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.

Electrochemical performances of LiFePO_4/C composites prepared by molten salt method

LiFePO4/C composites were synthesized by a molten salt (MS) method using the mixture of LiCl,LiOH and NaCl.The prepared LiFePO4/C composites are characterized by X-ray diffractometry (XRD),field emission scanning electron microscopy (FESEM) and charge-discharge test.XRD patterns indicate that LiFePO4 prepared in the temperature range of 550-700 ℃ crystallizes well in an olivine-type structure.Through FESEM images,the sphere-like and homogeneous particles of 0.2 μm can be observed.The charge-discharge test shows that the materials prepared at 600 ℃ for 12 h have good electrochemical performance.At the rates of 0.2C (34 mA/g) and 0.5C,the discharge capacities are 144.6 and 122.3 mA·h/g,respectively,together with good cycle performances.

Preparation of CeO_(2) abrasives by reducing atmosphere-assisted molten salt method for enhancing their chemical mechanical polishing performance on SiO_(2)substrates

Ce^(3+)as the active site on the CeO_(2)abrasive surface is the key to enhancing the material removal rate(MRR).The CeO_(2)abrasives with high chemical activity were prepared by the molten salt method under a reducing atmosphere.The crystal structure and morphology of CeO_(2)abrasive s were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Fourier transform infrared spectroscopy(FT-IR),ultraviolet—visible diffuse reflectance spectroscopy(UV-Vis DRS),and X-ray photoelectron spectroscopy(XPS).The CeO_(2)abrasives were obtained under different atmospheres(Air,Ar,and Ar/H_(2)).With the enhancement of the reducing atmosphere,the morphology of the abrasives transforms from spherical to octahedral,while more oxygen vacancies and Ce^(3+)are generated on the surface of CeO_(2)abrasives.The CMP experiments show that the MRRs of the CeO_(2)-Air,CeO_(2)-Ar,and CeO_(2)-Ar/H_(2)abrasives on SiO_(2)substrates are 337.60,578.74,and 691.28 nm/min,respectively.Moreover,as confirmed by atomic force microscopy(AFM),the substrate surfaces exhibit low roughness(20.5 nm)after being polished using all of the prepared samples.Especially,the MRR of CeO_(2)-Ar/H_(2)abrasives is increased by 104.76%compared with CeO_(2)-air abrasives.The improved CMP performance is attributed to the increased Ce^(3+)concentration and the octahedral morphology of the abrasives enhancing the chemical reaction and mechanical removal at the abrasive-substrate interface.

One-pot molten salt method for constructing CdS/C_(3)N_(4) nanojunctions with highly enhanced photocatalytic performance for hydrogen evolution reaction

The construction of heterojunction photocatalysts for efficiently utilizing solar energy has attracted considerable attention to solve the energy crisis and reduce environmental pollution.In this study,we use the energy released from an easily-occurred exothermic chemical reaction to serve as the drive force to trigger the formation of Cd S and C_(3)N_(4) nanocomposites which are successfully fabricated with cadmium nitrate and thiourea without addition of any solvents and protection of inert gas at initial temperature,a little higher than the melting point of thiourea.The as-prepared Cd S/C_(3)N_(4) materials exhibit high efficiency for photocatalytic hydrogen evolution reaction(HER)with the HER rate as high as 15,866μmol/(g·hr)under visible light irradiation(λ>420 nm),which is 89 and 9 times those of pristine C_(3)N_(4) and Cd S,respectively.Also,the apparent quantum efficiency(AQE)of Cd S/C_(3)N_(4)–1:2–200–2(Cd S/C_(3)N_(4)–1:2–200–2 means the ratio of Cd to S is 1:2 and the reaction temperature is set at 200℃ for two hours)reaches 3.25%atλ=420±15 nm.After irradiated for more than 24 hr,the HER efficiencies of Cd S/C_(3)N_(4) do not exhibit any attenuation.The DFT calculation suggests that the charge difference causes an internal electric field from C_(3)N_(4) pointing to Cd S,which can more effectively promote the transfer of photogenerated electrons from Cd S to C_(3)N_(4).Therefore,most HER should occur on C_(3)N_(4) surface where photogenerated electrons accumulate,which largely protects Cd S from photo-corrosion.

Two tetravalent uranium silicate and germanate crystals with three membered single-ring by molten salt method:K_(2)USi_(3)O_(9)and Cs_(2)UGe_(3)O_(9)

Two tetravalent uranium silicate and germanate M_(2)U^(Ⅳ)T_(3)O_(9)(M=K,Cs;T=Si,Ge)crystals were crystalized under inert gas by molten salt flux growth method.K_(2)USi_(3)O_(9)(1)crystallizes in the monoclinic space group P1_(21)/n1 with lattice parameters a=7.1076?,b=10.4776?,c=12.2957?,γ=120°and V=915.67?^(3).Cs_(2)UGe_(3)O_(9)(2)crystallizes in a hexagonal space group P-6 with lattice constants of a=7.5138?,b=7.5138?,c=11.0114?,γ=120°and V=538.38?^(3).Bond valence calculations indicate tetravalent uranium in both structures,which contain three-membered single-ring T_(3)O_(9)^(6-) trimers.K_(2)USi_(3)O_(9) is the first uranium silicate that contains the Si_(3)O_(9)^(6-) trimers.

Structural and Piezoelectric Properties of Sr_(0.6)Ba_(0.4)Nb_2O_6 Micro-rods Synthesized by Molten-Salt Method

Sr0.6 Ba0.4 Nb2 O6 micro-rods are prepared by the molten-salt method with K2 SO4,KCl-K2 SO4,and KCl as fluxes.It reveals that the Sr0.6 Ba0.4 Nb2 O6 synthesized with KCl as a flux exhibits a single phase with tetragonal tungsten bronze structure.The measurement of X-ray diffraction indicates that the Sr0.6 Ba0.4 Nb2 O6 micro-rods synthesized at 1 300℃are anisotropic.The morphology of the powers is examined by transmission electron microscope.It reveals that the length-diameter ratio of Sr0.6 Ba0.4 Nb2 O6 micro-rods increases with increasing annealing temperature from 900℃to 1 300℃.At 1 300℃,the rod possesses a large length-diameter ratio of 8∶1.Moreover,the analysis of the piezoelectric properties of single micro-rods using apiezo-response force microscope indicates that the domains of the material are arranged along its radial direction.

Effects of indium doping concentration on the morphology and electrical properties of one-dimensional SnO_2 nanostructures prepared by a molten salt method

In this paper,indium doped SnO2 nanorods and nanowires have been prepared by the molten salt method,and the effects of indium doping concentration on the morphology and electrical properties of one-dimensional(1D) SnO2 nanostructures have been studied.It is found that indium doping concentration can affect the epitaxial growth,morphology and the electrical conductance of 1D SnO2 nanostructures.It is also found that the element made by using 6 mol% indium doped SnO2 nanorods responds to nitrogen gas.

MgFeSiO_4 prepared via a molten salt method as a new cathode material for rechargeable magnesium batteries

Well-crystallized MgFeSiO4 microparticles were synthesized at different temperatures by a simple molten salt method using KCl flux. As a new cathode for rechargeable magnesium batteries,the material shows a reversible Mg2+ intercalation-deintercalation process. In 0.25 mol/L Mg(AlCl2EtBu) 2/THF electrolyte,MgFeSiO4 synthesized at 900°C can deliver a 125.1 mAh/g initial dis-charge capacity and a 91.4% capacity retention on the 20th cycle at a rate of 0.1C(about 15.6 mA/g) . The results show that MgFeSiO4 could be a good host for Mg2+ intercalation,and a potential cathode material for high-energy rechargeable magnesium batteries.

COMPUTERIZED SIMULATION OF MOLTEN SALT SOLUTION OF Li,KF,Cl SYSTEM BY MOLECULAR DYNAMIC METHOD

The structure and properties of molten salt solution o J Li,K|F,Cl system have been investiged by computerized simulation of molecular dynamic method.The partial RDF,the partial molar energy of mixing and the diffusion coeffients of Li^+,K^+,F^- and Cl^- have been calculated. The results are in agreement with the experimental values.The regularities of the distribution of ions and mieroscopic holes are discussed based on the results of computerized simulation.

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.

Preparation of titanium dioxide from titania-rich slag by molten NaOH method

Preparing titanium dioxide from titania-rich slag （TiO2 73wt%） by molten NaOH method has been developed. The effects of temperature and reaction time on the titanium conversion were investigated. The results showed that temperature had significant influence on the titanium conversion as well as the structure of the product. About 92% of titanium in the titania-rich slag could be converted after reacting with NaOH at 500℃ for 1 h. Metatitanic acid was formed through the steps of washing treatment, acid dissolution, and hydrolysis. Well-dispersed spherical titanium dioxide particles with an average size of 0.1-0.4μm can be obtained by calcination of metatitanic acid. In addition, the content of titanium dioxide in the product is up to 98.6wt%, which can be used as pigments after further treatment of coating and crushing.

The protective performance of a molten salt frozen wall in the process of fluoride volatility of uranium

The fluoride volatility method (FVM) is a technique tailored to separate uranium from fuel salt of molten salt reactors. A key challenge in R&D of the FVM is corrosion due to the presence of molten salt and corrosive gases at high temperature. In this work, a frozen-wall technique was proposed to produce a physical barrier between construction materials and corrosive reactants. The protective performance of the frozen wall against molten salt was assessed using FLiNaK molten salt with introduced fluorine gas, which was regarded as a simulation of the FVM process. SS304, SS316L, Inconel 600 and graphite were chosen as the test samples. The extent of corrosion was characterized by an analysis of weight loss and scanning electron microscope studies. All four test samples suffered severe corrosion in the molten salt phase with the corrosion resistance as: Inconel 600>SS316L>graphite>SS304. The presence of the frozen wall could protect materials against corrosion by molten salt and corrosive gases, and compared with materials exposed to molten salt, the corrosion rates of materials protected by the frozen wall were decreased by at least one order of magnitude.

COMPUTERIZED SIMULATION OF THERMODYNAMICS FOR MOLTEN LiF-KF SOLUTION BY MONTE CARLO METHOD

The structure and behaviour of LiF-KF solution,as a typical common-anion system,has been simulated by Monte Carlo method.The calculation of partial radial distribution function of ions,heat of mixing and potential energy distribution shows that the average distance be- tween Li^+ and F^- ions will significantly narrow after mixing of molten LiF and KF.This is very similar to the lean-on-one-side effect in molten LiF-KCl solution.The calculated heat of mixing is in fair agreement with the measured one.The dominant source of the energy of mixing may be that the decrease of the repulsion energy between cations,the decrease of the attraction energy between cations and anions,and the decrease of the repulsion energy be- tween anions.

COMPUTER SIMULATION OF STRUCTURE OF MOLTEN DyF_3－BaF_2－LiF SYSTEM BY MONTE CARLO METHOD

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熔盐辅助合成硼化铪工艺研究

这是一篇冶金工程领域的论文。以氧化铪和碳化硼为原料,采用氯化钠为熔盐介质,通过硼/碳热还原法合成了纯度较高的硼化铪粉体。研究了反应温度、保温时间等合成工艺参数以及原料配比对材料晶相组成和显微结构的影响。结果表明,以氯化钠为熔盐介质时,氧化铪在1300℃的合成温度下开始转化为硼化铪,其温度远低于传统的硼化铪合成所需温度。在硼过量20%,反应温度和保温时间分别为1400℃和2 h所制备的硼化铪粉体纯度较高,X射线衍射中可以明显观察到硼化铪结晶峰,且在扫描电镜中可以观察到紧密团聚形貌的硼化铪。

The potassium storage performance of carbon nanosheets derived from heavy oils

As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the relationship between heavy oil composition and potassium storage performance remains unclear.Using heavy oils containing distinct chemical groups as the carbon source,namely fluid catalytic cracking slurry(FCCS),petroleum asphalt(PA)and deoiled asphalt(DOA),three carbon nanosheets(CNS)were prepared through a molten salt method,and used as the anodes for PIBs.The composition of the heavy oil determines the lamellar thicknesses,sp3-C/sp2-C ratio and defect concentration,thereby affecting the potassium storage performance.The high content of aromatic hydrocarbons and moderate amount of heavy component moieties in FCCS produce carbon nanosheets(CNS-FCCS)that have a smaller layer thickness,larger interlayer spacing(0.372 nm),and increased number of folds than in CNS derived from the other three precursors.These features give it faster charge/ion transfer,more potassium storage sites and better reaction kinetics.CNS-FCCS has a remarkable K^(+)storage capacity(248.7 mAh g^(-1) after 100 cycles at 0.1 A g^(-1)),long cycle lifespan(190.8 mAh g^(-1) after 800 cycles at 1.0 A g^(-1))and excellent rate capability,ranking it among the best materials for this application.This work sheds light on the influence of heavy oil composition on carbon structure and electrochemical performance,and provides guidance for the design and development of advanced heavy oil-derived carbon electrodes for PIBs.

NdF_(3)在LiF熔盐中的溶解及离子结构

LiF-NdF_(3)熔盐体系中离子的构成形式对解析电解钕工艺的电解过程至关重要,本文采用冰点降低法分析LiF-NdF_(3)熔盐体系的离子结构。通过Temkin和Flood模型及热力学计算分析熔盐体系内可能存在的离子团簇,结果表明,NdF_(3)在LiF中的溶解模型符合TemkinⅠ、TemkinⅡ、TemkinⅥ、TemkinⅦ和FloodⅡ、FloodⅥ、FloodⅦ,在LiF-NdF_(3)熔盐体系中主要形成含有1~2个Nd^(3+)的分子团簇,NdF_(3)在LiF内溶解主要形成游离的Nd^(3+)、F-、Li^(+)以及Li^(+)·[NdF_(4)]^(-)、Li^(+)·[Nd2F7]-、2Li^(+)·[Nd_(2)F_(8)]^(2-)分子团簇。

(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵陶瓷的低温制备及吸波性能

寻求具有良好耐高温及力学性能的新型陶瓷材料是吸波材料领域的研究热点之一。高熵碳化物陶瓷具有高温热稳定性及抗氧化性好等优点,但合成温度高且吸波性能研究较少,限制了其在高温吸波材料领域的应用。本工作采用熔盐法合成了多晶岩盐晶型(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵碳化物陶瓷,研究了其物相组成、微观形貌及吸波特性。结果表明:随着反应温度的升高,样品的衍射峰逐渐锐化,吸波性能明显提高。当反应温度为1500℃时,3.72 GHz时最低反射损耗达-34.68 dB;与已报道的高熵碳化物陶瓷相比,在相同的有效吸收带宽(2.3 GHz)下,涂层厚度减少了13.3%(1.5 mm降低到1.3 mm),其介电损耗主要来源于极化损耗和导电损耗。本工作制备的高熵碳化物陶瓷可以为研究制备新型环境适应、耐高温、抗冲击的高性能单相吸波材料提供新途径。

铝-空气电池废电解液制备片状氧化铝的研究

以铝-空气电池废电解液为原材料,用硫酸铝调节pH值,用硫酸钾作为熔盐制备片状氧化铝(α-Al_(2)O_(3)),研究了合成温度、晶种添加量对α-Al_(2)O_(3)粉体体积分数、粒度大小及粒度分布的影响规律。通过X射线衍射仪、扫描电子显微镜和激光粒度仪等,对加入不同晶种量的α-Al_(2)O_(3)粉体的结构和形貌进行表征。结果表明,添加晶种后可以提高α-Al_(2)O_(3)粉体的体积分数,减小α-Al_(2)O_(3)粉体的粒度,使α-Al_(2)O_(3)粉体的粒度分布更集中,同时使α-Al_(2)O_(3)粉体更分散。此外,当晶种添加量为5%(质量分数)时,制备出的片状α-Al_(2)O_(3)的体积分数可达97.0%,平均粒度约为7.24μm。

Ba_(3)(VO_(4))_(2):Sm^(3+)荧光粉的熔盐法合成及其温度传感特性

采用熔盐法成功合成了Ba_(3-x)(VO_(4))_(2):xSm^(3+)(x=0.02~0.16)一系列荧光粉,探讨了合成条件、Sm^(3+)掺杂对样品结构和发光性能的影响,并探究了样品的温度传感性能。结果表明:合成样品的适宜反应条件是煅烧温度为900℃、煅烧时间为1 h、原料与熔盐质量比为1∶3,所得样品相纯度和结晶度均较高。样品微观形貌呈片状,厚度约1.5~3 mm。在318 nm激发下,Ba_(3-x)(VO_(4))_(2):xSm^(3+)的发射光谱中可同时观察到VO_(4)^(3-)基团的宽带发射和Sm^(3+)的特征发射,样品的发光颜色集中在黄白光区域。随着Sm^(3+)掺杂浓度(x)从0.02增大到0.16,Sm^(3+)的特征发射峰强度呈现出先升后降的变化趋势,当x=0.10时,发射峰强度达到最高值。导致其浓度猝灭的主要原因是电偶极-电偶极(d-d)相互作用。在298~473 K的温度范围内,Ba_(2.9)(VO_(4))_(2):0.10Sm^(3+)荧光粉中Sm^(3+)(652 nm)和VO_(4)^(3-)基团(504 nm)发射的荧光强度比呈现明显的温度依赖性,其最大绝对灵敏度为0.36 K^(-1),最大相对灵敏度为1.99%K^(-1)。因此,Sm^(3+)掺杂Ba_(3)(VO_(4))_(2)的荧光粉具有优异的温度传感性能,在非接触式光学测温中具有潜在的应用价值。