Co-N-C催化剂的制备及“一锅法”合成N-亚苄基苯胺

doi:10.11949/0438-1157.20200906

摘要/Abstract

摘要：

以甲酰胺为氮源和碳源，乙酸钴为钴源，采用预先缩合/高温焙烧两步法制备了一系列Co-N-C催化剂，利用XRD、TEM、N₂吸附-脱附以及XPS等表征了催化剂结构，考察了催化剂用于硝基苯与苯甲醇“一锅法”合成 N-亚苄基苯胺的催化性能及其稳定性。结果表明，焙烧温度和掺杂氮元素对Co-N-C催化剂性能影响显著，催化剂Co-N-C/800具有最好的催化性能，0.6 MPa氮气气氛下，温度140℃，反应12 h，硝基苯转化率达99%，N-亚苄基苯胺选择性达99%，催化剂重复使用5次，其活性无明显下降。

关键词: 碳材料, 氮掺杂, 纳米结构, 催化合成, N-亚苄基苯胺, 一锅法

Abstract:

A series of Co-N-C catalysts were prepared by a two-step process including pre-condensation and high-temperature calcination, as well as formamide was used as both nitrogen and carbon sources, and cobalt acetate was employed as the source of cobalt. Then the characterizations of XRD, TEM, N₂ adsorption-desorption, and XPS were carried out to investigate the morphology and textural properties of as-prepared Co-N-C catalysts. Moreover, the catalytic activity and reusability of such Co-N-C catalysts were further studied for one-pot synthesis of N-benzyl aniline from nitrobenzene and benzyl alcohol. The results demonstrated that the annealing temperature and nitrogen-doping have remarkable influence on the catalytic activity of Co-N-C catalysts. The Co-N-C/800 catalyst exhibited the best catalytic performance, in which the conversion of nitrobenzene was 99%, and the selectivity of N-benzyl aniline was 99% under 0.6 MPa nitrogen, temperature of 140℃, and reaction time of 12 h. The catalyst was used repeatedly for 5 times, and its activity did not decrease significantly.

Key words: carbon material, nitrogen doping, nanostructure, catalytic synthesis, N-benzyl aniline, one-pot

中图分类号:

TQ 127.1

冷杰,罗晶晶,宋崇虎,周言,李章敏,陶端健. Co-N-C催化剂的制备及“一锅法”合成N-亚苄基苯胺[J]. 化工学报, 2020, 71(11): 5016-5024.

Jie LENG,Jingjing LUO,Chonghu SONG,Yan ZHOU,Zhangmin LI,Duanjian TAO. Preparation of Co-N-C catalysts and “one-pot method” for synthesis of N-benzyl aniline[J]. CIESC Journal, 2020, 71(11): 5016-5024.

图/表 10

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Catalyst	S_BET^①/(m²/g)	V^②/(cm³/g)	D^③/nm
Co-N-C/600	95	0.19	7.2
Co-N-C/800	299	0.28	4.3
Co-N-C/1000	47	0.10	7.5

Catalyst	S_BET^①/(m²/g)	V^②/(cm³/g)	D^③/nm
Co-N-C/600	95	0.19	7.2
Co-N-C/800	299	0.28	4.3
Co-N-C/1000	47	0.10	7.5

催化剂	1转化率/ %	3产率/ %	4产率/ %
Co-N-C/800	99	98	<1
Co-N-C/600	54	53	<1
Co-N-C/1000	63	62	<1
Co-N-C/800(酸洗)	33	33	-
Co-C/800	2	2	-

催化剂	1转化率/ %	3产率/ %	4产率/ %
Co-N-C/800	99	98	<1
Co-N-C/600	54	53	<1
Co-N-C/1000	63	62	<1
Co-N-C/800(酸洗)	33	33	-
Co-C/800	2	2	-

底物1a	底物2a	产物3a	1a转化率/%	3a产率/%
			82	80
			97	95
			98	96
			100	98
			97	95
			91	90
			98	97
			98	97
			96	94