对苯二胺功能化还原氧化石墨烯的结构和官能团变化

doi:10.7503/cjcu20150682

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

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. 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 Hongjuan^2,^3,^*(), PENG Tongjiang^3,⁴

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/Abstract

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^- $H 3 +$ 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^- $H 3 +$ 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

中图分类号:

O641
O613.71

TrendMD:

赵小龙, 孙红娟, 彭同江. 对苯二胺功能化还原氧化石墨烯的结构和官能团变化. 高等学校化学学报, 2016, 37(4): 728.

ZHAO Xiaolong, SUN Hongjuan, PENG Tongjiang. Changes of Structure and Functional Group of Reduction of Graphene Oxide with p-Phenylene Diamine^†. Chem. J. Chinese Universities, 2016, 37(4): 728.

图/表 8

Fig.1 FTIR spectra of membranesa. GO; b. GOP-2; c. GOP-4; d. GOP-6; e. GOP-8.

Fig.2 XPS(A) and N1s spectra(B) of the samples a. GO; b. GOPJ-2; c. GOPJ-4; d. GOPJ-6; e. GOPJ-8.

Fig.3 C1s spectra of GO(A), GOPJ-2(B), GOPJ-4(C) and GOPJ-6(D)

Fig.4 XRD patterns of membrane presoaked in 90% EtOH-H2O(A) Dry state; (B) wet state. a. GO; b. GOP-2; c. GOP-4; d. GOP-6; e. GOP-8.

Fig.5 Change in d-spacing for GO and GOP-X membranes in dry(a) and wet(b) state(A) and schematic of d-spacing change(B)

Fig.6 SEM images of GO(A), GOP-2(B), GOP-4(C) and GOP-6(D)

Fig.7 UV-Vis absorption of membranesa. GO; b. GOP-2; c. GOP-4; d. GOP-6; e. GOP-8.

Fig.8 Process of the functionalization and reduction of grahene preparation with PPD(A) and schematic representation of covalent interaction(B)

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对苯二胺功能化还原氧化石墨烯的结构和官能团变化

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

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对苯二胺功能化还原氧化石墨烯的结构和官能团变化

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

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