钇离子在氯化物熔盐中的电化学还原

利用循环伏安法、计时电位法和卷积伏安法研究了钇离子在LiCl-KCl熔盐体系中,钼电极上的阴极过程。结果表明,钇离子的电化学还原反应是简单的一步反应,阴极过程在较低扫描速度下接近于可逆过程,且受扩散控制。阴极产物为固态钇。     

YF3-LiF熔盐体系中氧化物电解共沉积钇镁合金的阴极过程研究

采用循环伏安法分别以钨丝和铂丝为参比和工作电极，光谱纯石墨棒为辅助电极，在820℃下研究了添加Y2O3和MgO的YF3-LiF熔盐体系中Y^3＋和Mg＆2＋在钨电极上的电化学还原过程。结果表明：Y^3＋和Mg^2＋的析出是可逆的简单电荷传递反应，且过程受扩散控制。其反应分别为：Mg^2＋＋2e→Mg；Y^3＋＋3e→Y。随着混合氧化物中Y2O3比例的增大，Y的析出电位向正方向移动，Mg的析出电位向负方向移动，两者的析出电位差减小，当Y2O3：MgO=4：1时钇离子和镁离子共放电析出。     

熔盐电沉积稀土金属及其合金的研究：中山大学电化学研究工作介绍

熔盐电沉积稀土金属及其合金的研究——中山大学电化学研究工作介绍①杨绮琴（中山大学化学与化学工程学院广州５１０２７５）稀土金属及其合金具有许多优异的特殊性能，在国民经济中的应用日益广泛，是发展现代高新科学技术不可缺少的材料，例如磁性、磁光、超导、贮氢、...     

在LiCl-KCl-ZnCl_2熔盐体系中电化学共还原提取钕

针对镧系元素钕,本文通过循环伏安、开路计时电位、方波伏安等方法研究了773 K时Nd(III)在钼电极上在LiCl-KCl-ZnCl2熔盐体系中的电化学行为及Zn-Nd合金的形成过程.结果表明:在LiCl-KCl-ZnCl2熔盐中,Nd(III)在预先沉积的Zn阴极上欠电位沉积形成三种Zn-Nd金属间化合物.基于电化学行为研究,采用恒电位电解提取Nd并用方波伏安曲线测量来检测Nd(III)离子浓度的变化,然后通过电解前后Nd(III)离子浓度变化评估了Nd的电解提取效率.实验结果表明:-1.84 V恒电位电解进行50 h后,Nd(III)离子浓度接近于零,提取效率为99.67%.在973 K时通过恒电流电解提取Nd并获得了Zn-Nd合金,通过X射线衍射(XRD)和扫描电子显微镜(SEM)附带能量散射谱(EDS)对合金的相组成和微观形貌进行了分析.XRD分析表明在Zn-Nd合金中存在Nd2Zn17,LiZn和Zn相,EDS能谱分析表明Nd在合金中的原子分数高达14.99%.     

熔盐电化学还原二氧化碳制备碳材料研究进展北大核心CSCD

二氧化碳浓度持续升高导致的温室效应已在全球范围内引发极端天气、冰川融化等一系列生态环境问题。为降低二氧化碳含量,改善气候变暖带来的恶劣影响,研发高效、绿色、安全的二氧化碳处理技术,促进碳资源循环可持续发展刻不容缓。熔盐离子液体作为一种良好的电化学转化介质,为二氧化碳还原提供了一条极具应用前景的技术路线。综述了国内外近几年高温熔盐中二氧化碳的捕获与电化学还原的研究,简述了熔盐电沉积碳的电化学机理和热力学机制,对不同形貌高附加值碳材料:无定形碳、碳球和碳纳米管的制备进行了总结,最后对未来发展方向做出展望。     

熔盐电化学的新进展

本文主要介绍熔盐体系、熔盐电池、熔盐电沉积金属以及合金、电合成化合物材料等方面的新进展 ,预期熔盐电化学在能源、环境保护和资源利用等领域中的应用 .     

用透明电解槽研究镧,钕在氯化物熔盐中的溶解过程

采用透明电解槽技术首次观察了金属镧、钕分别在LaCl_3_KCl、NdCl_3+KCl以及KCl+NaCl熔盐中的溶解过程。实验发现镧、钕在各自熔盐中溶解时均产生黑色的金属雾。在电解条件下,镧、钕的溶解扩散受到很小的抑制。金属钕的溶解扩散明显快于金属镧的溶解扩散。形成的镧、钕金属雾主要由低价离子和部分金屈粒子(或原子)组成。     

在LiCl-KCl-ZnCl2熔盐体系中电化学共还原提取钕

针对镧系元素钕,本文通过循环伏安、开路计时电位、方波伏安等方法研究了773 K时Nd（Ⅲ）在钼电极上在LiCl-KCl-ZnCl₂熔盐体系中的电化学行为及Zn-Nd合金的形成过程. 结果表明：在LiCl-KCl-ZnCl₂熔盐中,Nd（Ⅲ）在预先沉积的Zn 阴极上欠电位沉积形成三种Zn-Nd金属间化合物. 基于电化学行为研究,采用恒电位电解提取Nd并用方波伏安曲线测量来检测Nd（Ⅲ）离子浓度的变化,然后通过电解前后Nd（Ⅲ）离子浓度变化评估了Nd的电解提取效率. 实验结果表明：-1.84 V恒电位电解进行50 h后,Nd（Ⅲ）离子浓度接近于零,提取效率为99.67%. 在973 K时通过恒电流电解提取Nd并获得了Zn-Nd合金,通过X射线衍射（XRD）和扫描电子显微镜（SEM）附带能量散射谱（EDS）对合金的相组成和微观形貌进行了分析. XRD分析表明在Zn-Nd合金中存在Nd₂Zn₁₇,LiZn 和Zn相,EDS能谱分析表明Nd在合金中的原子分数高达14.99%.     

熔盐电解法制备稀土合金研究进展

熔盐电解法制备稀土合金具有成本低、成份均匀且容易控制、质量较好、易实现连续化生产等优势.本文结合稀土合金在金属结构材料、磁性材料和贮氢材料中的应用,在介绍熔盐电解的知识进展的基础上,综述了稀土分别与镁、铝、铁、钴、镍、铜等组成的合金的熔盐电解制备研究进展,并对以后的研究工作进行展望.     

在LiCl-KCl-AlCl3熔盐中直接电化学还原Sm2O3及Al-Sm合金的形成

在803 K LiCl-KCl熔盐中, 研究了通过添加助剂AlCl₃直接电化学还原Sm₂O₃和Al-Sm合金的形成。以SmCl₃为原料作为参照, 采用循环伏安和方波伏安方法, 研究了Sm₂O₃在LiCl-KCl-AlCl₃熔盐体系中的电化学行为。通过对比发现在两个体系中, 峰的数量和位置基本一致, 这说明在LiCl-KCl熔盐中, 加入AlCl₃之后, 可以将Sm₂O₃有效氯化。计时电位结果表明, 当阴极电流比-139.8 mA·cm^-2更负时, Al和Sm共同还原。为了提取Sm, 采用恒电流从LiCl-KCl-AlCl₃-Sm₂O₃熔盐中电解得到Al-Sm合金样品, 并进行XRD表征, 结果表明可以通过调节AlCl₃和Sm₂O₃的浓度得到不同相的Al-Sm合金。     

Ba-K-Bi-O超导体熔盐阳极电结晶研究

用ＸＰＳ和ＸＲＤ表征了Ｂａ－Ｋ－Ｂｉ－Ｏ超导体熔盐电结晶的阳极和阴 极产物，用ＳＥＭ分析了Ｂａ－Ｋ－Ｂｉ－Ｏ单生长形态。结果表明，阳极产物是Ｂａ－Ｋ－Ｂｉ－Ｏ超导体单晶，以台阶式方式生长。－Ｋ－Ｂ－     

The Coordination Chemistry of f-Block Elements in Molten Salts

The coordination chemistry of f-block elements (lanthanide and actinide) in molten salts has become a resounding topic in view of its great importance to the research and development (R&D) of molten salt reactors and pyroprocessing. In this Review article, a general overview of the coordination chemistry of f-block elements in molten salts is provided including past achievements and recent advances. Particular emphases are placed on the oxidation state, speciation, and solution structure of f-block metal ions in molten salts, as well as their relationships with the salt composition. Furthermore, this review briefly discusses the spectroscopic and theoretical methods that complement each other in revealing the coordination properties.     

NaCl-KCl-CeCl3熔盐体系电解精炼铈的研究

用Ce作为模拟金属,开展了NaCl-KCl-CeCl3熔盐体系电解精炼提纯金属Ce的研究,为乏燃料干法后处理提纯U, Pu等金属提供了研究基础。研究了CeCl3浓度、电解温度和阴极电流密度对电解精炼Ce的收率和电流效率的影响,得到优化的工艺条件为:CeCl3浓度为20%~25%,电解精炼温度为900~950℃,阴极电流密度为0.35~0.45 A·cm^-2,得到了成型致密的金属铈锭,产品的收率大于70%。杂质元素Al, Fe, Cu, Cr,Mn的含量均有大幅度的下降,尤其是Fe的去除效果明显从1300×10^-6降低为200×10^-6。     

Pure and Metal-confining Carbon Nanotubes through Electrochemical Reduction of Carbon Dioxide in Ca-based Molten Salts

To be successfully implemented, an efficient conversion, affordable operation and high values of CO₂-derived products by electrochemical conversion of CO₂ are yet to be addressed. Inspired by the natural CaO-CaCO₃ cycle, we herein introduce CaO into electrolysis of SnO₂ in affordable molten CaCl₂-NaCl to establish an in situ capture and conversion of CO₂. In situ capture of anodic CO₂ from graphite anode by the added CaO generates CaCO₃. The consequent co-electrolysis of SnO₂ and CaCO₃ confines Sn in carbon nanotube (Sn@CNT) in cathode and increases current efficiency of O₂ evolution in graphite anode to 71.9 %. The intermediated CaC₂ is verified as the nuclei to direct a self-template generation of CNT, ensuring a CO₂-CNT current efficiency and energy efficiency of 85.1 % and 44.8 %, respectively. The Sn@CNT integrates confined responses of Sn cores to external electrochemical or thermal stimuli with robust CNT sheaths, resulting in excellent Li storage performance and intriguing application as nanothermometer. The versatility of the molten salt electrolysis of CO₂ in Ca-based molten salts for template-free generation of advanced carbon materials is evidenced by the successful generation of pure CNT, Zn@CNT and Fe@CNT.     

Inorganic Molten Salts as Solvents for Cellulose

Inorganic molten salts can be used as efficient solvents for cellulose in a wide range of degrees of polymerization. Furthermore, molten salts can be applied as reaction medium for the derivatization of cellulose. For both dissolution and derivatization of cellulose, knowledge of the solution state as well as information about chemical interactions with the solvent system is essential. Using the melts of LiClO₄·3H₂O, NaSCN/KSCN/LiSCN·2H₂O and LiCl/ZnCl₂/H₂O as cellulose solvents, factors which determine the dissolving ability will be discussed. Besides the specific structure of the molten salt hydrate, the cation and the water content of the melt are the most important factors for the dissolving capability of a molten salt hydrate system. FT-Raman spectroscopy, ⁷Li and ¹³C NMR spectroscopy were applied to describe solvent–cellulose interactions and the state of cellulose dissolved in the molten salts. Using Raman and solid state NMR spectroscopy it was proved that cellulose is amorphous in the frozen solvent system. The application of inorganic molten salts as a medium for cellulose functionalization is demonstrated for cellulose carboxymethylation and acetylation.     

Electrophilic Chlorine from Chlorosulfonium Salts: A Highly Chemoselective Reduction of Sulfoxides

Herein, we describe a selective late-stage deoxygenation of sulfoxides based on a novel application of chlorosulfonium salts and demonstrate a new process using these species generated in situ from sulfoxides as the source of electrophilic chlorine. The use of highly nucleophilic 1,3,5-trimethoxybenzene (TMB) as the reducing agent is described for the first time and applied in the deoxygenation of simple and functionalized sulfoxides. The method is easy to handle, economic, suitable for gram-scale operations, and readily applied for poly-functionalized molecules, as demonstrated with more than 45 examples, including commercial medicines and analogues. We also report the results of competition experiments that define the more reactive sulfoxide and we present a mechanistic proposal based on substrate and product observations.     

熔盐体系及有关应用的新进展

介绍近年来熔盐体系的概况,着重室温熔盐的发展.熔盐在电化学制备合金和功能材料、能源、分析和分离、用作反应介质和催化剂、环境保护等方面应用前景良好.     

Catalytic Reduction of Pyridinium, Pyrylium, and Thiopyrylium Salts. (Review)

Published data and the results of the authors' own investigations on the synthesis of six-membered saturated N-, O-, and S-containing heterocycles by catalytic reduction of pyridinium, pyrylium, and thiopyrylium salts are reviewed. The conditions, laws, and special characteristics of the reactions are considered.     

含氧酸盐熔盐Raman光谱V1峰位移的解释

若干含氧酸盐熔盐Raman光谱表明:含氧酸根离子的v₁峰(对称伸缩振动散射)位置随阳离子不同而异,James在解释NO₃^-在熔盐中的Raman光谱时,认为正电场较强的阳离子可能使NO₃^-中N-O键电子云密度增加,从而使力常数增大,v₁峰频率上升。为了探讨这一观点是否正确以及它对其它含氧酸根离子是否适用,我们用EHMO方法计算了若干由碱金属离子Me⁺和含氧酸根离子XO_m^m-(包括NO₃^-、NO₂^-、IO₃^-等)组成的原子簇(Me⁺)_x(XO_n^m-)中的X-O键的重叠集居数和原子净电荷,并考察其与相应的熔盐的Raman光谱v₁峰位置的关系。以探讨v₁峰位移的物理实质。     

绿色化学与铬盐工业的新一代产业革命

本文介绍了铬盐生产的绿色化学研究的内容和方法, 所开拓的熔盐液相氧化-高浓介质单向分离-介稳态相分离-碳化循环转化的多相反应与分离系统的绿色化学新原理, 资源深度利用-反应介质内循环-零排放的完整绿色工业化学体系。