高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (4): 728-735.doi: 10.7503/cjcu20150682

• 物理化学 • 上一篇    下一篇

对苯二胺功能化还原氧化石墨烯的结构和官能团变化

赵小龙1, 孙红娟2,3(), 彭同江3,4   

  1. 1. 西南科技大学理学院, 绵阳 621010
    2. 固体废物处理与资源化利用教育部重点实验室, 绵阳 621010
    3. 矿物材料及应用研究所, 绵阳 621010
    4. 分析测试中心, 绵阳 621010
  • 收稿日期:2015-08-28 出版日期:2016-04-10 发布日期:2016-03-10
  • 基金资助:
    国家自然科学基金(批准号: 41272051)和西南科技大学博士基金(批准号: 11ZX7135)资助

Changes of Structure and Functional Group of Reduction of Graphene Oxide with p-Phenylene Diamine

ZHAO Xiaolong1, SUN Hongjuan2,3,*(), PENG Tongjiang3,4   

  1. 1. School of Science, Mianyang 621010, China
    2. Key Laboratory of Ministry of Education for Solid Waste Treatment and Resource Recycle, Mianyang 621010, China
    3. Institute of Mineral Materials & Application, Mianyang 621010, China
    4. Center of Forecasting and Analysis, Southwest University of Science and Technology, Mianyang 621010, China
  • Received:2015-08-28 Online:2016-04-10 Published:2016-03-10
  • Contact: SUN Hongjuan E-mail:sunhongjuan@swust.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.41272051) and the Doctor Foundation of Southwest University of Science and Technology, China(No.11ZX7135)

摘要:

采用一步水热回流法, 选取对苯二胺(PPD)对氧化石墨烯(GO) 进行还原与改性处理, 制备了功能化还原氧化石墨烯(GOP-X). 采用傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)及X射线衍射(XRD)等研究了PPD与GO的反应作用类型及结构变化. 结果表明, 随着PPD与GO质量比的增加, GOP-X层间距(d值)先增大后减小, GOP-X共轭结构逐渐恢复, 与溶剂分子作用时, 层间距增幅呈减小趋势, 并最终趋于恒定. PPD 单体与 GO 反应时存在3种键合类型: (1) GO含氧官能团和PPD分子之间的氢键作用(C—OH…H2N—X); (2) 质子化PPD与弱酸性GO带负电位置之间的离子键作用(—COO-H3+N—X); (3) PPD中氨基(NH2)与GO含氧官能团之间形成的共价键作用. 与GO中羧基(COOH) 的酰胺化反应将先于与环氧基(C—O—C)的亲核取代反应. 提出了相应的作用机理.

关键词: 对苯二胺, 功能化还原氧化石墨烯, 质子化, 层间距, 反应次序

Abstract:

The p-phenylene diamine(PPD) were selected as reducion and modification agent to prepare functionalized and reduced graphene(GOP-X) by one-step simple refluxing method. Infrared spectrum(FTIR), X-ray photoelectron spectroscopy(XPS), X-ray diffraction(XRD) and UV-Vis absorption spectrum were used to investigate the reaction types and structure changes between PPD and graphene oxide(GO). The results show that the d-spacing of GOP-X layers increases firstly and then decreases with the increase of X(the mass ratio of PPD and GO), and the conjugated structure gradually restored; when the solvent molecular interaction, the amplification of the d-spacing decrease to a steady figure. Three types of bonds between PPD and GO were proposed: (Ⅰ) hydrogen-bonding interaction between the oxygen-containing functional groups of GO and the PPD molecules(C—OH…H2N—X); (Ⅱ) ionic bonding in protonating amine by the weakly acidic sites of the GO layers(—COO-H3+N—X); (Ⅲ) covalent bonding from amidation and nucleophilic addition reactions between the amie in PPD(NH2 ) and the oxygen containing groups of GO. Furthermore, the NH2 prefers to react first with the carboxyl group(COOH) and then with the epoxide group(C—O—C), and the relative action mechanisms were also described.

Key words: p-Phenylene diamine, Functionalization and reduction of grapheme, Protonation, d-Spacing, Reaction sequence

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