含Mn碱式碳酸铜电催化剂催化溴氨酸芳胺化反应研究

doi:10.11949/0438-1157.20250307

摘要/Abstract

摘要：

为解决1-氨基-4-溴蒽醌-2-磺酸（溴氨酸）芳胺化反应催化剂Cu⁺易失活、影响溴氨酸芳胺化反应效率的问题，设计并制备了一种促Cu²⁺释放的含Mn碱式碳酸铜电催化剂，并在两电极体系中采用电化学还原方法进行溴氨酸芳胺化反应。利用循环伏安法（CV）、扫描电镜（SEM）、电化学阻抗谱（EIS）等研究了还原电压、电催化剂组成对芳胺化反应的影响，并进行了底物拓展和放大实验。结果表明，所制备的含Mn碱式碳酸铜电催化剂能有效促进Cu²⁺释放，并在-0.4 V的还原电压下被还原为Cu⁺原位催化溴氨酸与2,4,6-三甲基-1,3-二氨基苯磺酸（M酸）的芳胺化，反应收率达93%，脱溴副产仅3%。对于苯胺、间乙酰氨基苯胺及对乙酰氨基苯胺这三种底物，本策略均能使其芳胺化反应收率达90%以上。此外，在20 g（溴氨酸）级的放大反应中，使溴氨酸与M酸的芳胺化反应取得90%的收率，具有优异的放大制备潜力。

关键词: 溴氨酸芳胺化, 碱式碳酸铜, 成核, 一价铜离子, 电化学还原, 沉淀, 溶解性

Abstract:

In order to solve the problem of easy inactivation of Cu⁺ in 1-amino-4-bromoanthraquinone-2-sulfonic acid (bromaminic acid) amination reaction, a basic copper carbonate electrocatalyst containing Mn to promote Cu²⁺ release was designed and prepared, and the amination of bromaminic acid was carried out by electrochemical reduction method in a two-electrode system. The effects of reduction voltage and electrocatalyst composition on the arylation reaction were studied by cyclic voltammetry (CV), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and substrate expansion and amplification experiments were carried out. The results showed that the prepared basic copper carbonate electrocatalyst containing Mn could effectively promote the release of Cu²⁺, and could be reduced to Cu⁺in situ to catalyze the amination of bromaminic acid with 2,4,6-trimethyl-1,3-diaminobenzenesulfonic acid (M acid) at a reduction voltage of -0.4 V, with the yield reaching 93% and the debromination byproduct only 3%. The amination yields of aniline, 3-acetylaminoaniline and 4-acetylaminoaniline could reach more than 90% by this strategy. In addition, the amination reaction of bromaminic acid with M acid in 20 g (bromaminic acid) grade achieved 90% yield, which has excellent amplification potential.

Key words: amination of bromaminic acid, basic copper carbonate, nucleation, monovalent copper ion, electrochemical reduction, precipitation, solubility

中图分类号:

TQ 151.5

唐志成, 王添巍, 吕荣文, 张淑芬. 含Mn碱式碳酸铜电催化剂催化溴氨酸芳胺化反应研究[J]. 化工学报, 2025, 76(11): 5923-5932.

Zhicheng TANG, Tianwei WANG, Rongwen LYU, Shufen ZHANG. Amination of bromaminic acid catalyzed by Mn-containing basic copper carbonate electrocatalyst based on electrochemical reduction[J]. CIESC Journal, 2025, 76(11): 5923-5932.

图/表 14

图1 不同扫速下的石墨电极在含0.1 g碱式碳酸铜的0.1 mol/L碳酸氢钠溶液中的循环伏安曲线

Fig.1 Cyclic voltammetry curves of graphite electrodes at different scanning speeds in a 0.1 mol/L sodium bicarbonate solution containing 0.1 g of basic copper carbonate

图2 溴氨酸与M酸芳胺化反应中溴氨酸转化率、芳胺化产物收率及脱溴副产与还原电压的关系

Fig.2 The relationship between the conversion rate of bromamic acid, the yields and the by-product of debromination with the reduction voltage in amination reaction of bromamic acid and M-acid

表1 还原电压对溴氨酸与M酸芳胺化反应的影响

Table 1 Effect of reduction voltage on amination of bromaminic acid with M acid

编号	还原电压/V	溴氨酸转化率/%	收率/%	脱溴副产/%
1	-0.1	61	55	2
2	-0.2	69	63	3
3	-0.3	86	78	4
4	-0.4	100	90	4
5	-0.5	93	85	5
6	-0.6	82	76	5
7	-0.7	74	66	4
8	-0.8	63	52	6

表2 电还原与化学还原催化溴氨酸芳胺化结果比较

Table 2 Comparison of results of amination of bromaminic acid catalyzed by electroreduction and chemical reduction

编号	催化方式	溴氨酸转化率/%	收率/%	脱溴副产/%
1	含Mn碱式碳酸铜，电化学还原，-0.4 V	100	93	3
2	硫酸铜，电化学还原，-0.4 V	97	88	3
3	无外加铜源，电化学还原，-0.4 V	0	0	0
4	硫酸铜	69	63	3
5	硫酸铜+抗坏血酸	98	87	8
6	硫酸铜+葡萄糖	99	90	6

图3 含Mn碱式碳酸铜电催化剂与空白样的XRD谱图

Fig.3 XRD patterns of Mn containing basic copper carbonate electrocatalyst and blank sample

图4 含Mn电催化剂在100 nm(a)、10 nm(b)、5 nm[(c), (d)]尺度下的SEM图

Fig.4 SEM images of manganese containing electrocatalysts at scale of 100 nm (a), 10 nm (b), and 5 nm[(c), (d)]

表3 含Mn碱式碳酸铜电催化剂的晶格条纹信息

Table 3 Lattice fringe information of Mn containing basic copper carbonate electrocatalysts

物种	条纹编号	晶格尺寸/nm	晶面
CuCO₃	Ⅲ	0.286	(20-1)
Cu₂(OH)₂CO₃	Ⅱ	0.218	(041)
	Ⅳ	0.278	(21-1)
	Ⅷ	0.267	(122)
Na₂Cu(CO₃)₂·3H₂O	Ⅳ	0.278	(311)
Na₂Cu(CO₃)₂·3H₂O	Ⅶ	0.284	(114)
Na₃Cu₂(CO₃)₃(OH)₄·H₂O	Ⅴ, Ⅵ	0.267	—
MnCO₃	Ⅰ	0.239	(110)

图5 醋酸锰在0.1 mol/L NaHCO3溶液中沉淀的XRD谱图

Fig.5 XRD pattern of manganese acetate precipitation in 0.1 mol/L NaHCO3 solution

图6 80℃下不同铜催化剂在0.1 mol/L NaHCO3溶液中释放的Cu2+浓度随时间变化

Fig.6 Variation of Cu2+ concentration with time released by different copper catalysts in 0.1 mol/L NaHCO3 solution at 80℃

图7 石墨电极在含0.1 g电催化剂的10 ml 0.1 mol/L碳酸氢钠溶液中以-0.4 V电解3 h后的Nyquist图

Fig.7 Nyquist diagram of graphite electrode after electrolysis at -0.4 V for 3 h in 10 ml 0.1 mol/L sodium bicarbonate solution containing 0.1 g electrocatalyst

图8 石墨电极在含0.1 g电催化剂的10 ml 0.1 mol/L碳酸氢钠溶液中以0 V(a)、-0.1 V(b)、-0.4 V(c)、-1 V(d)电解3 h后的TEM图

Fig.8 TEM images of graphite electrodes after electrolysis for 3 h in 10 ml 0.1 mol/L sodium bicarbonate solution containing 0.1 g of electrocatalyst at 0 V (a), -0.1 V (b), -0.4 V (c), -1 V (d)

图9 石墨电极在含0.1 g电催化剂的10 ml 0.1 mol/L碳酸氢钠溶液中以-0.4 V电解3 h后的XRD谱图(a)及XPS全谱(b)、Cu 2p(c)、Cu LMM(d)图

Fig.9 XRD pattern (a) and XPS survey (b), Cu 2p (c), Cu LMM(d) patterns of the graphite electrode after electrolysis in 10 ml 0.1 mol/L NaHCO3 solution containing 0.1 g of electrocatalyst at -0.4 V for 3 h

表4 含Mn碱式碳酸铜及电化学还原催化溴氨酸芳胺化反应底物拓展

Table 4 Substrate scope for Mn containing basic copper carbonate and electrochemical reduction catalyzed amination of bromaminic acid

还原电压/V	溴氨酸转化率/%	收率/%	脱溴副产/%
-0.2	95	89	3
-0.3	100	90	3
-0.4	94	89	4
-0.3	91	80	3
-0.4	100	93	3
-0.5	95	89	4
-0.4	90	82	5
-0.5	100	91	5
-0.6	94	85	6

图10 溴氨酸与M酸芳胺化放大反应的反应液LC-MS图

Fig.10 Liquid chromatography mass spectrum of reaction solution in enlarged scale of amination of bromaminic acid with M acid

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