碳膜包覆的氧化铁纳米颗粒:一种高效的芳硝基化合物加氢催化剂

引用本文: 王莹钰, 石娟娟, 张子豪, 傅杰, 吕秀阳, 侯昭胤. 碳膜包覆的氧化铁纳米颗粒:一种高效的芳硝基化合物加氢催化剂[J]. 催化学报, 2017, 38(11): 1909-1917. doi: 10.1016/S1872-2067(17)62917-6 shu

Citation: Yingyu Wang, Juanjuan Shi, Zihao Zhang, Jie Fu, Xiuyang Lü, Zhaoyin Hou. Carbon film encapsulated Fe₂O₃:An efficient catalyst for hydrogenation of nitroarenes[J]. Chinese Journal of Catalysis, 2017, 38(11): 1909-1917. doi: 10.1016/S1872-2067(17)62917-6 shu

碳膜包覆的氧化铁纳米颗粒:一种高效的芳硝基化合物加氢催化剂

王莹钰 ^a, ,
石娟娟 ^a, ,
张子豪 ^b, ,
傅杰 ^b, ,
吕秀阳 ^b, ,
侯昭胤 ^a,

a 浙江大学化学系, 生物质化工教育部重点实验室, 浙江杭州 310028;
b 浙江大学化学与生物工程学院, 浙江杭州 310027
基金项目:
国家自然科学基金（21473155，21273198）；浙江省自然科学基金（LZ12B03001）.

摘要: 铁是地球上最丰富的元素之一，它在生命反应中起到至关重要的作用.目前，铁基催化剂广泛应用于合成氨、费托合成、NO_x的选择性催化还原等.最近，铁因其含量丰富、价格低廉、无毒等优势而在多相催化方面引起了重点关注.最新研究发现，铁基催化剂在甲烷直接偶联制乙烯、氧还原以及芳硝基化合物的选择性加氢等领域具有突出表现，其中芳硝基化合物选择性加氢是一类具有重要应用前景的反应，这是因为苯胺（AN）是一种重要的精细化学品和有机中间体，广泛用于医药、染料、农药等行业，苯胺的年产量超过了400万吨，目前使用的催化剂主要有Raney Ni、负载镍、Ru/SnO₂及少量铂碳、钯碳催化剂.但是，在Ni基催化剂上，硝基苯加氢主要经过间接缩合途径，同时会伴有氧化偶氮苯（AOB）、偶氮苯（AB）和氢化偶氮苯（HAB）等副产物生成，这些高沸点的副产物会带来一系列问题，如产物分离困难、产品纯度较低以及催化剂失活等.在这种情况下，为了加速苯胺生成，工业上一般采用过量的Raney Ni催化剂.贵金属（如Pt，Pd和Ru等）对催化芳硝基化合物加氢具有极高的活性，且苯胺的生成主要经过直接加氢途径.然而，由于成本过高，贵金属催化剂的大规模应用还存在一定的困难.
本文采用简易的方法制备了一种铁基催化剂，在这个催化剂中氧化铁纳米颗粒被碳膜包覆并嵌入至平板碳中（Fe₂O₃@G-C）.该催化剂由活性炭、苯胺及醋酸亚铁热解所得.通过扫描电镜（SEM）、拉曼光谱（Raman）及X射线衍射（XRD）分析，我们证实在原始碳颗粒上形成了新的碳膜.同时高倍透射电镜图也清楚地揭示了氧化铁纳米颗粒被碳膜包覆的结构.实验发现，Fe₂O₃@G-C-900催化剂（900 ℃热解所得）在芳硝基化合物选择性加氢反应中具有很高的活性.在2 MPa H₂，70 ℃条件下反应2 h，硝基苯（NB）转化率达到95.4%，苯胺选择性达到99.1%，远远高于其他载体（活性炭、SiO₂、Al₂O₃和MgO）负载的铁基催化剂.表征结果发现，Fe₂O₃@G-C-900催化剂的高活性可能与其具有较大的比表面积（573.7 m²/g）、孔体积（0.22 cm³/g，孔径小于2 nm）、高度分散的氧化铁纳米颗粒以及氧化铁纳米颗粒和其表面碳膜的协同作用密切相关.此外，催化剂中引入的氮原子不仅可以在包覆的碳膜上形成缺陷，也能进一步增强包覆在氧化铁纳米颗粒表面的碳膜的催化活性.通过对Fe₂O₃@G-C-900催化剂在硝基苯加氢反应中的循环使用活性的考察，发现该催化剂在循环使用5次后，仍具有良好的活性.更重要的是，在Fe₂O₃@G-C-900催化剂上硝基苯的加氢主要是直接途径，反应中没有高沸点AOB，AB和HAB等副产物生成.
鉴于Fe₂O₃@G-C-900催化剂对NB加氢具有优异的活性，我们还进行了一系列含有不同取代基团的芳硝基化合物的加氢实验，发现对位取代的底物相对于间位及邻位的底物更容易发生加氢还原反应，这应归因于该催化剂的孔径较小（0.52nm）.这些研究方法可以扩展至其他金属催化剂的制备，以促进高效益和可持续的工业生产的发展.

关键词:

碳膜
/ 封装
/ 铁催化
/ 热解
/ 加氢
/ 芳硝基化合物

English

Carbon film encapsulated Fe₂O₃:An efficient catalyst for hydrogenation of nitroarenes

a Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China;
b Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
Received Date: 02 August 2017
Revised Date: 17 September 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21473155, 21273198) and Natural Science Foundation of Zhejiang Province (LZ12B03001).

Abstract: Iron catalysis has attracted a wealth of interdependent research for its abundance, low price, and nontoxicity. Herein, a convenient and stable iron oxide (Fe₂O₃)-based catalyst, in which active Fe₂O₃ nanoparticles (NPs) were embedded into carbon films, was prepared via the pyrolysis of iron-polyaniline complexes on carbon particles. The obtained catalyst shows a large surface area, uniform pore channel distribution, with the Fe₂O₃ NPs homogeneously dispersed across the hybrid material. Scanning electron microscopy, Raman spectroscopy and X-ray diffraction analyses of the catalyst prepared at 900℃ (Fe₂O₃@G-C-900) and an acid-pretreated commercial activated carbon confirmed that additional carbon materials formed on the pristine carbon particles. Observation of high-resolution transmission electron microscopy images also revealed that the Fe₂O₃ NPs in the hybrid were encapsulated by a thin carbon film. The Fe₂O₃@G-C-900 composite was highly active and stable for the direct selective hydrogenation of nitroarenes to anilines under mild conditions, where previously noble metals were required. The synthetic strategy and the structure of the iron oxide-based composite may lead to the advancement of cost-effective and sustainable industrial processes.

Key words:

1. [1] P. A. Frey, G. H. Reed, ACS Chem. Biol., 2012, 7, 1477-1481.
2. [2] G. Papanikolaou, K. Pantopoulos, Toxicol. Appl. Pharmacol., 2005, 202, 199-211.
3. [3] A. C. Rosenzweig, H. Brandstetter, D. A. Whittington, P. Nordlund, S. J. Lippard, C. A. Frederick, Proteins:Struc., Funct., Genetics, 1997, 29, 141-152.
4. [4] Q. Fu, W. X. Li, Y. X. Yao, H. Y. Liu, H. Y. Su, D. Ma, X. K. Gu, L. M. Chen, Z. Wang, H. Zhang, B. Wang, X. H. Bao, Science, 2010, 328, 1141-1144.
5. [5] R. Schlögl, Angew. Chem. Int. Ed., 2003, 42, 2004-2008.
6. [6] T. Kandemir, M. E. Schuster, A. Senyshyn, M. Behrens, R. Schlöegl, Angew. Chem. Int. Ed., 2013, 52, 12723-12726.
7. [7] A. Vojvodic, A. J. Medford, F. Studt, F. Abild-Pedersen, T. S. Khan, T. Bligaard, J. K. Nörskov, Chem. Phys. Lett., 2014, 598, 108-112.
8. [8] X. Q. Chen, D. H Deng, X. L. Pan, X. H. Bao, Chin. J. Catal., 2015, 36, 1631-1637.
9. [9] X. H. Gao, J. L. Zhang, N. Chen, Q. X. Ma, S. B. Fan, T. S. Zhao, N. Tsu-baki, Chin. J. Catal., 2016, 37, 510-516.
10. [10] Y. Xia, W. C. Zhan, Y. Guo, Y. L. Guo, G. Z. Lu, Chin. J. Catal., 2016, 37, 2069-2078.
11. [11] X. B. Wang, S. G. Wu, W. X. Zou, S. H. Yu, K. T. Gui, L. Dong, Chin. J. Catal., 2016, 37, 1314-1323.
12. [12] X. Y. Shi, H. He, L. J. Xie, Chin. J. Catal., 2015, 36, 649-656.
13. [13] X. G. Guo, G. Z. Fang, G. Li, H. Ma, H. J. Fan, L. Yu, C. Ma, X. Wu, D. H. Deng, M. M. Wei, D. L. Tan, R. Si, S. Zhang, J. Q. Li, L. T. Sun, Z. C. Tang, X. L. Pan, X. H. Bao, Science, 2014, 344, 616-619.
14. [14] M. Lefevre, E. Proietti, F. Jaouen, J. P. Dodelet, Science, 2009, 324, 71-74.
15. [15] R. V. Jagadeesh, A. E. Surkus, H. Junge, M. M. Pohl, J. Radnik, J. Rabeah, H. Huan, V. Schunemann, A. Brükner, M. Beller, Science, 2013, 342, 1073-1076.
16. [16] H. U. Blaser, Science, 2006, 313, 312-313.
17. [17] C. H. Li, Z. X. Yu, K. F. Yao, S. F. Ji, J. Liang, J. Mol. Catal. A, 2005, 226, 101-105.
18. [18] A. S. Travis, in:Z. Rappoport ed., The Chemistry of Anilines, John Wiley and Sons, Hoboken, 2007, 715-782.
19. [19] X. H. Yan, J. Q. Sun, Y. W. Wang, J. F. Yang, J. Mol. Catal. A, 2006, 252, 17-22.
20. [20] J. Xiong, J. X. Chen, J. Y. Zhang, Catal. Commun., 2007, 8, 345-350.
21. [21] J. H. Wang, Z. L. Yuan, R. F. Nie, Z. Y. Hou, X. M. Zheng, Ind. Eng. Chem. Res., 2010, 49, 4664-4669.
22. [22] B. J. Zuo, Y. Wang, Q. L. Wang, J. L. Zhang, N. Z. Wu, L. D. Peng, L. L. Gui, X. D. Wang, R. M. Wang, D. P. Yu, J. Catal., 2004, 222, 493-498.
23. [23] R. F. Nie, J. H. Wang, L. N. Wang, Y. Qin, P. Chen, Z. Y. Hou, Carbon, 2012, 50, 586-596.
24. [24] A. Corma, P. Concepcion, P. Serna, Angew. Chem. Int. Ed., 2007, 46, 7266-7269.
25. [25] V. Höller, D. Wegricht, I. Yuranov, L. Kiwi-Minsker, A. Renken, Chem. Eng. Technol., 2000, 23, 251-255.
26. [26] A. Corma, P. Serna, Science, 2006, 313, 332-334.
27. [27] X. C. Meng, H. Y. Cheng, Y. Akiyama, Y. F. Hao, W. B. Qiao, Y. C. Yu, F. Y. Zhao, S. I. Fujita, M. Arai, J. Catal., 2009, 264, 1-10.
28. [28] W. C. Du, S. X. Xia, R. F. Nie, Z. Y. Hou, Ind. Eng. Chem. Res., 2014, 53, 4589-4594.
29. [29] R. F. Nie, J. J. Shi, W. C. Du, W. S. Ning, Z. Y. Hou, F. S. Xiao, J. Mater. Chem. A, 2013, 1, 9037-9045.
30. [30] X. Y. Zeng, C. H. You, L. M. Leng, D. Dang, X. C. Qiao, X. H. Li, Y. W. Li, S. J. Liao, R. R. Adzic, J. Mater. Chem. A, 2015, 3, 11224-11231.
31. [31] J. L. Chen, X. P. Yan, J. Mater. Chem., 2010, 20, 4328-4332.
32. [32] J. J. Shi, M. S. Zhao, Y. Y. Wang, J. Fu, X. Y. Lu, Z. Y. Hou, J. Mater. Chem. A, 2016, 4, 5842-5848.
33. [33] Z. S. Wu, A. Winter, L. Chen, Y. Sun, A. Turchanin, X. L. Feng, K. Müllen, Adv. Mater., 2012, 24, 5130-5135.
34. [34] P. Chen, T. Y. Xiao, Y. H. Qian, S. S. Li, S. H. Yu, Adv. Mater., 2013, 25, 3192-3196.
35. [35] J. J. Shi, Y. Y. Wang, W. C. Du, Z. Y. Hou, Carbon, 2016, 99, 330-337.
36. [36] J. K. Hu, M. Noked, E. Gillette, F. D. Han, Z. Gui, C. S. Wang, S. B. Lee, J. Mater. Chem. A, 2015, 3, 21501-21510.
37. [37] M. L. Xiao, J. B. Zhu, L. G. Feng, C. P. Liu, W. Xing, Adv. Mater., 2015, 27, 2521-2527.
38. [38] Q. G. He, Q. Li, S. Khene, X. M. Ren, F. E. López-Suárez, D. Loza-no-Castelló, A. Bueno-López, G. Wu, J. Phys. Chem. C, 2013, 117, 8697-8707.
39. [39] G. Wu, K. L. More, P. Xu, H. L. Wang, M. Ferrandon, A. J. Kropf, D. J. Myers, S. G. Ma, C. M. Johnston, P. Zelenay, Chem. Commun., 2013, 49, 3291-3293.
40. [40] R. V. Jagadeesh, K. Natte, H. Junge, M. Beller, ACS Catal., 2015, 5, 1526-1529.
41. [41] D. F. Su, J. Wang, H. Y. Jin, Y. T. Gong, M. M. Li, Z. F. Pang, Y. Wang, J. Mater. Chem. A, 2015, 3, 11756-11761.
42. [42] Y. Hu, J. O. Jensen, W. Zhang, L. N. Cleemann, W. Xing, N. J. Bjerrum, Q. F. Li, Angew. Chem. Int. Ed., 2014, 53, 3675-3679.
43. [43] D. H. Deng, L. Yu, X. Q. Chen, G. X. Wang, L. Jin, X. L. Pan, J. Deng, G. Q. Sun, X. H. Bao, Angew. Chem. Int. Ed., 2013, 52, 371-375.
44. [44] J. P. Paraknowitsch, A. Thomas, M. Antonietti, J. Mater. Chem., 2010, 20, 6746-6758.
45. [45] P. F. Zhang, Y. T. Gong, H. R. Li, Z. R. Chen, Y. Wang, Nat. Commun., 2013, 4, 1593.
46. [46] H. D. Burge, D. J. Collins, B. H. Davis, Ind. Eng. Chem. Prod. Res. Dev., 1980, 19, 389-391.

扫一扫看文章

计量

PDF下载量: 4
文章访问数: 745
HTML全文浏览量: 30

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

碳膜包覆的氧化铁纳米颗粒:一种高效的芳硝基化合物加氢催化剂

English

Carbon film encapsulated Fe₂O₃:An efficient catalyst for hydrogenation of nitroarenes

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

碳膜包覆的氧化铁纳米颗粒:一种高效的芳硝基化合物加氢催化剂

English

Carbon film encapsulated Fe2O3:An efficient catalyst for hydrogenation of nitroarenes

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Carbon film encapsulated Fe₂O₃:An efficient catalyst for hydrogenation of nitroarenes

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs