反应性模板剂诱导原位超交联法制备层次孔聚合物和碳材料

doi:10.6023/A15020099

化学学报 ›› 2015, Vol. 73 ›› Issue (6): 600-604.DOI: 10.6023/A15020099 上一篇下一篇

所属专题：共价有机多孔聚合物

研究通讯

反应性模板剂诱导原位超交联法制备层次孔聚合物和碳材料

蔡力锋^a,b, 陈鹭义^a, 梁业如^a, 陆志涛^a, 徐飞^a, 符若文^a, 吴丁财^a

a 中山大学化学与化学工程学院材料科学研究所教育部聚合物复合材料及功能材料重点实验室广州 510275;
b 莆田学院环境与生物工程学院莆田 351100

投稿日期:2015-02-04 发布日期:2015-04-21
通讯作者: 吴丁财 E-mail:wudc@mail.sysu.edu.cn
基金资助:
项目受广东省自然科学杰出青年基金项目(No. S2013050014408)、国家自然科学基金项目(Nos. 51422307, 51372280, 51173213, 51172290, 51232005)、中国博士后科学基金(No. 2014M560686).

Reactive-Template Induced in-situ Hypercrosslinking Procedure to Hierarchical Porous Polymer and Carbon Materials

Cai Lifeng^a,b, Chen Luyi^a, Liang Yeru^a, Lu Zhitao^a, Xu Fei^a, Fu Ruowen^a, Wu Dingcai^a

a Materials Science Institute, PCFM Laboratory, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, 510275;
b College of Environmental and Biological Engineering, Putian University, Putian, 351100

Received:2015-02-04 Published:2015-04-21
Supported by:
Project supported by the Guangdong Natural Science Funds for Distinguished Young Scholar (No. S2013050014408), the National Natural Science Foundation of China (Nos. 51422307, 51372280, 51173213, 51172290, 51232005), the China Postdoctoral Science Foundation (No. 2014M560686), the Program for New Century Excellent Talents in University (No. NCET-12-0572), the Program for Pearl River New Star of Science and Technology in Guangzhou (No. 2013J2200015), the National Key Basic Research Program of China (No. 2014CB932402) and the Science and technology project of the education department of Fujian province (No. JK2014043).

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摘要/Abstract

首先设计合成出新颖反应性SiO₂模板剂(即表面含苄基氯化学官能团的SiO₂纳米球), 然后利用1,4-对二氯苄(DCX)作为自交联功能单体, 成功地发展了一种“反应性模板剂诱导原位超交联法”制备层次孔聚合物(HPP)及其层次孔碳材料(HPC)的新思路: 一方面, DCX作为有机单体分子, 可与SiO₂纳米球表面的苄基氯化学官能团原位反应形成共价键, 极大地增强了聚合物前驱体和模板剂的相互作用力, 有利于模板剂的高度单分散和表面均匀包覆共价有机聚合物; 另一方面, DCX分子可以发生自交联反应, 免去交联剂的额外添加, 简化了制备流程. 利用该法所得HPP具有独特的微孔-中孔-大孔呈层次化分布的孔结构特征: 微孔壳-大孔腔空心纳米球之间相互交联堆叠形成丰富的中孔和大孔, 各层次纳米孔道紧密相连. 进一步地, HPP的共价有机骨架具有超交联化学结构, 可确保这类层次孔纳米结构在高温碳化过程中的稳定继承, 由此制得HPC, 其BET比表面积为756 m²·g^-1.

关键词: 反应性模板剂, 原位超交联, 自交联功能单体, 层次孔聚合物, 层次孔碳

Porous polymers have attracted increasing research interest because of their potential to merge the properties of both porous materials and organic polymers. As a novel class of porous polymers, hierarchical porous polymers (HPPs) that simultaneously possess micro-, meso-, and/or macropores are expected to exhibit the advantage of each class of hierarchical pores in a synergistic manner and thus are currently finding wide applications in many fields including energy, environment, catalysis, adsorption, and medicine. However, easy fabrication of well-defined hierarchical porous polymers remains a great challenge. Herein, we successfully developed a facile and effective procedure of reactive-template induced in-situ hypercrosslinking for fabrication of a novel class of hierarchical porous polymer. The key to this procedure is design and employment of SiO₂ nanospheres containing 4-(chloromethyl)phenyl groups as the reactive templates. The 4-(chloromethyl)phenyl groups on the surface of the reactive SiO₂ nanosphere templates can react with the self-crosslinkable monomer 1, 4-dichloro-p-xylol (DCX) to in-situ form a stable covalent bond at their interface. Such a strong covalent interaction facilitates the hypercrosslinking of DCX onto the surface of SiO₂ nanospheres, thus leading to high monodispersion of SiO₂ nanosphere templates and formation of uniform polymeric coating. The as-prepared HPP contains three types of pores: (i) micropores induced by hypercrosslinking of DCX, (ii) meso-/macroporous network formed through the crosslinking of reactive moiety on the periphery of colliding nanospheres with each other in various directions, and (iii) well-defined macropores obtained by removal of sacrificial silica nanospheres. Furthermore, the hypercrosslinked structure characteristic of HPP ensures good carbonization transformation and nanomorphology stability during heating treatment at high temperatures, leading to the formation of hierarchical porous carbon (HPC). New micropores of about 0.6 nm in diameter are generated during carbonization, possibly because of burn-off of noncarbon elements and carbon-containing compounds or disordered packing of microcrystalline carbon sheets and clusters. These HPP and HPC materials could hold considerable promise in applications as advanced adsorbents, catalyst supports, energy-storage materials and others. We hope that the reactive-template induced in-situ hypercrosslinking strategy may open the doors for preparation of various advanced hierarchical porous materials.

Key words: reactive template, in-situ hypercrosslinking, self-crosslinkable monomers, hierarchical porous polymer, hierarchical porous carbon

引用此文

蔡力锋, 陈鹭义, 梁业如, 陆志涛, 徐飞, 符若文, 吴丁财. 反应性模板剂诱导原位超交联法制备层次孔聚合物和碳材料[J]. 化学学报, 2015, 73(6): 600-604.

Cai Lifeng, Chen Luyi, Liang Yeru, Lu Zhitao, Xu Fei, Fu Ruowen, Wu Dingcai. Reactive-Template Induced in-situ Hypercrosslinking Procedure to Hierarchical Porous Polymer and Carbon Materials[J]. Acta Chim. Sinica, 2015, 73(6): 600-604.

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参考文献

[1] Wu, D. C.; Xu, F.; Sun, B.; Fu, R. W.; He, H. K.; Matyjaszewski, K. Chem. Rev. 2012, 112, 3959.
[2] Ding, S. Y.; Wang, W. Chem. Soc. Rev. 2013, 42, 548.
[3] Li, B.; Guan, Z.; Yang, X.; Wang, W. D.; Wang, W.; Hussain, I.; Song, K. P.; Tan, B. E.; Li, T. J. Mater. Chem. A 2014, 2, 11930.
[4] Chen, Q.; Liu, D. P.; Luo, M.; Feng, L. J.; Zhao, Y. C.; Han, B. H. Small 2014, 10, 308.
[5] Ben, T.; Ren, H.; Ma, S. Q.; Cao, D. P.; Lan, J. H.; Jing, X. F.; Wang, W. C.; Xu, J.; Deng, F.; Simmons, J. M.; Qiu, S. L.; Zhu, G. S. Angew. Chem. 2009, 121, 9621.
[6] Liu, S. H.; Wang, X. Q.; Huang, T. H.; Deng, Y. H.; Wu, Y.; Feng, S. H.; Bai, J. F.; Tian, Z. F. Chin. J. Org. Chem. 2015, 35, 390. (刘绍华, 王希庆, 黄天辉, 邓勇辉, 吴彦, 冯守爱, 白家峰, 田兆福, 有机化学, 2015, 35, 390.)
[7] Wang, W.; Yang, Z. J.; Yuan, Y.; Sun, F. X.; Zhao, M.; Ren, H.; Zhu, G. S. Acta Chim. Sinica 2014, 72, 557. (王维, 闫卓君, 元野, 孙福兴, 赵明, 任浩, 朱广山, 化学学报, 2014, 72, 557.)
[8] Lu, X.; Wu, R. X.; Li, B. B.; Zhu, Y. F.; Li, L. Q. Acta Chim. Sinica 2013, 71, 427. (陆霞, 吴仁香, 李波波, 朱云峰, 李李泉, 化学学报, 2013, 71, 427.)
[9] Liu, B.; Jin, Z. G.; Qu, X. Z.; Yang, Z. Z. Macromol. Rapid Commun. 2007, 28, 322.
[10] Li, Y.; Duan, G. T.; Liu, G. Q.; Cai, W. P. Chem. Soc. Rev. 2013, 42, 3614.
[11] Yang, H.; Jiang, P. Langmuir 2010, 26, 13173.
[12] Li, Z. H.; Wu, D. C.; Liang, Y. R.; Fu, R. W.; Matyjaszewski, K. J. Am. Chem. Soc. 2014, 136, 4805.

[13] Wang, G.; Dou, B. J.; Wang, J. H.; Wang, W. Q.; Hao, Z. P. RSC Adv. 2013, 3, 20523.
[14] Dawson, R.; Adams, D. J.; Cooper, A. I. Chem. Sci. 2011, 2, 1173.
[15] Grant, N. C.; Cooper, A.; Zhang, H. F. ACS Appl. Mater. Interfaces 2010, 2, 1400.
[16] Hao, S. L.; Wang, Y. Z.; Wang, B. C.; Deng, J.; Zhu, L. C.; Cao, Y. Mater. Sci. Eng. C 2014, 39, 113.
[17] Shi, S.; Chen, C.; Wang, M.; Ma, J. P.; Ma, H.; Xu, J. Chem. Commun. 2014, 50, 9079.
[18] Xu, S. J.; Song, K. P.; Li, T.; Tan, B. J. Mater. Chem. A 2015, 3, 1272.
[19] Kou, Y.; Xu, Y.; Guo, Z.; Jiang, D. Angew. Chem., Int. Ed. 2011, 50, 8753.
[20] Liu, R.; Cho, S. I.; Lee, S. B. Nanotechnology 2008, 19, No. 215710.
[21] Zhang, Z. B., Zhao, Q.; Yuan, J. Y.; Antonietti, M.; Huang, F. H. Chem. Commun. 2014, 50, 2595.
[22] Yu, G. R.; Li, Q. Z.; Li, N.; Man, Z. W.; Pu, C. H.; Asumana, C.; Chen, X. C. Polym. Eng. Sci. 2014, 54, 59.
[23] Zeng, Q.; Wu, D.; Zou, C.; Xu, F.; Fu, R.; Li, Z. H.; Liang, Y. R.; Su, D. S. Chem. Commun. 2010, 46, 5927.
[24] Wu, D. C.; Hui, C. M.; Dong, H. C.; Pietrasik, J.; Ryu, H. J.; Li, Z. H.; Zhong, M. J.; He, H. K.; Kim, E. K.; Jaroniec, M.; Kowalewski, T.; Matyjaszewski, K. Macromolecules 2011, 44, 5846.
[25] Li, Z. H.; Wu, D. C.; Huang, X.; Ma, J. H.; Liu, H.; Liang, Y. R.; Fu, R. W.; Matyjaszewski, K. Energy Environ. Sci. 2014, 7, 3006.
[26] Xu, F.; Lai, Y. J.; Fu, R. W.; Wu, D. C. J. Mater. Chem. A 2013, 1, 5001.
[27] McGann, J. P.; Zhong, M. J.; Kim, E. K.; Natesakhawat, S.; Jaroniec, M.; Whitacre, J. F.; Matyjaszewski, K.; Kowalewski, T. Chem. Phys. 2012, 213, 1078.
[28] Wu, D. C.; Dong, H. C.; Pietrasik, J.; Kim, E. K.; Hui, C. M.; Zhong, M. J.; Jaroniec, M.; Kowalewski, T.; Matyjaszewski, K. Chem. Mater. 2011, 23, 2024.
[29] Tuinstra, F.; Koenig, J. L. J. Chem. Phys. 1970, 53, 1126.

反应性模板剂诱导原位超交联法制备层次孔聚合物和碳材料

Reactive-Template Induced in-situ Hypercrosslinking Procedure to Hierarchical Porous Polymer and Carbon Materials

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