Acta Chim. Sinica ›› 2015, Vol. 73 ›› Issue (6): 600-604.DOI: 10.6023/A15020099 Previous Articles     Next Articles

Special Issue: 共价有机多孔聚合物



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   

  1. 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
  • 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 Lifenga,b, Chen Luyia, Liang Yerua, Lu Zhitaoa, Xu Feia, Fu Ruowena, Wu Dingcaia   

  1. 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).

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