物理化学学报 >> 2017, Vol. 33 >> Issue (2): 413-418.doi: 10.3866/PKU.WHXB201610241

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氧化石墨阳离子交换容量测定过程中结构的变化

王泉珺1,孙红娟2,*(),彭同江2,3,冯明珠2   

  1. 1 西南科技大学理学院,四川绵阳621010
    2 西南科技大学矿物材料及应用研究所,四川绵阳621010
    3 西南科技大学分析测试中心,四川绵阳621010
  • 收稿日期:2016-08-26 发布日期:2017-01-12
  • 通讯作者: 孙红娟 E-mail:sunhongjuan@swust.edu.cn
  • 基金资助:
    国家自然科学基金(41272051);西南科技大学博士基金(11ZX7135);西南科技大学研究生创新基金(15ycx073)

Structure Development during the Cation Exchange Processes of Graphite Oxide

Quan-Jun WANG1,Hong-Juan SUN2,*(),Tong-Jiang PENG2,3,Ming-Zhu FENG2   

  1. 1 School of Science, Southwest University of Science and Technology, Mianyang 621010, Sichuan Province, P. R. China
    2 Institute of Mineral Materials & Application, Southwest University of Science and Technology, Mianyang 621010, Sichuan Province, P. R. China
    3 Center of Forecasting and Analysis, Southwest University of Science and Technology, Mianyang 621010, Sichuan Province, P. R. China
  • Received:2016-08-26 Published:2017-01-12
  • Contact: Hong-Juan SUN E-mail:sunhongjuan@swust.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(41272051);Doctor Foundation of Southwest University of Science and Technology, China(11ZX7135);Postgraduate Innovation Fund Project by Southwest University of Science and Technology, China(15ycx073)

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摘要：

氧化石墨（GO）结构层上的碳羟基（-C-OH）和边缘羧基（-COOH）在水介质中发生质子化反应解离出的H+具有阳离子可交换性。实验采用甲醛缩合法测量了GO的阳离子交换容量（CEC），用X射线衍射（XRD）、傅里叶变换红外（FTIR）光谱和X射线光电子能谱（XPS）分析测试手段对GO阳离子交换过程中间产物的结构变化进行了分析。结果表明，GO的CEC高达541.48 mmol/100 g。NH4+和Ca2+交换后的GO，保持稳定的层状结构，c轴方向层间距分别增大了0.1499和0.2905 nm。NH4+和Ca2+主要以层间可交换阳离子形式存在于层间域中，并与水分子形成可交换水化阳离子层，部分以[NH4（H2O）6]+和[Ca（H2O）6]2+的形式存在于结构层的边缘附近，共同平衡结构层水解产生的负电荷。

关键词: 氧化石墨, 含氧官能团, 阳离子交换容量, 层间域, 结构变化

Abstract:

Oxygen-containing hydroxyl (-C-OH) and carboxyl (-COOH) functional groups on both the basal planes and edges of the graphite oxide (GO) structure can dissociate to form H+ in water, thus providing cation exchange ability. The cation exchange capacity (CEC) of GO was measured accurately using the Stiasny method and the intermediate products of cation exchange processes of oxygen-containing functional groups and structure development were analyzed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The results indicated that the CEC of GO was up to 541.48 mmol/100 g. After NH4+ and Ca2+ exchange processes, GO still maintained a stable lamellar structure, and the c axis spacing increased by 0.1499 and 0.2905 nm, respectively. NH4+ and Ca2+ were mainly in the form of exchangeable cations in the interlayer space of GO, and formed a hydrated cation layer with water molecules, part of the containing[NH4(H2O)6]+ or[Ca(H2O)6]2+ formed near the edge of the structural layer, balancing the negative charges originating from hydrolysis of the carboxyl groups of the GO structural layer.

Key words: Graphite oxide, Oxygen-containing functional group, Cation exchange capacity, Interlayer space, Structure development