Chair of Macromolecular Chemistry, Faculty of Chemistry and Food Chemistry, School of Science, Technische Universität Dresden, Mommsenstr. 4, 01062, Dresden, Germany.
Center for Advancing Electronics Dresden, Technische Universität Dresden, 01062, Dresden, Germany.
Nat Commun. 2018 Oct 3;9(1):4051. doi: 10.1038/s41467-018-06599-y.
Mass transport through graphene is receiving increasing attention due to the potential for molecular sieving. Experimental studies are mostly limited to the translocation of protons, ions, and water molecules, and results for larger molecules through graphene are rare. Here, we perform controlled radical polymerization with surface-anchored self-assembled initiator monolayer in a monomer solution with single-layer graphene separating the initiator from the monomer. We demonstrate that neutral monomers are able to pass through the graphene (via native defects) and increase the graphene defects ratio (Raman I/I) from ca. 0.09 to 0.22. The translocations of anionic and cationic monomers through graphene are significantly slower due to chemical interactions of monomers with the graphene defects. Interestingly, if micropatterned initiator-monolayers are used, the translocations of anionic monomers apparently cut the graphene sheet into congruent microscopic structures. The varied interactions between monomers and graphene defects are further investigated by quantum molecular dynamics simulations.
由于具有分子筛的潜力，石墨烯中的物质输运受到越来越多的关注。实验研究主要局限于质子、离子和水分子的迁移，而通过石墨烯的较大分子的结果则很少。在这里，我们在单体溶液中进行表面锚定的自组装引发剂单层的可控自由基聚合，单层石墨烯将引发剂与单体隔开。我们证明中性单体能够通过石墨烯（通过本征缺陷）并将石墨烯缺陷比（拉曼 I/I）从约 0.09 增加到 0.22。由于单体与石墨烯缺陷的化学相互作用，阴离子和阳离子单体通过石墨烯的迁移速度明显较慢。有趣的是，如果使用微图案化的引发剂单层，则阴离子单体的迁移显然会将石墨烯片切割成全等的微观结构。通过量子分子动力学模拟进一步研究了单体和石墨烯缺陷之间的各种相互作用。
