Na_(2)CO_(3)-K_(2)CO_(3)-NaVO_(3)熔盐结构的拉曼光谱和理论计算  

Raman Spectroscopy and Theoretical Calculation on Structure of Na_(2)CO_(3)-K_(2)CO_(3)-NaVO_(3)Molten Salts

作　　者：张一帆 胡宪伟 于江玉[1,2] 王兆文 ZHANG Yi-fan;HU Xian-wei;YU Jiang-yu;WANG Zhao-wen(School of Metallurgy,Northeastern University,Shenyang 110819,China;Key Laboratory for Ecological Metallurgy of Multimetallic Mineral(Ministry of Education),Northeastern University,Shenyang 110819,China)

机构地区：[1]东北大学冶金学院,辽宁沈阳110819 [2]东北大学多金属共生矿生态化冶金教育部重点实验室,辽宁沈阳110819

出　　处：《东北大学学报（自然科学版）》2024年第3期331-336,共6页Journal of Northeastern University(Natural Science)

基　　金：国家自然科学基金资助项目(51974081);中央高校基本科研业务费专项资金资助项目(N2225045);山东魏桥创业集团有限公司-教育部产学合作协同育人项目(2021021800102).

摘　　要：NaVO_(3)在Na_(2)CO_(3)-K_(2)CO_(3)熔盐体系中可原位催化电还原CO_(2)制备高附加值碳材料,对Na_(2)CO_(3)-K_(2)CO_(3)-NaVO_(3)体系熔盐结构进行研究有助于明晰电极过程机理和优化反应条件.本文采用拉曼光谱学和量子化学计算(基于Gaussian和Molclus程序)相结合的方法探究了1073 K下Na_(2)CO_(3)-K_(2)CO_(3)-NaVO_(3)熔盐体系的离子结构.结果表明,在该熔盐体系中,除了存在CO_(3)^(2-)以外,还存在由CO_(3)^(2-)和VO_(3)^(-)发生反应生成的VO_(4)^(3-),而不存在VO_(3)^(-);VO_(4)^(3-)所属C1空间点群,其中V-O键的对称伸缩振动模对应的拉曼特征峰位于802 cm^(-1)处;随着体系中NaVO_(3)质量分数由5%增加至15%,熔盐中VO_(4)^(3-)的相对含量急剧增加,而CO_(3)^(2-)的相对含量相应地减少.In the molten Na_(2)CO_(3)‐K_(2)CO_(3),NaVO_(3)can catalyze the in‐situ electroreduction of CO_(2)to prepare high value‐added carbon‐based products.Studying the molten salt structure of Na_(2)CO_(3)‐K_(2)CO_(3)‐NaVO_(3)system contributes to understand the electrode process mechanism and optimize the reaction conditions.The ionic structure of Na_(2)CO_(3)‐K_(2)CO_(3)‐NaVO_(3)molten salt system at 1073 K was investigated by a combination of Raman spectroscopy and quantum chemistry calculation using Gaussian and Molclus programs.The results show that VO_(4)^(3-)generated by the reaction of CO32-and VO_(3)-exists in the melts,apart from the presence of CO_(3)^(2-),but VO_(3)-doesn’t exist.VO_(4)^(3-)belongs to C1 point group symmetry,and the band located at 802 cm^(-1)in the Raman spectrum is caused by the symmetrical stretching vibration of the V-O bond in VO_(4)^(3-).As the mass fraction of NaVO_(3)in the system increases from 5%to 15%,the relative content of VO_(4)^(3-)increases dramatically,while that of CO_(3)^(2-)decreases accordingly in the molten salts.

关 键 词：NaVO_(3) Na_(2)CO_(3)-K_(2)CO_(3)熔盐 拉曼光谱 量子化学计算 VO_(4)^(3-) 

分 类 号：O433.4[机械工程—光学工程] O641[理学—光学]