g-C3N4锚定Cu(‍Ⅰ)高选择性催化CCl4合成2,4,4,4-四氯丁腈

doi:10.16085/j.issn.1000-6613.2023-0762

摘要/Abstract

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。

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

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.

Key words: 2,4,4,4-tetrachloronitrile, g-C₃N₄, Cu/CN catalyst, atom transfer radical addition (ATRA)

中图分类号:

肖自胜, 李金玲, 陈伊睿, 兰支利, 尹笃林. g-C₃N₄锚定Cu(‍Ⅰ)高选择性催化CCl₄合成2,4,4,4-四氯丁腈[J]. 化工进展, 2024, 43(6): 3293-3300.

XIAO Zisheng, LI Jinling, CHEN Yirui, LAN Zhili, YIN Dulin. g-C₃N₄ anchored Cu(‍Ⅰ) highly selective catalytic synthesis of 2,4,4,4-tetrachlorobutyronitrile using CCl₄ and acrylonitrile[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3293-3300.

图/表 6

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样品	ICP-OES测定	EDS测定
Cu/CN1	6.7	1.1
Cu/CN2	12.1	1.2
Cu/CN3	25.8	3.3

样品	ICP-OES测定	EDS测定
Cu/CN1	6.7	1.1
Cu/CN2	12.1	1.2
Cu/CN3	25.8	3.3

序号	催化剂	n(AN)∶n(CCl₄)	AN转化率 /%	TBN选择性 /%	TBN收率 /%
1	空白	1∶5	0	0	0
2	g-C₃N₄	1∶5	0	0	0
3	Cu(NO₃)₂·3H₂O	1∶5	56.2	68.5	38.5
4	Cu(NO₃)₂·3H₂O	5∶1	11.2	64.7	7.3
5	Cu(NO₃)₂·3H₂O	1∶1	60.6	70.6	42.8
6	Cu/CN1	1∶5	87.1	94.7	82.5
7	Cu/CN1	5∶1	17.5	90.3	15.8
8	Cu/CN1	1∶1	86.3	96.5	83.3
9	Cu/CN2	1∶5	82.2	88.9	73.1
11	Cu/CN2	5∶1	15.1	82.1	12.4
12	Cu/CN2	1∶1	83.5	89.2	74.5
13	Cu/CN3	1∶5	76.9	74.8	57.5
14	Cu/CN3	5∶1	16.3	71.8	12.7
15	Cu/CN3	1∶1	77.9	79.3	61.8

序号	催化剂	n(AN)∶n(CCl₄)	AN转化率 /%	TBN选择性 /%	TBN收率 /%
1	空白	1∶5	0	0	0
2	g-C₃N₄	1∶5	0	0	0
3	Cu(NO₃)₂·3H₂O	1∶5	56.2	68.5	38.5
4	Cu(NO₃)₂·3H₂O	5∶1	11.2	64.7	7.3
5	Cu(NO₃)₂·3H₂O	1∶1	60.6	70.6	42.8
6	Cu/CN1	1∶5	87.1	94.7	82.5
7	Cu/CN1	5∶1	17.5	90.3	15.8
8	Cu/CN1	1∶1	86.3	96.5	83.3
9	Cu/CN2	1∶5	82.2	88.9	73.1
11	Cu/CN2	5∶1	15.1	82.1	12.4
12	Cu/CN2	1∶1	83.5	89.2	74.5
13	Cu/CN3	1∶5	76.9	74.8	57.5
14	Cu/CN3	5∶1	16.3	71.8	12.7
15	Cu/CN3	1∶1	77.9	79.3	61.8

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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

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