PCuMo11/MG-800多相催化硝基苯还原制苯胺

doi:10.16085/j.issn.1000-6613.2024-1281

摘要/Abstract

摘要：

苯胺作为一种重要的化学合成中间体，主要由硝基苯还原制得。开发活性高、选择性好且稳定的硝基苯还原制苯胺催化剂是十分必要的。本文以原位合成法制备氮掺杂碳材料MG-800，负载多金属氧酸盐PCuMo₁₁，得到复合材料PCuMo₁₁/MG-800。通过傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、透射电子显微镜（TEM）、N₂吸附-脱附及X射线光电子能谱（XPS）等测试手段对复合材料进行表征。MG-800丰富的氮元素和高比表面积有助于PCuMo₁₁的均匀分散；PCuMo₁₁与MG-800的化学相互作用提高了催化剂的活性和稳定性。实验结果显示，含0.5mmol硝基苯的乙醇溶液中加入1.5mmol水合肼还原剂和10mg PCuMo₁₁/MG-800催化剂，80℃反应20min，硝基苯转化率达100%，苯胺选择性大于99.9%，催化剂的转化率（TOF）为0.15mol/(g·h)。催化剂经过5次循环使用后仍具有良好的稳定性，苯胺的收率保持在99%，是一种高效、稳定、可循环使用的硝基苯加氢制苯胺多相催化剂。

关键词: 复合材料, 多相反应, 还原, 硝基苯, 催化剂

Abstract:

As an important intermediate, aniline is mainly produced by reduction of nitrobenzene and development of the catalysts with high activity, good selectivity and stability is essential. Nitrogen-doped carbon material MG-800 was prepared by in-situ synthesis, and then loaded with polyoxometallate PCuMo₁₁ to obtain the composite material PCuMo₁₁/MG-800. The composite material was characterized by FTIR, XRD, TEM, N₂ adsorption-desorption, and XPS. The rich nitrogen content and high specific surface area of MG-800 contribute to the homogeneous dispersion of PCuMo₁₁, and the chemical interaction between PCuMo₁₁ and MG-800 promotes the activity and stability of the catalyst. The experimental results showed that the addition of 1.5mmol of hydrazine hydrate reductant and 10mg of PCuMo₁₁/MG-800 catalyst to 0.5mmol of nitrobenzene in ethanol solution for 20min at 80℃ resulted in 100% nitrobenzene conversion, 99.9% aniline selectivity, and the turn over frequency (TOF) of the catalyst was 0.15mol/(g·h). The catalyst maintained good stability after 5 cycles, with the yield of aniline remaining at 99%. It is an efficient, stable and recyclable heterogeneous catalyst for the hydrogenation of nitrobenzene to aniline.

Key words: composites, multiphase reaction, reduction, nitrobenzene, catalyst

中图分类号:

O643.36

高永平, 康家宁, 刘柏, 袁诗淇, 于泽广, 张志会, 高文秀. PCuMo₁₁/MG-800多相催化硝基苯还原制苯胺[J]. 化工进展, 2025, 44(10): 5764-5770.

GAO Yongping, KANG Jianing, LIU Bai, YUAN Shiqi, YU Zeguang, ZHANG Zhihui, GAO Wenxiu. Catalytic hydrogenation of nitrobenzene to aniline over heterogeneous catalyst PCuMo₁₁/MG-800[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5764-5770.

图/表 9

参考文献 24

[1]	DOHERTY Simon, KNIGHT Julian G, BACKHOUSE Tom, et al. Highly selective and solvent-dependent reduction of nitrobenzene to N-phenylhydroxylamine, azoxybenzene, and aniline catalyzed by phosphino-modified polymer immobilized ionic liquid-stabilized AuNPs[J]. ACS Catalysis, 2019, 9(6): 4777-4791.
[2]	徐天缘, 郑茜, 王连娟, 等. 焦粉高效活化过硫酸盐对苯胺的降解性能[J]. 化工进展, 2022, 41(6): 3314-3323.
	XU Tianyuan, ZHENG Xi, WANG Lianjuan, et al. Persulfate activation by coke powder for aniline degradation[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3314-3323.
[3]	王敏嘉, 周少东, 阮建成, 等. 氯代硝基苯选择性加氢催化剂研究现状与进展[J]. 化工进展, 2021, 40(8): 4223-4230.
	WANG Minjia, ZHOU Shaodong, RUAN Jiancheng, et al. Progress in the research of chloronitrobenzene selective hydrogenation catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4223-4230
[4]	Olga MARCHUT-MIKOŁAJCZYK, Piotr DROŻDŻYŃSKI, JANUSZEWICZ Bartłomiej, et al. Degradation of ozonized tire rubber by aniline—Degrading Candida methanosorbosa BP6 strain[J]. Journal of Hazardous Materials, 2019, 367: 8-14.
[5]	SEKI Masahiko, TAKAHASHI Yusuke. Regioselective C—H azidation of anilines and application to synthesis of key intermediate for pharmaceutical[J]. The Journal of Organic Chemistry, 2021, 86(11): 7842-7848.
[6]	WANG Hao, LIU Xiaohao, XU Guangyue, et al. In situ synthesis of Fe-N-C catalysts from cellulose for hydrogenation of nitrobenzene to aniline[J]. Chinese Journal of Catalysis, 2019, 40(10): 1557-1565.
[7]	SONG Jiajia, HUANG Zhenfeng, PAN Lun, et al. Oxygen-deficient tungsten oxide as versatile and efficient hydrogenation catalyst[J]. ACS Catalysis, 2015, 5(11): 6594-6599.
[8]	XIA Ziyi, WANG Bowei, LI Jiayi, et al. Metal-free hydrogenation with formic acid over N-oped carbon[J]. New Journal of Chemistry, 2023, 47(12): 5621-5624.
[9]	TANG Jinsheng, ZHANG Suoshu, CHEN Xue, et al. Highly efficient catalytic reduction of nitrobenzene using Cu@C based on a novel Cu-MOF precursor[J]. Catalysts, 2023, 13(6): 956.
[10]	LUO Shicheng, LONG Yu, LIANG Kun, et al. Unsaturated Mo in Mo₄O₄N₃ for efficient catalytic transfer hydrogenation of nitrobenzene using stoichiometric hydrazine hydrate[J]. Green Chemistry, 2021, 23(21): 8545-8553.
[11]	MA Yanshuang, ZHANG Liyun, SHI Wen, et al. Facile-fabricated iron oxide nanorods as a catalyst for hydrogenation of nitrobenzene[J]. Chinese Chemical Letters, 2019, 30(1): 183-186.
[12]	HU Xiwei, LONG Yu, FAN Mengying, et al. Two-dimensional covalent organic frameworks as self-template derived nitrogen-doped carbon nanosheets for eco-friendly metal-free catalysis[J]. Applied Catalysis B: Environmental, 2019, 244: 25-35.
[13]	HUANG Haigen, TAN Mingwu, WANG Xueguang, et al. Synthesis of mesoporous γ-alumina-supported Co-based catalysts and their catalytic performance for chemoselective reduction of nitroarenes[J]. ACS Applied Materials & Interfaces, 2018, 10(6): 5413-5428.
[14]	MA Zongyan, CHEN Jing, CHEN Ming, et al. Magnetically reusable carbon nanotube coated Co-based catalysts towards highly efficient transfer hydrogenation of nitroarenes[J]. ChemCatChem, 2024, 16(16): e202400336.
[15]	Young-Si JUN, LEE Eun Zoo, WANG Xinchen, et al. From melamine-cyanuric acid supramolecular aggregates to carbon nitride hollow spheres[J]. Advanced Functional Materials, 2013, 23(29): 3661-3667.
[16]	王静. 咪唑功能化有机—无机杂化材料固载磷钼杂多化合物催化剂的制备及烯烃环氧化性能[D]. 长春: 吉林大学, 2014.
	WANG Jing. Preparation of imidazole functionalized organic-inorganic hybrid material supported phosphomolybdic heteropoly catalyst and its olefin epoxidation performance[D]. Changchun: Jilin University, 2014.
[17]	SONG Xiaojing, ZHU Wanchun, LI Kaige, et al. Epoxidation of olefins with oxygen/isobutyraldehyde over transition-metal-substituted phosphomolybdic acid on SBA-15[J]. Catalysis Today, 2016, 259: 59-65.
[18]	PATEL Anjali, PATHAN Soyeb. Keggin-type cesium salt of first series transition metal-substituted phosphomolybdates: One-pot easy synthesis, structural, and spectral analysis[J]. Journal of Coordination Chemistry, 2012, 65(17): 3122-3132.
[19]	谢远江, 罗明洪, 夏克坚. 功能化石墨烯多层膜载金催化剂的制备及其对肼的电催化氧化[J]. 复合材料学报, 2020, 37(7): 1695-1702.
	XIE Yuanjiang, LUO Minghong, XIA Kejian. Preparation of functionalized graphene multilayer films supported Au catalyst and its electro-oxidation for hydrazine[J]. Acta Materiae Compositae Sinica, 2020, 37(7): 1695-1702.
[20]	张素风, 赵东艳, 侯晨, 等. CuFe₂O₄/纳米纤维素磁性复合材料的制备及催化性能[J]. 复合材料学报, 2019, 36(1): 213-221.
	ZHANG Sufeng, ZHAO Dongyan, HOU Chen, et al. Synthesis and catalysis properties of magnetic CuFe₂O₄/cellulose composites[J]. Acta Materiae Compositae Sinica, 2019, 36(1): 213-221.
[21]	SUN Jian, YU Guangli, LIU Lulu, et al. Core-shell structured Fe₃O₄@SiO₂ supported cobalt(Ⅱ) or copper(Ⅱ) acetylacetonate complexes: Magnetically recoverable nanocatalysts for aerobic epoxidation of styrene[J]. Catalysis Science & Technology, 2014, 4(5): 1246-1252.
[22]	PHASAYAVAN Witchaya, INCEESUNGVORN Burapat, CHANSAI Sarayute, et al. MoO₃ catalysed hydrogenation of nitrobenzene to aniline at near room temperature[J]. Inorganic Chemistry Communications, 2024, 164: 112416.
[23]	MA Zongyan, CHEN Jing, CHEN Ming, et al. An unconventional direct path for the chemoselective hydrogenation of nitroarenes over a metal-free catalyst[J]. Molecular Catalysis, 2023, 547: 113372.
[24]	ZHANG Huaxin, FAN Weiwei, XIA Qinghua, et al. Protein-assisted synthesis of zeolite-supported pseudo-single-atom cobalt catalyst for nitrobenzene hydrogenation[J]. Chemical Engineering Journal, 2023, 469: 143870.

样品	比表面积/m²·g^-1	孔容/cm³·g^-1	最可几孔径/nm
MG-800	574	1.90	1.14
PCuMo₁₁/MG-800	277	1.23	1.27

样品	比表面积/m²·g^-1	孔容/cm³·g^-1	最可几孔径/nm
MG-800	574	1.90	1.14
PCuMo₁₁/MG-800	277	1.23	1.27

序号	催化剂	硝基苯用量/mmol	催化剂用量/mg	还原剂	温度/℃	时间	转化率/%	TOF/mol·g^-1·h^-1	循环次数	文献
1	WO_2.72	160	800	H₂	150	15h	53	7×10^-3	5	[7]
2	α-MoO₃	0.125	25	N₂H₄·H₂O	35	4h	88.6	1.1×10^-3	—	[22]
3	PNC-900	0.5	20	N₂H₄·H₂O	90	1h	100	25×10^-3	6	[23]
4	CN-900	0.25	20	HCOOH	160	12h	70	0.73×10^-3	—	[8]
5	Co@CN@HZM（空心分子筛微球）	0.5	70	H₂	100	4h	99.3	1.8×10^-3	8	[24]
6	Fe-N-C	0.5	50	H₂	120	12h	100	0.83×10^-3	5	[6]
7	20Co-NC/γ-MA	1	20	N₂H₄·H₂O	40	45min	>99	66×10^-3	—	[13]
8	PCuMo₁₁/MG-800	0.5	10	N₂H₄·H₂O	80	20min	100	150×10^-3	6	本文

序号	催化剂	硝基苯用量/mmol	催化剂用量/mg	还原剂	温度/℃	时间	转化率/%	TOF/mol·g^-1·h^-1	循环次数	文献
1	WO_2.72	160	800	H₂	150	15h	53	7×10^-3	5	[7]
2	α-MoO₃	0.125	25	N₂H₄·H₂O	35	4h	88.6	1.1×10^-3	—	[22]
3	PNC-900	0.5	20	N₂H₄·H₂O	90	1h	100	25×10^-3	6	[23]
4	CN-900	0.25	20	HCOOH	160	12h	70	0.73×10^-3	—	[8]
5	Co@CN@HZM（空心分子筛微球）	0.5	70	H₂	100	4h	99.3	1.8×10^-3	8	[24]
6	Fe-N-C	0.5	50	H₂	120	12h	100	0.83×10^-3	5	[6]
7	20Co-NC/γ-MA	1	20	N₂H₄·H₂O	40	45min	>99	66×10^-3	—	[13]
8	PCuMo₁₁/MG-800	0.5	10	N₂H₄·H₂O	80	20min	100	150×10^-3	6	本文

PCuMo₁₁/MG-800多相催化硝基苯还原制苯胺

Catalytic hydrogenation of nitrobenzene to aniline over heterogeneous catalyst PCuMo₁₁/MG-800

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

序号	催化剂	催化剂用量/mg	n(硝基苯)∶n(水合肼)	温度/℃	溶剂	时间	转化率/%	TOF/mol·g^-1·h^-1
1	无	0	1∶10	80	乙醇	4h	5	—
2	PCuMo₁₁	10	1∶10	80	乙醇	4h	18	2×10^-3
3	MG-800	10	1∶10	80	乙醇	4h	96	12×10^-3
4	PCuMo₁₁/MG-800	10	1∶4	80	乙醇	15min	100	200×10^-3
5	PCuMo₁₁/MG-800	10	1∶3	80	乙醇	15min	93	186×10^-3
6	PCuMo₁₁/MG-800	10	1∶3	80	乙醇	20min	100	150×10^-3
7	PCuMo₁₁/MG-800	10	1∶2	80	乙醇	20min	74	111×10^-3
8	PCuMo₁₁/MG-800	10	1∶3	70	乙醇	20min	75	113×10^-3
9	PCuMo₁₁/MG-800	10	1∶3	60	乙醇	20min	37	56×10^-3
10	PCuMo₁₁/MG-800	10	1∶3	80	环己烷	20min	54	81×10^-3
11	PCuMo₁₁/MG-800	10	1∶3	80	甲苯	20min	95	143×10^-3
12	PCuMo₁₁/MG-800	5	1∶3	80	乙醇	20min	90	270×10^-3
13	PCuMo₁₁/MG-800	15	1∶3	80	乙醇	15min	100	133×10^-3

[1]	陈子朝, 何方书, 胡强, 杨扬, 陈汉平, 杨海平. 甲烷干重整抗积炭Ni基催化剂研究进展[J]. 化工进展, 2025, 44(9): 4968-4978.
[2]	王振, 张耀远, 吴芹, 史大昕, 陈康成, 黎汉生. 甲烷干重整用Ni/Al₂O₃基催化剂研究进展[J]. 化工进展, 2025, 44(9): 4979-4998.
[3]	张海鹏, 秦珊珊, 王俣萱, 于海彪. 3.0F-Ag _x Co催化剂的制备及其催化分解N₂O[J]. 化工进展, 2025, 44(9): 4999-5005.
[4]	孙梦圆, 陆诗建, 刘玲, 薛艳阳, 张云蓉, 董琦, 康国俊. 金属有机框架及衍生物在碳捕集领域的研究进展[J]. 化工进展, 2025, 44(9): 5339-5350.
[5]	王文君, 刘瑞鑫, 王军, 张庆磊, 侯立安. 浅析二氧化钛材料可见光降解室内VOCs的研究进展[J]. 化工进展, 2025, 44(9): 5351-5362.
[6]	曾金, 高艳, 王赵鹏, 谢雨芸, 刘俊, 梁旗, 王春英. NaYF₄:Yb,Tm复合TiO₂/Bi₂WO₆光催化降解2,4-二氯苯氧乙酸机制及产物毒性评价[J]. 化工进展, 2025, 44(9): 5416-5431.
[7]	李艳平, 杨涛, 王洪勋, 张城, 温国胜, 韩治成, 蓝公家, 严大洲. 三氯氢硅在氢气氛中的热分解及还原体系的反应分子动力学模拟[J]. 化工进展, 2025, 44(8): 4322-4330.
[8]	赵用明, 卜亿峰, 王涛, 杜冰, 门卓武. 费托合成催化剂动态置换与稳态工艺的集成优化[J]. 化工进展, 2025, 44(8): 4536-4544.
[9]	张巍, 梁垚城, 伍乔, 付业昊, 尹艳山, 成珊, 阮敏, 刘涛, 周昭仪, 张凯凯, 李丹聪. 基于金属离子改性的Cu-SSZ-13催化剂在NH₃-SCR脱硝中的应用[J]. 化工进展, 2025, 44(7): 3879-3891.
[10]	王惠, 刘家旭. SSZ-39分子筛的合成及其NH₃-SCR应用研究进展[J]. 化工进展, 2025, 44(7): 3892-3906.
[11]	卢朋, 张迪, 刘瑶瑶, 于万金, 刘武灿, 张建君. 气相脱氟化氢合成C₂氢氟烯烃催化剂的研究进展[J]. 化工进展, 2025, 44(7): 3907-3916.
[12]	高姣姣, 颜诗宇, 杨太顺, 谢尚志, 杨艳娟, 徐晶. 不同晶型Al₂O₃负载Ru催化剂对聚乙烯氢解的影响[J]. 化工进展, 2025, 44(7): 3917-3927.
[13]	陈东健, 孙雨倩, 银凤翔. FeNi₃-Fe₃O₄/CN催化剂的制备及其电催化析氧性能[J]. 化工进展, 2025, 44(7): 3928-3937.
[14]	于宁, 王秋月, 王志才, 高子怡, 柴永明, 董斌. 双位点协同调控增强钙钛矿氧化物的水氧化活性[J]. 化工进展, 2025, 44(7): 3976-3984.
[15]	刘文龙, 马秀清, 李长金, 何东洋, 高觊兴, 张杨, 李满意, 杨卫民, 李好义. LDPE/PEW熔喷超细纤维及其非织造布性能[J]. 化工进展, 2025, 44(7): 4032-4038.