary to deliver a timely review on this type of COcapturing materials, which will benefit the researchers working in both academic and industrial areas. In this work, we classified the molten saltsmodified MgO adsorbents into four categories:（1） homogenous molten salt-modified MgO adsorbents,（2） molten salt-modified double salts-based MgO adsorbents,（3） mixed molten salts-modified MgO adsorbents, and（4） molten salts-modified MgO-based mixed oxides adsorbents. This contribution critically reviews the recent developments in the synthetic method, adsorption capacity, reaction kinetics, promotion mechanism, operational conditions and regenerability of the molten salts-modified MgO COadsorbents. The challenges and prospects in this promising field of molten salts-modified MgO COadsorbents in real applications are also briefly mentioned.

Interfacial confinement of Ni-V2O3 in molten salts for enhanced electrocatalytic hydrogen evolution

Implementation of non-precious electrocatalysts is key-enabling for water electrolysis to relieve challenges in energy and environmental sustainability. Self-supporting Ni-V2O3 electrodes consisting of nanostrip-like V2O3 perpendicularly anchored on Ni meshes are herein constructed via the electrochemical reduction of soluble NaVO3 in molten salts for enhanced electrocatalytic hydrogen evolution. Such a special configuration in morphology and composition creates a well confined interface between Ni and V2O3. Experimental and Density-Functional-Theory results confirm that the synergy between Ni and V2O3 accelerates the dissociation of H2O for forming hydrogen intermediates and enhances the combination of H*for generating H2.

Sustainable recycling of titanium from TiO_(2) in spent SCR denitration catalyst via molten salt electrolysis

Spent catalyst used for denitration by selective catalytic reduction(spent SCR denitration catalysts) is one of the important urban mines due to the high content of TiO_(2)(~85 wt%) and the massive accumulation amount(over 100,000 tons),therefore,value-added reutilization of titanium in spent SCR catalysts is considerably meaningful.In this paper,a novel method is proposed for converting the titanium oxide in spent SCR denitration catalysts to metallic titanium.Specifically,titanium dioxide(TiO_(2)) was firstly obtained from spent SCR denitration catalysts after removing the impurities by hydrometallurgy process.Then,TiO_(2) is converted to Ti_(2)CO by carbothermic reduction method,and Ti_(2)CO was further purified by oleic acid capture.Finally,by utilizing the as-prepared Ti_(2)CO as the consumable anode in the NaCl-KCl molten salt,high-purity metallic titanium was deposited at cathode,all confirming the feasibility for the conversion of low-grade TiO_(2) in the spent catalysts,from 60 wt% to high-purity metallic Ti(99.5 wt%), furthermore,the energy consumption of this process is 3950 kWh tonne-1 Ti,which is lower than that of most traditional titanium metallurgy methods.The method herein can provide new insights for the value-added recycling of titanium resources in urban mines.

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.

U(VI) adsorption behavior onto polypyrrole coated 3R-MoS2 nanosheets prepared with the molten salt electrolysis method

To improve the separation capacity of uranium in aqueous solutions, 3R-MoS2 nanosheets were prepared with molten salt electro- lysis and further modified with polypyrrole (PPy) to synthesize a hybrid nanoadsorbent (PPy/3R-MoS2). The preparation conditions of PPy/3R- MoS2 were investigated and the obtained nanosheets were characterized with scanning electron microscope (SEM), high resolution transmis- sion electron microscope (HRTEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectro- scopy (XPS). The results showed that PPy/3R-MoS2 exhibited enhanced adsorption capacity toward U(VI) compared to pure 3R-MoS2 and PPy;the maximum adsorption was 200.4 mg/g. The adsorption mechanism was elucidated with XPS and FTIR: (1) negatively charged PPy/3R-MoS2 nanosheets attracted by an electrostatic interaction;(2) exposed C, N, Mo, and S atoms complexed with U(VI) through co- ordination;(3) Mo in the complex partly reduced the adsorbed U(VI) to U(IV), which further regenerated the adsorption point and continu- ously adsorbed U(VI). The design of the PPy/3R-MoS2 composite with a high adsorption capacity and chemical stability provides a new direc- tion for the removal of radionuclide.

Preparation and Characterization of Bi_4Ti_3O_(12) Platelets by a Novel Low-temperature Molten Salt System

Bismuth titanate （Bi4Ti3O12） platelets were prepared by molten salt method in a new salt system of CaCl2·NaCl at 650-750℃, using bismuth nitrate pentahydrate （Bi （NO3）3·H2O） and titanium butoxide （Ti （OC4H9）4） as raw materials. The synthesis temperature of Bi4Ti3O12 platelets was decreased to 650℃ from 900-1100℃. The phase compositions and crystalline morphology of Bi4Ti3O12 platelets were investigated by XRD and SEM. The experimental results indicate that Bi4Ti3O12 platelets containing tetragonal and orthorhombic phase with the size of 1-3μm can be synthesized at 650℃ for 2 h, and the orthorhombic phase becomes the dominant phase at 750℃ for 5 h. The size and proportion of Bi4Ti3O12 platelets increase with the increment of the calcining temperature and holding time. The proportion of platelets increases to about ninety percent, and the platelets grow up to about 3-10μm at 750℃ for 5 h from 1-2μm at 650℃ for 2 h. This technical route provides a new low-temperature molten salt system for preparing platelets by molten salt methods.

TiB2 coating formed on nickel substrates by electroplating in molten salt of fluoride

The TiB2 coatings deposited over nickel substrate by electroplating was investigated, which is in molten salt of a fluoride mixture involving KF, NaF, K2 TiF6 and KBF4. Effects of temperature, cathodic current density (Jc) and duration on the coating's formation were examined. The composition, morphology and structure of the coatings were characterized by scanning electron microscopy (SEM), energy dispersive X-ray detector (EDS) and X-ray diffraction (XRD). The results show that the coatings, with black, smooth and uniform appearance, are composed of predominating TiB2 and small amounts of nickel titanium oxide (Ni0.75 Ti0.125 O). The coatings show a nodular morphology and the grain size is dependent on the Jc and ranges about 1 - 10 μm. There is a linear relationship between the coating's thickness and the time of electrolysis within certain duration range. The reduction of the potassium can take place simultaneously with the electrochemical synthesis of TiB2 as the Jc is in excess of certain level. The hardness of the TiB2 coatings is likely to be deteriorated due to the presence of potassium and Ni0.75Ti0.125 O in the coatings.

p-Type CaFe_2O_4 semiconductor nanorods controllably synthesized by molten salt method

Pure phase, regular shape and well crystallized nanorods of p-type semiconductor CaFeOhave been fabricated for the first time by a facile molten salt assisted method, as confirmed by XRD, TEM, SEM and HRTEM. UV-vis diffuse reflectance spectra and Mott–Schottky plots show that the band structure of the CaFeOnanorods is narrower than that of the CaFeOnanoparticles synthesized by conventional method. The enhancement of the visible-light absorption is due to narrowness of the band gap in CaFeOnanorods. The appropriate ratio between the molten salt and the CaFeOprecursors plays an important role in inhibiting the growth of the crystals along the(201) plane to give the desired nanorod morphology. This work not only demonstrates that highly pure p-type CaFeOsemiconductor with tunable band structure and morphology could be obtained using the molten salt strategy, but also affirms that the bandgap of a semiconductor may be tunable by monitoring the growth of a particular crystal plane.Furthermore, the facile eutectic molten salt method developed in this work may be further extended to fabricate some other semiconductor nanomaterials with a diversity of morphologies.

Influence of Molten Salt on Luminescent Intensity and Particle Size of Y_2O_3:Eu^(3+) Phosphor

The Y-Eu oxalate precursor was prepared with a homogeneous precipitation method. And the additives, Na2CO3, S, NaCl or their combination, were introduced into the precursor to prepare Y2O3 ：Eu^3＋ red phosphors at 1000 1300 ℃ for 2 h. The effect of molten salts on particle size and luminescent intensity was studied. The experimental results showed that the complex molten salt （Na：CO3 ＋ S ＋ NaCl） was conductive to enhance the luminescent intensity of Y2O3 ：Eu^3＋. The emission intensity of the phosphor prepared with these additives at 1300 ℃ was about 45% higher than that of the one prepared without molten salt, and about 11% higher than that of the corresponding commercial phosphor. Meanwhile, the particle size of Y2O3 ：Eu^3＋ phosphor was controlled effectively with the molten salt.