Preparation of Co-N-C catalysts and “one-pot method” for synthesis of N-benzyl aniline

doi:10.11949/0438-1157.20200906

Abstract

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

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

CLC Number:

TQ 127.1

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.

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.

Figures/Tables 10

References 34

1	王树清, 高崇. 中间体N-亚苄基苯胺的合成研究[J]. 精细石油化工进展, 2006, 7(3): 45-47.
	Wang S Q, Gao C. Study on synthesis of N-benzalaniline as itermediate[J]. Advances in Fine Petrochemicals., 2006, 7(3): 45-47.
2	Naeimi H, Rabiei K. Montmorillonite as a heterogeneous catalyst in the efficient, mild and one pot synthesis of Schiff bases under solvent-free conditions[J]. J. Chin. Chem. Soc., 2012, 59: 208-212.
3	Wang K Z, Gao W B, Jiang P B, et al. Bi-functional catalyst of porous N-doped carbon with bimetallic FeCu for solvent-free resultant imines and hydrogenation of nitroarenes[J]. Mol. Catal., 2019, 465: 43–53.
4	Song T, Park J E, Chung Y K. Rhodium-catalyzed synthesis of imines and esters from benzyl alcohols and nitroarenes: change in catalyst reactivity depending on the presence or absence of the phosphine ligand[J]. J. Org. Chem., 2018, 83: 4197-4203.
5	Zhou P, Zhang Z H. One-pot reductive amination of carbonyl compounds with nitro compounds over the Co-N_xcatalyst by transfer hydrogenation[J]. ChemSusChem, 2017, 10(9): 1892-1897.
6	Guo B, Li H-X, Zhang S-Q, et al. C-N bond formation catalyzed by ruthenium nanoparticles supported on N-doped carbon via acceptorless dehydrogenation to secondary amines, imines, benzimidazoles and quinoxalines[J]. ChemCatChem, 2018, 10(24): 5627-5636.
7	时洪涛, 刘迎新. Au-Ru/TiO₂催化硝基苯和苯甲醛一锅法合成N-苄基苯胺[J]. 工业催化, 2012, 20(8): 61-64.
	Shi H T, Liu Y X. One-pot synthesis of benzylaniline from nitrobenzene and benzaldehyde over Au-Ru/TiO₂ catalyst[J]. Ind. Catal., 2012, 20(8): 61-64.
8	Böhmer M, Kampert F, Peris E, et al. Ir^III/Au^I and Rh^III/Au^I heterobimetallic complexes as catalysts for the coupling of nitrobenzene and benzylic alcohol[J]. Organometallics, 2018, 37: 4092-4099.
9	陆晓蕾, 张琳, 顾运江, 等. Ru/C催化剂上硝基苯与苯甲醇“一锅法” 合成N-亚苄基苯胺的研究[J].浙江化工, 2013, 44(10): 29-33.
	Lu X L, Zhang L, Gu Y J, et al. One-pot synthesis of N-benzalaniline from nitrobenzene and benzyl alcohol over Ru/C Catalyst[J]. Zhejiang Chem. Ind., 2013, 44(10): 29-33.
10	Zanardi A, Mata J A, Peris E. One-pot preparation of imines from nitroarenes by a tandem process with an Ir–Pd heterodimetallic catalyst[J]. Chem. Eur. J., 2010, 16: 10502-10506.
11	Zhang C H, Zhao P S, Zhang Z L. Co-N-C supported on SiO₂: a facile, efficient catalyst for aerobic oxidation of amines to imines[J]. RSC Adv., 2017, 7: 47366-47372.
12	Hirakawa H, Katayama M, Shiraishi Y, et al. One-pot synthesis of imines from nitroaromatics and alcohols by tandem photocatalytic and catalytic reactions on degussa (Evonik) P25 titanium dioxide[J]. ACS Appl. Mater. Inter., 2015, 6(7): 3797-3806.
13	Cui X J, Zhang C G, Shi F, et al. Au/Ag-Mo nano-rods catalyzed reductive coupling of nitrobenzenes and alcohols using glycerol as the hydrogen source [J]. Chem. Commun., 2012, 48: 9391-9393.
14	Tang C H, He L, Liu Y M, et al. Direct one-pot reductive N-alkylation of nitroarenes by using alcohols with supported gold catalysts[J]. Chem. Eur. J., 2011, 17: 7172-7177.
15	Tang L, Sun H, Li Y F, et al. Highly active and selective synthesis of imines from alcohols and amines or nitroarenes catalyzed by Pd/DNA in water with dehydrogenation[J]. Green Chem., 2012, 14: 3423.
16	Chen J, Huang S J, Lin J, et al. Recyclable palladium catalyst for facile synthesis of imines from benzyl alcohols and nitroarenes[J]. Appl. Catal. A-Gen., 2014, 470: 1-7.
17	Zhou P, Yu C L, Jiang L, et al. One-pot reductive amination of carbonyl compounds with nitro compounds with CO/H₂O as the hydrogen donor over non-noble cobalt catalyst[J]. J. Catal., 2017, 352: 264-273.
18	Li M S, Fernando C L, Keane M. Combined catalytic action of supported Cu and Au in imine production from coupled benzyl alcohol and nitrobenzene reactions[J]. Appl. Catal. A-Gen., 2018, 557: 145-153.
19	Sankar M, He Q, Dawson S, et al. Supported bimetallic nano-alloys as highly active catalysts for the one-pot tandem synthesis of imines and secondary amines from nitrobenzene and alcohols[J]. Catal. Sci. Technol., 2016, 6: 5473.
20	Wu Y H, Ye X G, Zhang S J, et al. Photocatalytic synthesis of Schiff base compounds in the coupled system of aromatic alcohols and nitrobenzene using Cd_XZn_1-_XS photocatalysts[J]. J. Catal., 2018, 359: 151-160.
21	Ye X G, Chen Y H, Ling C C, et al. One-pot synthesis of Schiff base compounds via photocatalytic reaction in the coupled system of aromatic alcohols and nitrobenzene using CdIn₂S₄ photocatalyst[J]. Dalton Trans., 2018, 47: 10915-10924.
22	Yu W W, Guo X W, Song C S, et al. Visible-light-initiated one-pot clean synthesis of nitrone from nitrobenzene and benzyl alcohol over CdS photocatalyst[J]. J. Catal., 2019, 370: 97-106.
23	Zhao X, Zhou Y, Tao D J, et al. Co-N-C catalysts synthesized by pyrolysis of Co-based deep eutectic solvents for aerobic oxidation of alcohols[J]. New J. Chem., 2018, 42: 15871-15878.
24	Dou Y B, Chen Y, Li J R, et al. Pd@ZIF-67 derived recyclable Pd-based catalysts with hierarchical pores for high-performance Heck reaction[J]. ACS Sustain. Chem. Eng., 2018, 6: 2103-2111.
25	Liu D, Yang P, Zhang H, et al. Direct reductive coupling of nitroarenes and alcohols catalysed by Co-N-C/CNT@AC[J]. Green Chem., 2019, 21: 2129-2137.
26	Zhao X, Zhou Y, Tao D J, et al. Ultralow loading cobalt-based nanocatalyst for benign and efficient aerobic oxidation of allylic alcohols and biobased olefins[J]. ACS Sustain. Chem. Eng., 2019, 2(7): 1901-1908.
27	An X C, Zhou Y, Tao D J, et al. Rapid capture and efficient removal of low-concentration SO₂ in simulated flue gas by hypercrosslinked hollow nanotube ionic polymers[J]. Chem. Eng. J., 2020, 394: 124859.
28	Jie S S, Yang C Q, Chen Y, et al. Facile synthesis of ultrastable Co-N-C catalysts using cobalt porphyrin and peptides as precursors for selective oxidation of ethylbenzene[J]. Mol. Catal., 2018, 458: 1-8.
29	Sun T G, Xu L B, Li S Y, et al. Cobalt-nitrogen-doped ordered macro-/mesoporous carbon for highly efficient oxygen reduction reaction[J]. Appl. Catal. B-Environ., 2016, 193: 1-8.
30	Lan G J, Wang Y, Yang Y, et al. Flour-derived N-doped mesoporous carbon extrudate as superior metal-free catalysts for acetylene hydrochlorination[J]. Chem. Commun., 2018, 54: 623.
31	Liu W G, Zhang L L, Yan W S, et al. Single-atom dispersed Co-N-C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes[J]. Chem. Sci., 2016, 7: 5758-5764.
32	Cui X L, Liang K, Tian M, et al. Cobalt nanoparticles supported on N-doped mesoporous carbon as a highly efficient catalyst for the synthesis of aromatic amines[J]. J. Coll. Inter. Sci., 2017, 501: 231-240.
33	Yu P, Wang L, Sun F, et al. Co nanoislands rooted on Co-N-C nanosheets as efficient oxygen electrocatalyst for Zn-air batteries[J]. Adv. Mater., 2019, 31(30): 1901666.
34	Chen Y Z, Wang C, Wu Z Y, et al. From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis[J]. Adv. Mater., 2015, 27: 5010-5016.

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