Hu Zhongliang, Li Xuefeng, Xi Liujiang, Jiang Haiyun, Chen Xianhong, Huang Zhi
College of Metallurgic Engineering, Hunan University of Technology, Zhuzhou 412007, China.
College of Packing Materials and Engineering, Hunan University of Technology, Zhuzhou 412007, China.
J Nanosci Nanotechnol. 2018 Mar 1;18(3):1970-1976. doi: 10.1166/jnn.2018.14229.
The intercalation properties of graphite oxide are important; however, the specific processes and mechanisms associated with intercalation have rarely been elucidated. In this paper, two types of surfactants, polyvinylpyrrolidone and tetradecyltrimethylammonium bromide, were used to thoroughly explore the intercalation properties of graphite oxide. The polyvinylpyrrolidone and tetradecyltrimethylammonium bromide-intercalated graphite oxide composites were synthesized under different conditions and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray energy dispersive spectroscopy, and transmission electron microscopy. It was found that polyvinylpyrrolidone could be directly intercalated into the graphite oxide layers and tetradecyltrimethylammonium bromide could not effectively react with the waterdispersed graphite oxide. With a low quantity of polyvinylpyrrolidone, only a part of the graphite oxide was intercalated, and the interlayer spacing of the polyvinylpyrrolidone-intercalated composites increased as the polyvinylpyrrolidone: graphite oxide mass ratio increased. When the graphite oxide was dispersed in a 0.05 N NaOH solution, the tetradecyltrimethylammonium bromide rapidly reacted with the graphite oxide, while the mixture of polyvinylpyrrolidone and graphite oxide could not be effectively separated. The intercalated spacing of the tetradecyltrimethylammonium bromideintercalated graphite oxide increased with the tetradecyltrimethylammonium bromide: graphite oxide mass ratio, but its crystalline structure was not as ordered as the polyvinylpyrrolidone-intercalated graphite oxide prepared in the water solution. The infrared spectra of the two surfactant-intercalated graphite oxide samples revealed that the polyvinylpyrrolidone is bonded to the graphite oxide via hydrogen bonding, while the tetradecyltrimethylammonium bromide is bonded via ionic bonding. The mechanism analysis indicated that the polyvinylpyrrolidone could directly enter the graphite oxide layers in the water solution because of the driving force of hydrogen bonding. However, processes such as graphite oxide exfoliation, reactions between the graphite oxide and tetradecyltrimethylammonium bromide, and reaggregation of the graphite oxide sheets are necessary for the formation of tetradecyltrimethylammonium bromide-intercalated graphite oxide.
氧化石墨的插层性质很重要;然而,与插层相关的具体过程和机制却很少得到阐明。本文使用了两种表面活性剂,聚乙烯吡咯烷酮和十四烷基三甲基溴化铵,来全面探究氧化石墨的插层性质。在不同条件下合成了聚乙烯吡咯烷酮和十四烷基三甲基溴化铵插层的氧化石墨复合材料,并通过X射线衍射、傅里叶变换红外光谱、扫描电子显微镜、X射线能量色散光谱和透射电子显微镜对其进行了表征。结果发现,聚乙烯吡咯烷酮可以直接插入氧化石墨层间,而十四烷基三甲基溴化铵不能与水分散的氧化石墨有效反应。当聚乙烯吡咯烷酮用量较少时,只有部分氧化石墨被插层,随着聚乙烯吡咯烷酮与氧化石墨质量比的增加,聚乙烯吡咯烷酮插层复合材料的层间距增大。当氧化石墨分散在0.05N的NaOH溶液中时,十四烷基三甲基溴化铵能迅速与氧化石墨反应,而聚乙烯吡咯烷酮与氧化石墨的混合物无法有效分离。十四烷基三甲基溴化铵插层氧化石墨的插层间距随十四烷基三甲基溴化铵与氧化石墨质量比的增加而增大,但其晶体结构不如在水溶液中制备的聚乙烯吡咯烷酮插层氧化石墨有序。两种表面活性剂插层氧化石墨样品的红外光谱表明,聚乙烯吡咯烷酮通过氢键与氧化石墨结合,而十四烷基三甲基溴化铵通过离子键结合。机理分析表明,由于氢键的驱动力,聚乙烯吡咯烷酮可以在水溶液中直接进入氧化石墨层间。然而,氧化石墨的剥离、氧化石墨与十四烷基三甲基溴化铵之间的反应以及氧化石墨片的重新聚集等过程对于形成十四烷基三甲基溴化铵插层氧化石墨是必要的。