The knowledge on the ionic structure of YCl_(3)-KCl molten system is of guiding significance for the practical production of yttrium metals and yttrium alloys via molten salt electrolysis using this system as electrol...The knowledge on the ionic structure of YCl_(3)-KCl molten system is of guiding significance for the practical production of yttrium metals and yttrium alloys via molten salt electrolysis using this system as electrolyte.In this paper,the theoretical Raman spectra of the ionic groups which may exist in YCl_(3)-KCl molten system are simulated by quantum chemical calculation using Gaussian09 and Gauss View 5.0 programs based on density functional theory(DFT).Then the ionic structures of 20 mol%-60 mol%YCl_(3)-KCl molten salt systems are studied by comparing the Raman shift values of the bands in the theoretical Raman spectra of different ionic groups with the experimental spectra of this system.YCl_(6)^(3-),Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)are thought to exist in the molten system.With the increase of temperature,the relative content of YCl_(6)^(3-)ionic groups increases while those of Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)ionic groups decrease.Moreover,the"lifetime"of all ionic groups decreases within the temperature range of 692-730℃.Meanwhile,the relative contents of Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)increase with the increase of YCl_(3)content,while that of YCl_(6)^(3-)decreases.The wave function analysis of the four ionic groups(YCl_(6)^(3-),Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-),and Y_(2)Cl_(9)^(3-))is carried out by Multiwfn program.The net charge in each group,the direction of electron migration during the formation of each group,the sites where electrophilic and nucleophilic reactions are most likely to occur in each ionic group,and the order of bond breaking during chemical reactions for the four groups are obtained.展开更多
ZnSe is one of the important and excellent II-VI semiconductor materials, which has direct transition band structure. In this paper, ZnSe thin films were prepared by an electrochemical deposition method, and the forma...ZnSe is one of the important and excellent II-VI semiconductor materials, which has direct transition band structure. In this paper, ZnSe thin films were prepared by an electrochemical deposition method, and the formation mechanism of ZnSe was studied systematically. Voltammerry and chronoamperometry combined with X-ray diffraction （XRD） and Raman techniques were used to analyze the deposition processes. It is found that the substrate and deposition potentials have a great influence on the phase composition of deposited thin film, and Zn substrate is beneficial to the preparation ZnSe films. Strong selenium-substrate interaction results in the formation of selenimn compounds involving electrode materials. The addition of Zn（II） source can affect the reduction potential of Se, and results in the change of reducing mechanism of Se（0） from Se（IV）. Se（0） formed from H2Se because the formation of H2Se is more active than forming Se（0） directly from Se（IV）, and H2Se can recombine with the substrate material, forming selenium-substrate compounds more quickly.展开更多
基金The authors are grateful for the financial supports from the Fundamental Research Funds for the Central Universities,China(N182503033,N172502003)Postdoctoral Research Foundation of China(2018M640258)+1 种基金the National Natural Science Foundation of China(51804070)Guangxi Innovation-driven Development Program,China(GUIKE AA18118030).
基金financial supports from the National Natural Science Foundation of China(Nos.52004062,52074084,51804070)the Natural Science Foundation of Liaoning Province of China(No.2020-MS-084)the Guangxi Innovation-Driven Development Program,China(No.GUIKE AA18118030)。
基金Project(2017YFC0805100)supported by the National Key R&D Program of ChinaProject(GUIKE AA18118030)supported by Guangxi Innovation-driven Development Program,ChinaProject(N172502003)supported by the Fundamental Research Funds for the Central Universities,China.
基金financially supported by the National Natural Science Foundation of China (No.51974081)the Fundamental Research Funds for the Central Universities (No.N2225045)MOE of China and WEIQIAO Industry-Education Cooperation Project (No.2021021800102)。
文摘The knowledge on the ionic structure of YCl_(3)-KCl molten system is of guiding significance for the practical production of yttrium metals and yttrium alloys via molten salt electrolysis using this system as electrolyte.In this paper,the theoretical Raman spectra of the ionic groups which may exist in YCl_(3)-KCl molten system are simulated by quantum chemical calculation using Gaussian09 and Gauss View 5.0 programs based on density functional theory(DFT).Then the ionic structures of 20 mol%-60 mol%YCl_(3)-KCl molten salt systems are studied by comparing the Raman shift values of the bands in the theoretical Raman spectra of different ionic groups with the experimental spectra of this system.YCl_(6)^(3-),Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)are thought to exist in the molten system.With the increase of temperature,the relative content of YCl_(6)^(3-)ionic groups increases while those of Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)ionic groups decrease.Moreover,the"lifetime"of all ionic groups decreases within the temperature range of 692-730℃.Meanwhile,the relative contents of Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)increase with the increase of YCl_(3)content,while that of YCl_(6)^(3-)decreases.The wave function analysis of the four ionic groups(YCl_(6)^(3-),Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-),and Y_(2)Cl_(9)^(3-))is carried out by Multiwfn program.The net charge in each group,the direction of electron migration during the formation of each group,the sites where electrophilic and nucleophilic reactions are most likely to occur in each ionic group,and the order of bond breaking during chemical reactions for the four groups are obtained.
基金financially supported by the National Natural Science Foundation of China (Nos.51574071. 51322406 and 21501023)the Fundamental Research Funds for the Central Universities(No.140205001)
文摘ZnSe is one of the important and excellent II-VI semiconductor materials, which has direct transition band structure. In this paper, ZnSe thin films were prepared by an electrochemical deposition method, and the formation mechanism of ZnSe was studied systematically. Voltammerry and chronoamperometry combined with X-ray diffraction （XRD） and Raman techniques were used to analyze the deposition processes. It is found that the substrate and deposition potentials have a great influence on the phase composition of deposited thin film, and Zn substrate is beneficial to the preparation ZnSe films. Strong selenium-substrate interaction results in the formation of selenimn compounds involving electrode materials. The addition of Zn（II） source can affect the reduction potential of Se, and results in the change of reducing mechanism of Se（0） from Se（IV）. Se（0） formed from H2Se because the formation of H2Se is more active than forming Se（0） directly from Se（IV）, and H2Se can recombine with the substrate material, forming selenium-substrate compounds more quickly.
