Liu Gang, Komatsu Naoki
Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan.
Chemphyschem. 2016 Jun 3;17(11):1557-67. doi: 10.1002/cphc.201600187. Epub 2016 Mar 22.
Thin-layer 2D materials have been attracting enormous interest, and various processes have been investigated to obtain these materials efficiently. In view of their practical applications, the most desirable source for the preparation of these thin-layer materials is the pristine bulk materials with stacked layers, such as pristine graphite. There are many options in terms of conditions for the exfoliation of thin-layer materials, and these include wet and dry processes, with or without additives, and the kind of solvent. In this context, we found that the versatile exfoliant hexahydroxytriphenylene works efficiently for the exfoliation of typical 2D materials such as graphene, MoS2 , and hexagonal boron nitride (h-BN) by both wet and dry processes by using sonication and ball milling, respectively, in aqueous and organic solvents. As for graphene, stable dispersions with relatively high concentrations (up to 0.28 mg mL(-1) ) in water and tetrahydrofuran were obtained from graphite in the presence of hexahydroxytriphenylene by a wet process with the use of bath sonication and by a dry process involving ball milling. Especially, most of the graphite was exfoliated and dispersed as thin-layer graphene in both aqueous and organic solvents through ball milling, even on a large scale (47-86 % yield). In addition, the exfoliant was easily removed from the precipitated composite by heat treatment without disturbing the graphene structure. Bulk MoS2 and h-BN were also exfoliated by both wet and dry processes. Similar to graphene, dispersions of MoS2 and h-BN of high concentrations in water and DMF were produced in high yields through ball milling.
二维薄层材料一直备受关注,人们已经研究了各种方法来高效制备这些材料。考虑到它们的实际应用,制备这些薄层材料最理想的原料是具有堆叠层的原始块状材料,如原始石墨。薄层材料的剥离条件有很多选择,包括湿法和干法,有无添加剂以及溶剂种类。在这种背景下,我们发现多功能剥离剂六羟基三亚苯通过湿法和干法分别在水性和有机溶剂中使用超声处理和球磨,能有效地剥离典型的二维材料,如石墨烯、二硫化钼和六方氮化硼(h-BN)。对于石墨烯,在六羟基三亚苯存在下,通过使用浴式超声处理的湿法和涉及球磨的干法,从石墨中在水和四氢呋喃中获得了相对高浓度(高达0.28 mg mL(-1))的稳定分散体。特别是,通过球磨,即使是大规模(产率47 - 86 %),大部分石墨也能在水性和有机溶剂中剥离并分散为薄层石墨烯。此外,通过热处理可以轻松地从沉淀的复合物中除去剥离剂,而不会破坏石墨烯结构。块状二硫化钼和六方氮化硼也通过湿法和干法进行了剥离。与石墨烯类似,通过球磨以高产率制备了在水和N,N-二甲基甲酰胺中高浓度的二硫化钼和六方氮化硼分散体。