碳纳米管限域效应对肉桂醛选择加氢产物分布的影响

催化学报 ›› 2017, Vol. 38 ›› Issue (8): 1315-1321.

碳纳米管限域效应对肉桂醛选择加氢产物分布的影响

马宏飞^a,b,c,d, 于铁^b, 潘秀莲^b, 包信和^a,b,d

a 中国科学院上海高等研究院, 上海 201210;
b 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023;
c 中国科学院大学, 北京 100049;
d 上海科技大学, 上海 201210

收稿日期:2017-02-22 修回日期:2017-03-14 出版日期:2017-08-18 发布日期:2017-08-04
通讯作者: 潘秀莲, 包信和
基金资助:
国家自然科学基金（21621063，21425312）.

Confinement effect of carbon nanotubes on the product distribution of selective hydrogenation of cinnamaldehyde

Hongfei Ma^a,b,c,d, Tie Yu^b, Xiulian Pan^b, Xinhe Bao^a,b,d

a Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China;
b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c University of Chinese Academy of Sciences, Beijing 100049, China;
d ShanghaiTech University, Shanghai 201210, China

Received:2017-02-22 Revised:2017-03-14 Online:2017-08-18 Published:2017-08-04
Supported by:
The work was supported by the National Natural Science Foundation of China (21621063, 21425312).

摘要/Abstract

摘要：

碳纳米管因其独特的电子结构和性能引起了研究者们广泛的兴趣，尤其是它有序的纳米级管腔结构，可以为催化剂和催化反应提供一种独特的一维限域环境.碳纳米管的限域效应主要由于其管腔几何和电子结构可以使反应物发生富集、对金属纳米颗粒的尺寸限制以及对电子结构的调变作用.一系列研究表明，碳纳米管的限域效应可以对催化剂的活性进行调变，但是对产物选择性的影响方面研究得较少，特别是管径小于4 nm的碳纳米管的限域体系.
因此，本文以肉桂醛选择性加氢反应为探针，研究限域效应对产物选择性的影响规律.采用管径为1-3 nm的碳纳米管，基于气相填充的方法将Ru纳米团簇分散于碳纳米管的管腔中，得到碳纳米管限域的Ru催化剂（Ru@CNT）；采用浸渍法制备了碳纳米管管外壁负载的催化剂（Ru/CNT）来进行对比.肉桂醛含有共轭的C=C和C=O键，由于C=C键能低于C=O，前者更易发生加氢反应.结果表明，分散在碳纳米管外壁的Ru催化剂可以催化肉桂醛中的C=C加氢，得到氢化肉桂醛（HCAL）；而Ru@CNT催化剂不仅可以催化C=C加氢得到氢化肉桂醛HCAL，还可以催化C=O键加氢得到肉桂醇，以及氢化肉桂醇.通过高分辨透射电镜、拉曼、程序升温还原、程序升温脱附对催化剂进行了表征.发现碳纳米管限域的纳米团簇金属颗粒的粒径大约为1-2 nm，与管外负载的金属颗粒相近，但是Ru@CNT催化剂上仍有部分金属纳米团簇分布在管外壁，这可能是Ru@CNT催化剂上有C=C键加氢产物的一个原因.碳纳米管独特的限域效应促进了Ru物种的还原，在H₂气氛下管内Ru物种的还原温度比管外低20℃.金属与碳纳米管的内、外壁之间的电子相互作用，纳米管腔的空间限制作用及管腔富集作用可能是产物分布产生差异的原因.

关键词: 碳纳米管, 限域催化, 钌, 选择性加氢, 肉桂醛, 产物选择性调变

Abstract:

The catalytic activity of metal catalysts can be modulated by confinement within the channels of carbon nanotubes (CNTs). Here, we show that the product distribution of cinnamaldehyde hydrogenation can be modified by confinement of Ru nanoparticles in CNTs. A catalyst composed of Ru nanoparticles dispersed on the exterior walls of CNTs gave hydrocinnamaldehyde as product. In contrast, confinement of the Ru nanoparticles within CNT channels facilitated hydrogenation of C=O bonds and complete hydrogenation, and both cinnamyl alcohol and hydrocinnamyl alcohol formed in addition to hydrocinnamaldehyde. High-resolution transmission electron microscopy, Raman spectroscopy, hydrogen temperature-programmed reduction, and hydrogen temperature-programmed desorption were used to investigate the characteristics of the catalysts. The results indicate that the different interactions between the confined Ru nanoparticles and the exterior and interior walls of the CNTs, as well as spatial restriction and enrichment within the narrow channels likely play important roles in modulation of the product distribution.

Key words: Carbon nanotubes, Confined catalysis, Ruthenium, Selective hydrogenation, Cinnamaldehyde, Selectivity modulation

马宏飞, 于铁, 潘秀莲, 包信和. 碳纳米管限域效应对肉桂醛选择加氢产物分布的影响[J]. 催化学报, 2017, 38(8): 1315-1321.

Hongfei Ma, Tie Yu, Xiulian Pan, Xinhe Bao. Confinement effect of carbon nanotubes on the product distribution of selective hydrogenation of cinnamaldehyde[J]. Chinese Journal of Catalysis, 2017, 38(8): 1315-1321.

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参考文献

[1] P. M. Ajayan, Chem. Rev., 1999, 99, 1787-1799.
[2] D. Ugarte, A. Chatelain, W. A. de Heer, Science, 1996, 274, 1897-1899.
[3] L. Maggini, M. E. Fustos, T. W. Chamberlain, C. Cebrian, M. Natali, M. Pietraszkiewicz, O. Pietraszkiewicz, E. Szekely, K. Kamaras, L. De Cola, A. N. Khlobystov, Bonifazi D, Nanoscale, 2014, 6, 2887-2894.
[4] A. Pollack, S. Alnemrat, T. W. Chamberlain, A. N. Khlobystov, J. P. Hooper, S. Osswald, Small, 2014, 10, 5077-5086.
[5] W. Chen, X. L. Pan, X. H. Bao, J. Am. Chem. Soc., 2007, 129, 7421-7426.
[6] W. Chen, X. L. Pan, M. G. Willinger, D. S. Su, X. H. Bao, J. Am. Chem. Soc., 2006, 128, 3136-3137.
[7] M. Menon, A. N. Andriotis, G. E. Froudakis, Chem. Phys. Lett., 2000, 320, 425-434.
[8] S. J. Guo, X. L. Pan, H. L. Gao, Z. Q. Yang, J. J. Zhao, X. H. Bao, Chem. Eur. J., 2010, 16, 5379-5384.
[9] W. Chen, Z. L. Fan, X. L. Pan, X. H. Bao, J. Am. Chem. Soc., 2008, 130, 9414-9419.
[10] R. M. M. Abbaslou, A. Tavassoli, J. Soltan, A. K. Dalai, Appl. Catal. A, 2009, 367, 47-52.
[11] X. L. Pan, Z. L. Fan, W. Chen, Y. J. Ding, H. Y. Luo, X. H. Bao, Nat. Mater., 2007, 6, 507-511.
[12] X. Yang, W. B. Wang, L. P. Wu, X. J. Li, T. J. Wang, S. J. Liao, Appl. Catal. A, 2016, 526, 45-52.
[13] F. Zhang, F. Jiao, X. L. Pan, K. Gao, J. P. Xiao, S. Zhang, X. H. Bao. ACS Catal., 2015, 5, 1381-1385.
[14] E. Castillejos, P. J. Debouttiere, L. Roiban, A. Solhy, V. Martinez, Y. Kihn, O. Ersen, K. Philippot, B. Chaudret, P. Serp, Angew. Chem. Int. Ed., 2009, 48, 2529-2533.
[15] T. Trang Nguyen, P. Serp, ChemCatChem, 2013, 5, 3595-3603.
[16] H. B. Zhang, X. L. Pan, X. H. Bao, J. Energy Chem., 2013, 22, 251-256.
[17] F. Zhang, X. L. Pan, Y. F. Hu, L. Yu, X. Q. Chen, P. Jiang, H. B. Zhang, S. B. Deng, J. Zhang, T. B. Bolin, S. Zhang, Y. Y. Huang, X. H. Bao, Proc. Natl. Acad. Sci. USA, 2013, 110, 14861-14866.
[18] J. S. Qiu, H. Z. Zhang, X. N. Wang, H. M. Han, C. H. Liang, C. Li, React. Kinet. Catal. Lett., 2006, 88, 269-275.
[19] D. Wang, Y. J. Zhu, C. G. Tian, L. Wang, W. Zhou, Y. L. Dong, H. J. Yan, H. G. Fu, ChemCatChem, 2016, 8, 1718-1726.
[20] S. Galvagno, G. Capannelli, G. Neri, A. Donato, R. Pietropaolo J. Mol Catal., 1991, 64, 237-246.
[21] C. L. Liu, K. S. Kim, J. Baek, Y. M. Cho, S. W. Han, S. W. Kim, N. K. Min, Y. M. Choi, J. U. Kim, C. J. Lee, Carbon, 2009, 47, 1158-1164.
[22] Y. Wang, Z. M. Rong, Y. Wang, P. Zhang, Y. Wang, J. P. Qu, J. Catal., 2015, 329, 95-106.
[23] J. Guan, X. L. Pan, X. Liu, X. H. Bao, J. Phys. Chem. C, 2009, 113, 21687-21692.
[24] P. Kondratyuk, J. T. Yates Jr, Acc. Chem. Res., 2007, 40, 995-1004.