Dudko Volodymyr, Ottermann Katharina, Rosenfeldt Sabine, Papastavrou Georg, Breu Josef
Department of Inorganic Chemistry I, Bavarian Polymer Institute, University of Bayreuth, Universitätsstraße 30, 95440 Bayreuth, Germany.
Department of Physical Chemistry II, Bavarian Polymer Institute, University of Bayreuth, Universitätsstraße 30, 95440 Bayreuth, Germany.
Langmuir. 2021 Jan 12;37(1):461-468. doi: 10.1021/acs.langmuir.0c03113. Epub 2020 Dec 27.
Repulsive osmotic delamination is thermodynamically allowed "dissolution" of two-dimensional (2D) materials and therefore represents an attractive alternative to liquid-phase exfoliation to obtain strictly monolayered nanosheets with an appreciable aspect ratio with quantitative yield. However, osmotic delamination was so far restricted to aqueous media, severely limiting the range of accessible 2D materials. Alkali-metal intercalation compounds of MoS or graphite are excluded because they cannot tolerate even traces of water. We now succeeded in extending osmotic delamination to polar and aprotic organic solvents. Upon complexation of interlayer cations of synthetic hectorite clay by crown ethers, either 15-crown-5 or 18-crown-6, steric pressure is exerted, which helps in reaching the threshold separation required to trigger osmotic delamination based on translational entropy. This way, complete delamination in water-free solvents like aprotic ethylene and propylene carbonate, -methylformamide, -methylacetamide, and glycerol carbonate was achieved.
排斥性渗透分层是二维(2D)材料在热力学上允许的“溶解”,因此是液相剥离的一种有吸引力的替代方法,可用于获得具有可观长径比且产率定量的严格单层纳米片。然而,到目前为止,渗透分层仅限于水性介质,严重限制了可获得的二维材料的范围。MoS或石墨的碱金属插层化合物被排除在外,因为它们甚至无法耐受痕量的水。我们现在成功地将渗透分层扩展到极性和非质子有机溶剂。通过冠醚(15-冠-5或18-冠-6)与合成锂皂石粘土的层间阳离子络合,施加空间压力,这有助于达到基于平移熵触发渗透分层所需的阈值分离。通过这种方式,在无水溶剂如非质子碳酸亚乙酯和碳酸亚丙酯、N-甲基甲酰胺、N-甲基乙酰胺和碳酸甘油酯中实现了完全分层。