摘要
以尿素和Cu(NO_(3))_(2)·3H_(2)O为前体,采用热缩合法制备了不同Cu负载量的氮化碳(g-C_(3)N_(4))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CCl_(4)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CCl_(4)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-C_(3)N_(4)载体的协同作用机制,为CCl_(4)深加工开发高效的催化体系提供了新的思路。
CuCNn(n=1,2,3)catalysts with different Cu loading amounts were prepared by thermal condensation using urea and Cu(NO_(3))_(2)·3H_(2)O 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 CCl_(4)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 CCl_(4)and AN catalyzed by Cu/CN was proposed.The results of experiments revealed the synergistic mechanism of Cu and g-C_(3)N_(4),providing a new idea for the development of efficient catalytic systems for CCl_(4)deep processing.
作者
肖自胜
李金玲
陈伊睿
兰支利
尹笃林
XIAO Zisheng;LI Jinling;CHEN Yirui;LAN Zhili;YIN Dulin(College of Chemistry and Chemical Engineering,Hunan Normal University,Changsha 410081,Hunan,China;National&Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources,Changsha 410081,Hunan,China)
出处
《化工进展》
EI
CAS
CSCD
北大核心
2024年第6期3293-3300,共8页
Chemical Industry and Engineering Progress
基金
国家自然科学基金(21776068)。
