Bordes Emilie, Morcos Bishoy, Bourgogne David, Andanson Jean-Michel, Bussière Pierre-Olivier, Santini Catherine C, Benayad Anass, Costa Gomes Margarida, Pádua Agílio A H
Centre National de la Recherche Scientifique, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, Université Clermont Auvergne, Clermont-Ferrand, France.
UMR 5265 Centre National de la Recherche Scientifique, Université de Lyon, Villeurbanne, France.
Front Chem. 2019 Apr 16;7:223. doi: 10.3389/fchem.2019.00223. eCollection 2019.
The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. Because ionic liquids can be easily obtained with chosen molecular structures and tuneable physicochemical properties, they can be use as media to optimize the exfoliation of graphite. The understanding of the interactions involved between graphite and various chemical functions in the solvent ions will be helpful to find liquids capable of dissociating and stabilizing important quantities of large graphene layers. After a step of sonication, as a mechanical precursor, samples of suspended exfoliated graphene in different ionic liquids have been characterized experimentally in terms of flake size, number of layers, total concentration and purity of the exfoliated material. Nine different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate anions have been tested. UV-vis, Raman and X-ray photoelectron in addition to high resolution transmission electron and atomic force microscopy have been selected to characterize suspended exfoliated graphene in ionic liquids. The number of layers in the flakes exfoliated, the size and concentration depend of the structure of the ionic liquid selected. In order to obtain large flake sizes, ionic liquids with bis(trifluoromethylsulfonyl)imide anions and a cation with an alkyl chain of medium length should be selected. Smaller cation and anion favors the exfoliation of graphene. The exfoliation caused the formation of C-H bonds and the oxidation of the graphitic surface.
石墨的液相剥离是提高石墨烯产量和商业可得性最具前景的方法之一。由于离子液体可以通过选择分子结构和可调的物理化学性质轻松获得,它们可作为优化石墨剥离的介质。了解石墨与溶剂离子中各种化学官能团之间的相互作用,将有助于找到能够解离并稳定大量大尺寸石墨烯层的液体。经过超声处理这一步骤(作为机械预处理)后,已通过实验对悬浮在不同离子液体中的剥离石墨烯样品的薄片尺寸、层数、剥离材料的总浓度和纯度进行了表征。已测试了九种基于咪唑鎓、吡咯烷鎓和铵阳离子以及双(三氟甲基磺酰)亚胺、三氟甲磺酸盐、双氰胺、三氰甲烷化物和甲基硫酸盐阴离子的不同离子液体。除了高分辨率透射电子显微镜和原子力显微镜外,还选择了紫外可见光谱、拉曼光谱和X射线光电子能谱来表征离子液体中悬浮的剥离石墨烯。剥离薄片中的层数、尺寸和浓度取决于所选离子液体的结构。为了获得大的薄片尺寸,应选择具有双(三氟甲基磺酰)亚胺阴离子和中等长度烷基链阳离子的离子液体。较小的阳离子和阴离子有利于石墨烯的剥离。剥离导致了C-H键的形成和石墨表面的氧化。