MIL-101负载Ni@Pd核壳纳米粒子催化芳香硝基类化合物加氢

引用本文: 简思平, 李映伟. MIL-101负载Ni@Pd核壳纳米粒子催化芳香硝基类化合物加氢[J]. 催化学报, 2016, 37(1): 91-97. doi: 10.1016/S1872-2067(15)60940-8 shu

Citation: Siping Jian, Yingwei Li. Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction[J]. Chinese Journal of Catalysis, 2016, 37(1): 91-97. doi: 10.1016/S1872-2067(15)60940-8 shu

MIL-101负载Ni@Pd核壳纳米粒子催化芳香硝基类化合物加氢

简思平 ,
李映伟 ^,

1.
华南理工大学化学与化工学院, 制浆造纸工程国家重点实验室, 广东广州510640

通讯作者: 李映伟

基金项目:
国家自然科学基金(21322606, 21436005) (21322606, 21436005)

高等学校博士学科点专项科研基金(20120172110012) (20120172110012)

华南理工大学中央高校基本科研业务费专项资金

广东省自然科学基金(S2011020002397, 2013B090500027). (S2011020002397, 2013B090500027)

摘要: 金属有机骨架(MOFs)材料是一种新型的沸石类多孔材料,是由金属离子和有机配体通过配位键键合而成的拓扑结构.相比其他多孔材料,MOFs拥有更高的比表面积、孔隙率以及结构可调控性.在催化方面,MOFs复合材料在多相催化领域已经引起了广泛的研究兴趣.贵金属纳米颗粒是一种在化学、化工、生物和医学等许多领域有着广泛应用的高性能材料.但是,催化反应往往都是发生在纳米颗粒的表面,而位于颗粒内部的金属没能得到利用;从原子经济性的角度来看,以廉价金属作核、贵金属作壳的双金属纳米粒子能有效解决这个问题,而且还能利用双金属之间的协调作用.目前文献中也已经报道了多种非贵金属和贵金属组成的核壳双金属纳米粒子,都展现出了比单纯贵金属更好的催化活性.
芳香胺类化合物是一种在工业上非常重要的有机中间体,广泛应用于农药、药物、染料和色素等等.目前,商业化生产的芳香胺化合物都是通过计量的还原剂,如连二硫酸钠、硼氢化钠、水合肼和氨水中的铁、锡、锌等非催化还原相应的芳硝基化合物得到,这样往往会带来严重的环境污染问题.而通过多相催化加氢还原方法来制备芳香胺化合物,不仅能高效催化芳硝基化合物加氢,而且催化剂可以回收利用,大大降低反应对环境的污染.
本文综合贵金属原子经济观点和芳硝基类化合物加氢反应催化剂设计,在油胺和三正辛基膦中通过热还原二价的镍和钯,制备出以Ni为核Pd为壳的双金属纳米粒子.通过透射电镜观察,镍钯核壳纳米粒子的粒径约为8-9nm.选用具有高比表面积和高稳定性的金属有机骨架材料MIL-101作为载体,通过浸渍法首次将镍钯核壳纳米粒子负载在MIL-101上制备出不同Ni:Pd比的Ni@Pd/MIL-101复合材料.利用X射线粉末衍射(XRD)、N₂吸附-脱附、红外光谱、透射电子显微镜和X射线能谱对复合材料结构进行了表征.从XRD谱图能看出负载纳米粒子后的MIL-101材料结构依然保持完整,表明催化剂制备过程不会破坏载体结构.红外光谱测试结果表明,负载了镍钯纳米粒子的Ni@Pd/MIL-101复合材料中含有两种C-H键伸缩振动2852和2926cm^-¹处两个特征峰,分别对应于-CH₂-和-CH₃中C-H键的特征吸收峰,可能是残留的油胺,也可能是三正辛基膦在与镍和钯形成配合物时的残留.X射线能谱测试发现,N元素在负载后已不存在,而P元素依旧存在,结合红外光谱可以确认,纳米粒子在负载前后三正辛基膦依然与纳米粒子稳定络合,进而可被MIL-101上未饱和的Cr固定.通过透射电镜可以观察到镍钯核壳纳米粒子高度分散在载体上.
将Ni@Pd/MIL-101材料应用于硝基苯催化加氢反应.在30℃,0.1MPaH₂条件下,0.26%Ni@0.46%Pd/MIL-101催化剂具有最高的加氢活性,其转换频率(TOF)值最高可达375h^-1,是单金属负载钯催化剂的近2倍,展示出非贵金属替代部分贵金属的可行性.在循环使用方面,重复使用5次后的Ni@Pd/MIL-101催化剂依然保持较高的催化活性和选择性.同时考察了底物的兼容性,该催化体系对多种不同基团(包括不饱和基团)取代的硝基苯化合物的催化加氢,大都表现出很高的催化活性和选择性,TOF值最高可达495h^-1.

关键词:

English

Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction

Siping Jian ,
Yingwei Li ^,

1.
State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guanzhou 510640, Guangdong, China;

Corresponding author: 李映伟

Received Date: 07 June 2015
Fund Project:
国家自然科学基金(21322606, 21436005)

高等学校博士学科点专项科研基金(20120172110012)

华南理工大学中央高校基本科研业务费专项资金

广东省自然科学基金(S2011020002397, 2013B090500027).

Abstract: Ni@Pd core-shell nanoparticles with a mean particle size of 8-9 nm were prepared by solvothermal reduction of bivalent nickel and palladium in oleylamine and trioctylphosphine. Subsequently, the first-ever deposition of Ni@Pd core-shell nanoparticles having different compositions on a metal-organic framework (MIL-101) was accomplished by wet impregnation in n-hexane. The Ni@Pd/MIL-101 materials were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy and also investigated as catalysts for the hydrogenation of nitrobenzene under mild reaction conditions. At 30 ℃ and 0.1 MPa of H₂ pressure, the Ni@Pd/MIL-101 gives a TOF as high as 375 h^-1 for the hydrogenation of nitrobenzene and is applicable to a wide range of substituted nitroarenes. The exceptional performance of this catalyst is believed to result from the significant Ni-Pd interaction in the core-shell structure, together with promotion of the conversions of aromatics by uncoordinated Lewis acidic Cr sites on the MIL-101 support.

Key words:

1. [1] J. L. Pinilla, A. B. García, K. Philippot, P. Lara, E. J. García-Suárez, M. Millan, Fuel, 2014, 116, 729.[1] J. L. Pinilla, A. B. García, K. Philippot, P. Lara, E. J. García-Suárez, M. Millan, Fuel, 2014, 116, 729.
2. [2] G. Z. Chen, S. J. Wu, H. L. Liu, H. F. Jiang, Y. W. Li, Green Chem., 2013, 15, 230.[2] G. Z. Chen, S. J. Wu, H. L. Liu, H. F. Jiang, Y. W. Li, Green Chem., 2013, 15, 230.
3. [3] B. Z. Yuan, Y. Y. Pan, Y. W. Li, B. L. Yin, H. F. Jiang, Angew. Chem. Int. Ed., 2010, 49, 4054.[3] B. Z. Yuan, Y. Y. Pan, Y. W. Li, B. L. Yin, H. F. Jiang, Angew. Chem. Int. Ed., 2010, 49, 4054.
4. [4] F. R. Wang, S. S. Tang, Y. H. Yu, L. F. Wang, B. L .Yin, X H. Li, Chin. J. Catal., 2014, 35, 1921.[4] F. R. Wang, S. S. Tang, Y. H. Yu, L. F. Wang, B. L .Yin, X H. Li, Chin. J. Catal., 2014, 35, 1921.
5. [5] M. R. Nabid, Y. Bide, N. Ghalavand, M. Niknezhad, Appl. Organomet. Chem., 2014, 28, 389.[5] M. R. Nabid, Y. Bide, N. Ghalavand, M. Niknezhad, Appl. Organomet. Chem., 2014, 28, 389.
6. [6] R. Ghosh Chaudhuri, S. Paria, Chem. Rev., 2012, 112, 2373.[6] R. Ghosh Chaudhuri, S. Paria, Chem. Rev., 2012, 112, 2373.
7. [7] Y. Z. Chen, Q. Xu, S. H. Yu, H. L. Jiang, Small, 2015, 11, 71.[7] Y. Z. Chen, Q. Xu, S. H. Yu, H. L. Jiang, Small, 2015, 11, 71.
8. [8] P. P. Zhang, Y. B. Hu, B. H. Li, Q. J. Zhang, C. Zhou, H. B. Yu, X. J. Zhang, L. Chen, B. Eichhorn, S. H. Zhou, ACS Catal., 2015, 5, 1335.[8] P. P. Zhang, Y. B. Hu, B. H. Li, Q. J. Zhang, C. Zhou, H. B. Yu, X. J. Zhang, L. Chen, B. Eichhorn, S. H. Zhou, ACS Catal., 2015, 5, 1335.
9. [9] Q. Sun, X. Q. Zhang, Y. Wang, A. H. Lu, Chin. J. Catal., 2015, 36, 683.[9] Q. Sun, X. Q. Zhang, Y. Wang, A. H. Lu, Chin. J. Catal., 2015, 36, 683.
10. [10] J. Hermannsdörfer, M. Friedrich, N. Miyajima, R. Q. Albuquerque, S. Kümmel, R. Kempe, Angew. Chem. Int. Ed., 2012, 51, 11473.[10] J. Hermannsdörfer, M. Friedrich, N. Miyajima, R. Q. Albuquerque, S. Kümmel, R. Kempe, Angew. Chem. Int. Ed., 2012, 51, 11473.
11. [11] S. U. Son, Y. Jang, J. Park, H. B. Na, H. M. Park, H. J. Yun, J. Lee, T. Hyeon, J. Am. Chem. Soc., 2004, 126, 5026.[11] S. U. Son, Y. Jang, J. Park, H. B. Na, H. M. Park, H. J. Yun, J. Lee, T. Hyeon, J. Am. Chem. Soc., 2004, 126, 5026.
12. [12] R. Massard, D. Uzio, C. Thomazeau, C. Pichon, J. L. Rousset, J. C.. Bertolini, J. Catal., 2007, 245, 133.[12] R. Massard, D. Uzio, C. Thomazeau, C. Pichon, J. L. Rousset, J. C.. Bertolini, J. Catal., 2007, 245, 133.
13. [13] M. M. Zhang, Z. X. Yan, Q. Sun, J. M. Xie, J. J. Jing, New J. Chem., 2012, 36, 2533.[13] M. M. Zhang, Z. X. Yan, Q. Sun, J. M. Xie, J. J. Jing, New J. Chem., 2012, 36, 2533.
14. [14] O. Metin, S. F. Ho, C. Alp, H. Can, M. N. Mankin, M. S. Gültekin, M. F. Chi, S. H. Sun, Nano Res., 2013, 6, 10.[14] O. Metin, S. F. Ho, C. Alp, H. Can, M. N. Mankin, M. S. Gültekin, M. F. Chi, S. H. Sun, Nano Res., 2013, 6, 10.
15. [15] H. S. Wei, X. Y. Liu, A. Q. Wang, L. L. Zhang, B. T. Qiao, X. F. Yang, Y. Q. Huang, S. Miao, J. Y. Liu, T. Zhang, Nat. Commun., 2014, 5, 5634.[15] H. S. Wei, X. Y. Liu, A. Q. Wang, L. L. Zhang, B. T. Qiao, X. F. Yang, Y. Q. Huang, S. Miao, J. Y. Liu, T. Zhang, Nat. Commun., 2014, 5, 5634.
16. [16] K. I. Shimizu, Y. Miyamoto, T. Kawasaki, T. Tanji, Y. Tai, A. Satsuma, J. Phys. Chem. C, 2009, 113, 17803.[16] K. I. Shimizu, Y. Miyamoto, T. Kawasaki, T. Tanji, Y. Tai, A. Satsuma, J. Phys. Chem. C, 2009, 113, 17803.
17. [17] W. W. Lin, H. Y. Cheng, J. Ming, Y. C. Yu, F. Y. Zhao, J. Catal., 2012, 291, 149.[17] W. W. Lin, H. Y. Cheng, J. Ming, Y. C. Yu, F. Y. Zhao, J. Catal., 2012, 291, 149.
18. [18] W. C. Du, G. Z. Chen, R. F. Nie, Y. W. Li, Z. Y. Hou, Catal. Commun., 2013, 41, 56.[18] W. C. Du, G. Z. Chen, R. F. Nie, Y. W. Li, Z. Y. Hou, Catal. Commun., 2013, 41, 56.
19. [19] K. Fuku, T. Sakano, T. Kamegawa, K. Mori, H. Yamashita, J. Mater. Chem., 2012, 22, 16243.[19] K. Fuku, T. Sakano, T. Kamegawa, K. Mori, H. Yamashita, J. Mater. Chem., 2012, 22, 16243.
20. [20] E. Kim, H. S. Jeong, B. M. Kim, Catal. Commun., 2014, 45, 25.[20] E. Kim, H. S. Jeong, B. M. Kim, Catal. Commun., 2014, 45, 25.
21. [21] J. R. Niu, X. Huo, F. W. Zhang, H. B. Wang, P. Zhao, W. Q. Hu, J. T. Ma, R. Li, ChemCatChem, 2013, 5, 349.[21] J. R. Niu, X. Huo, F. W. Zhang, H. B. Wang, P. Zhao, W. Q. Hu, J. T. Ma, R. Li, ChemCatChem, 2013, 5, 349.
22. [22] G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surblé, I. Margiolaki, Science, 2005, 309, 2040.[22] G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surblé, I. Margiolaki, Science, 2005, 309, 2040.
23. [23] H. L. Liu, Y. W. Li, H. F. Jiang, C. Vargas, R. Luque, Chem. Commun., 2012, 48, 8431.[23] H. L. Liu, Y. W. Li, H. F. Jiang, C. Vargas, R. Luque, Chem. Commun., 2012, 48, 8431.
24. [24] Y. Y. Pan, B. Z. Yuan, Y. W. Li, D. H. He, Chem. Commun., 2010, 46, 2280.[24] Y. Y. Pan, B. Z. Yuan, Y. W. Li, D. H. He, Chem. Commun., 2010, 46, 2280.
25. [25] Y. K. Hwang, D. Y. Hong, J. S. Chang, S. H. Jhung, Y. K. Seo, J. Kim, A. Vimont, M. Daturi, C. Serre, G. Férey, Angew. Chem. Int. Ed., 2008, 47, 4144.[25] Y. K. Hwang, D. Y. Hong, J. S. Chang, S. H. Jhung, Y. K. Seo, J. Kim, A. Vimont, M. Daturi, C. Serre, G. Férey, Angew. Chem. Int. Ed., 2008, 47, 4144.
26. [26] M. M. Zhang, Z. X. Yan, J. M. Xie, Electrochim. Acta, 2012, 77, 237.[26] M. M. Zhang, Z. X. Yan, J. M. Xie, Electrochim. Acta, 2012, 77, 237.
27. [27] Y. Pan, H. Y. Bai, L. Pan, Y. D. Li, M. C. Tamargo, M. Sohel, J. R.. Lombardi, J. Mater. Chem., 2012, 22, 23593.[27] Y. Pan, H. Y. Bai, L. Pan, Y. D. Li, M. C. Tamargo, M. Sohel, J. R.. Lombardi, J. Mater. Chem., 2012, 22, 23593.
28. [28] Y. Wu, D. S. Wang, Z. Q. Niu, P. C. Chen, G. Zhou, Y. D. Li, Angew. Chem. Int. Ed., 2012, 51, 12524.[28] Y. Wu, D. S. Wang, Z. Q. Niu, P. C. Chen, G. Zhou, Y. D. Li, Angew. Chem. Int. Ed., 2012, 51, 12524.
29. [29] P. Wang, F. W. Zhang, Y. Long, M. Xie, R. Li, J. T. Ma, Catal. Sci. Technol., 2013, 3, 1618.[29] P. Wang, F. W. Zhang, Y. Long, M. Xie, R. Li, J. T. Ma, Catal. Sci. Technol., 2013, 3, 1618.
30. [30] Z. K. Zhao, H. L. Yang, Y. Li, RSC Adv., 2014, 4, 22669.[30] Z. K. Zhao, H. L. Yang, Y. Li, RSC Adv., 2014, 4, 22669.

扫一扫看文章

计量

PDF下载量: 1
文章访问数: 873
HTML全文浏览量: 119

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

MIL-101负载Ni@Pd核壳纳米粒子催化芳香硝基类化合物加氢

通讯作者: 李映伟

English

Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction

Corresponding author: 李映伟

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

MIL-101负载Ni@Pd核壳纳米粒子催化芳香硝基类化合物加氢

通讯作者: 李映伟

English

Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction

Corresponding author: 李映伟

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

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs