不同铈盐体系(硝酸盐、硫酸盐、氯化盐)中CTAB与Ce^(3+)的相互作用机理  

Interaction mechanism of CTAB and Ce^(3+) in different cerium salt systems(nitrate,sulfate,chloride)

作　　者：孙德贇 胡艳宏[1,2,3] 刘鹏 唐茂 胡泽[1,2,3] 柳召刚 吴锦绣 SUN Deyun;HU Yanhong;LIU Peng;TANG Mao;HU Ze;LIU Zhaogang;WU Jinxiu(School of Materials and Metallurgy,Inner Mongolia University of Science and Technology,Baotou 014000,Inner Mongolia,China;Key Laboratory of Rare Earth Hydrometallurgy and Light Rare Earth Application,Inner Mongolia Autonomous Region,Baotou 014000,Inner Mongolia,China;Key Laboratory of Ministry of Education for Green Extraction and Efficient Utilization of Light Rare Earth Resources,Baotou 014000,Inner Mongolia,China)

机构地区：[1]内蒙古科技大学材料与冶金学院,内蒙古包头014000 [2]内蒙古自治区稀土湿法冶金与轻稀土应用重点实验室,内蒙古包头014000 [3]轻稀土资源绿色提取与高效利用教育部重点实验室,内蒙古包头014000

出　　处：《化工进展》2022年第6期3212-3220,共9页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(21666029);教育部创新团队项目(IPT1065);内蒙古自然科学基金(2016MS0223);草原英才个人培养项目。

摘　　要：采用十六烷基三甲基溴化铵(CTAB)为模板剂,利用Vienna AbInitio模拟软件包研究了3种不同铈盐体系(硝酸盐、硫酸盐、氯化盐)中CTAB与Ce^(3+)的相互作用以及成键稳定性。在不同铈盐体系的水环境中,CTAB中只有Br-会与Ce^(3+)发生相互作用并形成Ce—Br键。从晶体轨道哈密顿布居(COHP)、COHP的积分(ICOHP)以及径向分布函数的角度分析了不同体系下Ce—O键、Ce—Br键的成键稳定性。结果表明,不同铈盐体系下Ce^(3+)与H_(2)O所形成Ce—O键的ICOHP的值差距不大,成键比较稳定,但Ce^(3+)与CTAB中的Br-所形成Ce—Br键的稳定性具有较大差距,ICOHP的大小顺序为ICOHP_(硝酸体系)<ICOHP_(硫酸体系)<ICOHP_(氯化体系),说明CTAB在硝酸体系下对Ce^(3+)的控制作用最强,进而证明模板剂CTAB在硝酸体系下对制备二氧化铈晶体形核阶段具有较好的调控能力。Using cetyltrimethylammonium bromide(CTAB)as the template,Vienna Ab Initio simulation package was used to study the interaction of CTAB and Ce^(3+)in three different cerium salt systems(nitrate,sulfate,chloride)and the stability of the bond formation.In the water environment under different cerium salt systems,only Br-in CTAB interacted with Ce^(3+)and formed a Ce-Br bond.From the perspectives of COHP(crystal orbital hamiltonian population),ICOHP(integral of COHP)and radial distribution function(RDF),the bonding stability of Ce-O bond and Ce-Br bond in different systems was analyzed.The results showed that the ICOHP value of the Ce-O bond formed by Ce^(3+)and H_(2)O under different cerium salt systems was not much different,and the bond formation was relatively stable,while the Ce-Br bond formed by Ce^(3+)and Br-in CTAB had a big gap in stability.The order of ICOHP was:ICOHP_(nitric acid system)<ICOHP_(sulfuric acid system)<ICOHP_(chlorination system),which indicated that CTAB had the strongest control effect on Ce^(3+)under the nitric acid system.This proved that the templating agent CTAB had a better ability to control the nucleation stage of the preparation of ceria crystals under the nitric acid system.

关 键 词：计算机模拟 计算化学 密度泛函理论 十六烷基三甲基溴化铵 成核 

分 类 号：O611[理学—无机化学]