Strong and tough graphene papers constructed with pyrene-containing small molecules via π-π/Hbonding synergistic interactions  

基于π-π/H-键协同作用制备含芘小分子增强高韧性石墨烯纸

作　　者：Hong Yuan Liangbing Ge Kun Ni Xiukai Kan Si-Ming Chen Mengting Gao Fei Pan Jianglin Ye Fang Xu Na Shu Jieyun Li Tao Suo Shu-Hong Yu Yanwu Zhu 袁宏;葛良兵;倪堃;阚秀凯;陈思铭;高梦婷;潘飞;叶江林;许方;束娜;李婕云;索涛;俞书宏;朱彦武(Hefei National Laboratory for Physical Sciences at the Microscale&CAS Key Laboratory of Materials for Energy Conversion,Department of Materials Science and Engineering,iChEM,University of Science and Technology of China,Hefei 230026,China;Division of Nanomaterials and Chemistry,Hefei National Laboratory for Physical Sciences at the Microscale,CAS Center for Excellence in Nanoscience,Hefei Science Center of CAS,Collaborative Innovation Center of Suzhou Nano Science and Technology,Department of Chemistry,University of Science and Technology of China,Hefei 230026,China;School of Aeronautics,Northwestern Polytechnical University,Xi’an 710072,China)

机构地区：[1]Hefei National Laboratory for Physical Sciences at the Microscale&CAS Key Laboratory of Materials for Energy Conversion,Department of Materials Science and Engineering,iChEM,University of Science and Technology of China,Hefei 230026,China [2]Division of Nanomaterials and Chemistry,Hefei National Laboratory for Physical Sciences at the Microscale,CAS Center for Excellence in Nanoscience,Hefei Science Center of CAS,Collaborative Innovation Center of Suzhou Nano Science and Technology,Department of Chemistry,University of Science and Technology of China,Hefei 230026,China [3]School of Aeronautics,Northwestern Polytechnical University,Xi’an 710072,China

出　　处：《Science China Materials》2021年第5期1206-1218,共13页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China (51772282,51972299);funding from Hefei Center for Physical Science and Technology。

摘　　要：Lightweight yet strong paper with high toughness is desirable especially for impact protection. Herein we demonstrated electrically conductive and mechanically robust paper(AP/PB-GP) made of reduced graphene oxide via interfacial crosslinking with 1-aminopyrene(AP) and 1-pyrenebutyrat(PB) small molecules. The AP/PB-GP with thickness of over ten micrometer delivers a record-high toughness(~69.67 ± 15.3 MJ m^(-3) in average), simultaneously with superior strength(close to 1 GPa), allowing an impressive specific penetration energy absorption(~0.17 MJ kg^(-1)) at high impact velocities when used for ballistic impact protection. Detailed interfacial and structural analysis reveals that the reinforcement is synergistically determined by π-π interaction and H-bonding linkage between adjacent graphene lamellae. Especially, the defective pores within the graphene platelets benefit the favorable adsorption of the pyrene-containing molecules, which imperatively maximizes the interfacial binding, facilitating deflecting crack and plastic deformation under loading. Density functional theory simulation suggests that the coupling between the polar functional groups, e.g., –COOH, at the edges of graphene platelets and –NH_(2) and –COOH of AP/PB are critical to the formation of hydrogen bonding network.轻质高强且具备高韧性的石墨烯组装材料在抗冲击防护领域有着潜在的应用价值.在这项工作中,我们通过在还原氧化石墨烯层间界面交联1-氨基芘AP和1-芘丁酸PB共轭小分子,可以获得具有高导电、高韧性的超强复合石墨烯纸(AP/PB-GPs).结果表明,超过10μm厚度的复合石墨烯纸具有超高的平均韧性(~69.67±15.3 MJ m^(-3)),同时抗拉伸强度接近1 GPa;尤其在抗冲击性能方面,在高速弹道冲击速度下,仍然可以获得优异的比穿透能量吸收值(~0.17 MJ kg^(-1)).详细的界面和结构分析表明,界面增强是由相邻石墨烯层间与共轭分子之间的π-π相互作用和氢键连接共同决定的.尤其是石墨烯纳米片内的孔洞及边缘缺陷更有利于共轭小分子充分的吸附,这必然会使界面结合最大化,在连续高的加载应力下能够有效促进裂纹的偏转和塑性变形.密度泛函理论(DFT)模拟表明,石墨烯纳米片边缘的–COOH极性官能团与AP/PB分子表面的–NH_(2)、–COOH之间的耦合对氢键网络的形成起着关键作用.

关 键 词：graphene paper π-πinteraction H-BONDING synergistic reinforcement mechanical properties 

分 类 号：TQ127.11[化学工程—无机化工]