g-C3N4锚定Cu(Ⅰ)高选择性催化CCl4合成2,4,4,4-四氯丁腈
g-C3N4 anchored Cu(Ⅰ)highly selective catalytic synthesis of 2,4,4,4-tetrachlorobutyronitrile using CCl4 and acrylonitrile
肖自胜 1李金玲 1陈伊睿 1兰支利 1尹笃林1
作者信息
- 1. 湖南师范大学化学化工学院,湖南长沙 410081;石化新材料与资源精细利用国家地方联合工程实验室,湖南 长沙 410081
- 折叠
摘要
以尿素和Cu(NO3)2·3H2O为前体,采用热缩合法制备了不同Cu负载量的氮化碳(g-C3N4)基催化剂Cu/CNn(n=1、2、3),采用X射线衍射仪、傅里叶变换红外光谱、X射线光电子能谱、比表面积测试、扫描电子显微镜及透射电子显微镜对其结构和形貌进行了表征,比较了不同Cu负载量的Cu/CNn催化CCl4与丙烯腈(AN)的原子转移自由基加成(ATRA)反应合成 2,4,4,4-四氯丁腈(TBN)的催化性能.结果表明,Cu/CN1呈现优异的催化性能,以乙腈(MeCN)为溶剂,n(Cu/CN1)∶n(AN)=1∶1000,120℃反应12h,TBN 的选择性可达96.5%,产率可达83.3%,Cu/CN作为多相催化剂,经过滤处理便可重复利用,使用7次其催化活性仍能稳定保持.基于相关的实验结果,提出了Cu/CN催化 CCl4 和AN 的 ATRA反应的氧化-还原循环机理.实验结果揭示了Cu与g-C3N4载体的协同作用机制,为CCl4深加工开发高效的催化体系提供了新的思路.
Abstract
CuCNn(n=1,2,3)catalysts with different Cu loading amounts were prepared by thermal condensation using urea and Cu(NO3)2·3H2O as precursors,The structures and morphology of the catalysts were characterized by XRD,FTIR,XPS,BET,SEM and TEM.The catalytic performance of Cu/CNn with different Cu loading amounts was compared in the atom transfer radical addition(ATRA)reaction of CCl4 with acrylonitrile(AN)to synthesize 2,4,4,4-tetrachlorobutanitrile(TBN).The results showed that the Cu/CN1 exhibited excellent catalytic performance.Using acetonitrile(MeCN)as a solvent,n(Cu/CN1)∶n(AN)=1∶1000,120℃,for 12h,the selectivity and yield of TBN can reach 96.5%and 83.3%,respectively.As a heterogeneous catalyst,Cu/CN can be reused only after filtration treatment,and its catalytic activity can still be stably maintained after 7 times of use.Based on the relevant experimental results,the oxidation-reduction cycle ATRA reaction mechanism of CCl4 and AN catalyzed by Cu/CN was proposed.The results of experiments revealed the synergistic mechanism of Cu and g-C3N4,providing a new idea for the development of efficient catalytic systems for CCl4 deep processing.
关键词
2,4,4,4-四氯丁腈/氮化碳/Cu/CN催化剂/原子转移自由基加成Key words
2,4,4,4-tetrachloronitrile/g-C3N4/Cu/CN catalyst/atom transfer radical addition(ATRA)引用本文复制引用
出版年
2024
国家科技期刊平台
NSTL
万方数据