Separation of Neighboring REElementsfrom Sm_2O_3Eu_2O_3Gd_2O_3 System by a Stepwise ChlorinationChemical Vapor Transport Reaction

The mutual separation characteristics were investigated for the neighboring Sm, Eu and Gd from their ternary oxide mixture Sm 2O 3 Eu 2O 3 Gd 2O 3 by a stepwise chlorination chemical vapor transport reaction within 6 h using AlCl 3 as complex former. The rare earth chlorides were more readily transported and concentrated in the middle temperature range of 980～1100 K and the transport efficiency was in the order of Sm≈Gd>Eu. The separation factor, expressed as molar ratio for the resulting chlorides, was 1 70 for Eu∶Sm, 1 88 for Eu∶Gd, 1 24 for Sm∶Gd in the higher temperature region, and 2 76 for Sm∶Eu, 2 83 for Gd∶Eu and 1 12 for Gd∶Sm in the lower temperature region, respectively. All results are much higher than those of the conventional wet process.

Stepwise Chlorination-Chemical Vapor Transport Reactions for Bastnaesite Concentrate

Vapor phase extraction and mutual separation of rare earth (RE) elements from bastnaesite concentrate were investigated using stepwise chlorination chemical vapor transport reactions mediated by vapor complexes LnAl n Cl 3 n +3 (Ln=RE elements). The bastnaesite was heated to 800 K and chlorinated between 800～1300 K with C+Cl 2+SiCl 4 to remove CO 2, SiF 4 and high volatile chlorides. At the temperature of 1300 K for 6 h, the resulted RE chlorides were chemically transported and mutual separated with the vapor complexes while CaCl 2 and BaCl 2 were remained in the residues. Significantly different CVT characteristics were observed for gradually decreased and wave form temperature gradients.

Preparation of Anhydrous LnCl_3(Ln=Eu, Er, Lu) by Chemical Vapor Transport

Anhydrous lanthanide chlorides LnCl 3(Ln=Eu, Er, Lu) which are not easy to prepare in other ways were prepared by chemical vapor transport(CVT) method. Ln 2O 3 reacted with an excess of Al 2Cl 6 at 300 ℃ to produce LnCl 3. LnCl 3 reacted with Al 2Cl 6 at high temperature to form the gaseous complexes which decomposed at low temperature. LnCl 3 was then separated from other solids by controlling a proper temperature gradient. Residual Al 2Cl 6(g) was removed by the carrier of dry Cl 2 N 2 gases at 200 ℃. The yield rates are >90%, and the purity of products is >99 5%. The high purity of anhydrous lanthanide chlorides can be obtained by CVT method.

Highly crystalline ReSe2 atomic layers synthesized by chemical vapor transport

Two-dimensional (2D) anisotropic rhenium diselenide (ReSe2) has attracted lots ofattention due to its promising applications in electronics and optoelectronics. However,controlled synthesis of high quality ultrathin ReSe2 remains as a challenge.Here we developed an approach for synthesizing high quality 2D ReSe2 flakes witha thickness down to monolayer by chemical vapor transport (CVT) through carefullytuning the growth kinetics. The atomic structures and anisotropy of theobtained ReSe2 flakes were intensively characterized with scanning transmissionelectron microscope and angle-resolved polarized Raman spectroscopy. Fieldeffecttransistors fabricated on the CVT-grown ReSe2 flakes showed n-typesemiconducting behavior with an on/off current ratio of 105 and a mobility up to
5 cm2 V−1 s−1, which is comparable to mechanically exfoliated flakes and isobvious higher than the samples synthesized with other approaches. This study notonly make high quality 2D ReSe2 easily accessible for both fundamental and applicationexplorations but also sheds new lights on the chemical synthesis of otheranisotropic 2D materials.

Carbon agent chemical vapor transport growth of Ga2O3 crystal

Beta-type gallium oxide（β-Ga2O3） is a new attractive material for optoelectronic devices. Different methods had been tried to grow high quality β-Ga2O3 crystals. In this work, crystal growth of Ga2O3 has been carried out by chemical vapor transport（CVT） method in a closed quartz tube using C as transport agent and sapphire wafer as seed. The CVT mass flux has been analyzed by theoretical calculations based on equilibrium thermodynamics and 1D diffusional mass transport. The crystal growth experimental results are in agreement with the theoretical predictions. Influence factors of Ga2O3 crystal growth, such as temperature distribution, amount of C as transport agent used, have also been discussed. Structural（XRD） and optical（Raman spectroscopy, photoluminescence spectrum） properties of the CVT-Ga2O3 crystal are presented.

Preparation of Anhydrous Lutetiu m Chlorideby Chemical Vapor Transport

Anhydrous lutetium chloride, which is not easy to prepare in other ways, was prepared by chemical vapor transport (CVT) method. Lu2O3 reacted with Al2Cl6 at 300 degrees C to produce LuCl3, which was then separated from other solids by means of CVT at a temperature gradient from 400 degrees C to 180 degrees C. Residual Al2Cl6 was removed by dry Cl-2-N-2 gas at 200 degrees C. The purity of the product was > 99.9%.

Relationship between disorder,magnetism and band topology in Mn(Sb_(1-x)Bi_(x))_(2)Te_(4) single crystals

We investigate the evolution of magnetic properties as well as the content and distribution of Mn for Mn(Sb_(1-x)Bi_(x))_(2)Te_(4) single crystals grown by large-temperature-gradient chemical vapor transport method.It is found that the ferromagnetic MnSb_(2)Te_(4) changes to antiferromagnetism with Bi doping when x≥0.25.Further analysis implies that the occupations of Mn ions at Sb/Bi site Mn_(Sb/Bi) and Mn site Mn_(Mn) have a strong influence on the magnetic ground states of these systems.With the decrease of Mn_(Mn) increase of Mn_(Sb/Bi),the system will favor the ferromagnetic ground state.In addition,the rapid decrease of T_(C/N) with increasing Bi content when x ≤0.25 and the insensitivity of T_(N) to x when x> 0.25 suggest that the main magnetic interaction may change from the Ruderman-Kittel-Kasuya-Yosida type at low Bi doping region to the van-Vleck type in high Bi doped samples.

A Safe and Brief Way for Preparing Anhydrous LnCl_3 (Ln=Sc, Y, La to Lu)

Anhydrous lanthanide chlorides LnCl 3 (Ln=Sc, Y, La to Lu except for Pm), which are difficult to prepare in other ways, were prepared by chemical vapor transport (CVT) process. Rare earth oxide reacted with Al 2Cl 6 at 300℃ to produce LnCl 3, which was then separated from other solids by means of CVT at a temperature gradient from 400 to 180℃. Residual Al 2Cl 6 (g) was removed by carrier of dry N 2 gas at 200℃. The yielding rates were >90%, and the purity of products was >99.5%.

Morphology-controlled Tantalum Diselenide Structures as Self-optimizing Hydrogen Evolution Catalysts

Metallic layered transition metal dichalcogenides(TMDs)nanomaterials based on Group 5 transition metals are attracting substantial interests as alternative catalysts for hydrogen evolution reaction(HER).However,controllable preparation of tantalum diselenide(TaSe2)remains challenging,which has hindered the exploration on its application in HER.Herein,we develop a facile method named surface-assisted chemical vapor transport(SACVT)for controllable synthesis of TaSe2 plates and nanobelts,by regulating the molar ratio of selenium to tantalum and reaction temperature.Unique quasi-arrays and self-supported structure help TaSe2 nanobelt own more active sites and higher ability of charge transfer,so it is superior to TaSe2 plate in electrocatalytic HER.Interestingly,they both exhibit the ability to optimize their morphologies upon cycling for dramatically improved and robust electrocatalytic performance.The selfoptimized structures can increase the effective active surface by exposing more active sites on the basal-planes and edges,shorten the interlayer electron-transfer pathways at a thinned domain,and accelerate the charge transfer,which mainly derive from high basal-plane activity and weak interaction between layers of metallic TaSe2.This work provides a reliable way for controllable synthesis of different TaSe2 structures,motivating further efforts to explore new high-efficiency catalysts in the large family of metallic TMDs for electrochemical energy conversion.

Growth, characterization, and Raman spectra of the 1T phases of TiTe_(2), TiSe_(2), and TiS_(2)

High-quality large 1T phase of TiX_(2)(X = Te, Se, and S) single crystals have been grown by chemical vapor transport using iodine as a transport agent. The samples are characterized by compositional and structural analyses, and their properties are investigated by Raman spectroscopy. Several phonon modes have been observed, including the widely reported A_(1g) and E_(8) modes, the rarely reported E_(u) mode(-83 cm^(-1) for TiTe_(2), and -185 cm^(-1)for TiS_(2)), and even the unexpected K mode(-85 cm^(-1)) of TiTe_(2). Most phonons harden with the decrease of temperature, except that the K mode of TiTe_(2) and the E_(u) and “A_(2u)/Sh” modes of TiS_(2) soften with the decrease of temperature. In addition, we also found phonon changes in TiSe_(2) that may be related to charge density wave phase transition. Our results on TiX_(2) phonons will help to understand their charge density wave and superconductivity.

Facile and fast growth of high mobility nanoribbons of ZrTe5

Recently, ZrTe5 has received a lot of attention as it exhibits various topological phases, such as weak and strong topological insulators, a Dirac semimetal, a three-dimensional quantum Hall state, and a quantum spin Hall insulator in the monolayer limit. While most of studies have been focused on the three-dimensional bulk material, it is highly desired to obtain nanostructured materials due to their advantages in device applications. We report the synthesis and characterizations of ZrTe5 nanoribbons. Via a silicon-assisted chemical vapor transport method, long nanoribbons with thickness as thin as 20 nm can be grown. The growth rate is over an order of magnitude faster than the previous method for the bulk crystals.Moreover, transport studies show that the nanoribbons are of low unintentional doping and high carrier mobility, over30000 cm2/V·s, which enable reliable determination of the Berry phase of π in the ac plane from quantum oscillations. Our method holds great potential in growth of high quality ultra-thin nanostructures of ZrTe5.

Heterogeneous Growth of ZnO Crystal on GaN/Al_(2)O_(3) Substrate

Hydrothermal(HT)ZnO substrates were usually used as seeds for the vapor growth of ZnO crystals.In this work,ZnO bulk crystals were grown using the relatively low-cost GaN/AlOsubstrates as seeds by chemical vapor transport(CVT).With the increase of growth time,the dislocation densities in the crystal decreased from about 1×10^(6) to 6×10^(3) cm^(-2).The carrier concentration decreased from 1.24×10^(19) to 1.57×10^(17)cm^(-3),while the carrier mobility increased from 63.8 to 179 cm^(2)/(V·s).The optical transmittance in the VIS-NIR wavelength increased significantly in combination with the decreasing dislocation densities and impurity concentrations.The dislocation lines and related fast diffusion paths gradually decreased and disappeared in the late growth stage,and the crystal qualities were consequently improved.The experimental results show that the properties of as-grown ZnO crystals are comparable with bulk ZnO grown on the HT substrates to some extent.The GaN/Al_(2)O_(3) seeds may have a potential application value in the industrial production of ZnO single crystals.

A highly efficient Fe-doped Ni_(3)S_(2) electrocatalyst for overall water splitting

The development of efficient and stable electrocatalysts with earth-abundant elements for both oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)in the same electrolyte is incontrovertibly vital in water electrolysis.However,their large-scale fabrication remains a great challenge.Here,we report a self-supported electrocatalyst in the form of Fe-doped Ni_(3)S_(2) nanoparticles in-situ grown on three-dimensional(3D)conductive Fe−Ni alloy foam(Fe−Ni_(3)S_(2)/AF)by surface-assisted chemical vapor transport(SACVT)method.Homogeneous growth environment and scalability of SACVT method allow Fe−Ni3S2 nanoparticles uniformly growing on AF in large-scale.Fe−Ni_(3)S_(2)/AF exhibits high activity and durability when act as HER catalyst and OER precatalyst in alkaline media.The HER and OER overpotential at 10 mA/cm^(2) is considerably small,only 75 and 267 mV,respectively.Moreover,the electrolyzer assembled by Fe−Ni_(3)S_(2)/AF for overall water splitting exhibits a low cell voltage and high durability in long-term test.Based on experiments and theoretical calculation,the significantly enhanced activity could be originated from the incorporation of Fe,which contributed to increase the electrochemical active surface area,enhance electrical conductivity,optimize the hydrogen and H2O adsorption energy of Ni_(3)S_(2)(101)surface in HER,and form active bimetallic Ni−Fe(oxy)hydroxide in OER.The excellent durability of self-supported Fe−Ni_(3)S_(2)/AF could be benefited from the in-situ growth of Fe−Ni_(3)S_(2) nanoparticles on 3D AF,which could ensure closely mechanical adhesion between active materials and substrate,promote charge transport and increase surface area.This work provides a facile method for large-scale synthesis of electrocatalysts with high activity and long-term durability for efficient water electrolysis in alkaline media.

Ambipolar two-dimensional bismuth nanostructures in junction with bismuth oxychloride

Despite the unique properties of bismuth(Bi),there is a lack of two-dimensional(2D)heterostructures between Bi and other functional 2D materials.Here,a coherent strategy is reported to simultaneously synthesize rhombohedral phase Bi nanoflakes and bismuth oxychloride(BiOCI)nanosheets.The delicate balance between several reactions is mediated mainly for the reduction and chlorination in the chemical vapor transport(CVT)process.The Bi-BiOCI lateral heterostructures have been constructed via the coalescence of the two different 2D nanostructures.The characteristics of ambipolar conducting Bi and insulator-like BiOCI are elaborated by scanning microwave impedance microscopy(sMIM).This work demonstrates a way to construct a 2D Bi nanostructure in junction with its oxyhalide.