Rao Kodepelly Sanjeeva, Senthilnathan Jaganathan, Ting Jyh-Ming, Yoshimura Masahiro
Promotion Center for Global Materials Research (PCGMR), Department of Material Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan.
Department of Civil Engineering, Indian Institute of Technology Madras (IIT Madras), Chennai 600036, Tamil Nadu, India.
Nanomaterials (Basel). 2023 Jul 11;13(14):2043. doi: 10.3390/nano13142043.
The continuous production of high-quality, few-layer graphene nanosheets (GNSs) functionalized with nitrogen-containing groups was achieved via a two-stage reaction method. The initial stage produces few-layer GNSs by utilizing our recently developed glycine-bisulfate ionic complex-assisted electrochemical exfoliation of graphite. The second stage, developed here, uses a radical initiator and nitrogen precursor (azobisisobutyronitrile) under microwave conditions in an aqueous solution for the efficient nitrogen functionalization of the initially formed GNSs. These nitrile radical reactions have great advantages in green chemistry and soft processing. Raman spectra confirm the insertion of nitrogen functional groups into nitrogen-functionalized graphene (N-FG), whose disorder is higher than that of GNSs. X-ray photoelectron spectra confirm the insertion of edge/surface nitrogen functional groups. The insertion of nitrogen functional groups is further confirmed by the enhanced dispersibility of N-FG in dimethyl formamide, ethylene glycol, acetonitrile, and water. Indeed, after the synthesis of N-FG in solution, it is possible to disperse N-FG in these liquid dispersants just by a simple washing-centrifugation separation-dispersion sequence. Therefore, without any drying, milling, and redispersion into liquid again, we can produce N-FG ink with only solution processing. Thus, the present work demonstrates the 'continuous solution processing' of N-FG inks without complicated post-processing conditions. Furthermore, the formation mechanism of N-FG is presented.
通过两步反应法实现了连续生产含氮官能团功能化的高质量少层石墨烯纳米片(GNSs)。初始阶段利用我们最近开发的甘氨酸 - 硫酸氢盐离子络合物辅助的石墨电化学剥离法制备少层GNSs。本文开发的第二阶段,在微波条件下于水溶液中使用自由基引发剂和氮前驱体(偶氮二异丁腈)对最初形成的GNSs进行高效的氮官能化。这些腈基自由基反应在绿色化学和软加工方面具有很大优势。拉曼光谱证实氮官能团插入到了氮功能化石墨烯(N - FG)中,其无序度高于GNSs。X射线光电子能谱证实了边缘/表面氮官能团插入。N - FG在二甲基甲酰胺、乙二醇、乙腈和水中的分散性增强进一步证实了氮官能团的插入。实际上,在溶液中合成N - FG后,仅通过简单的洗涤 - 离心分离 - 分散步骤就可以将N - FG分散在这些液体分散剂中。因此,无需任何干燥、研磨和再次分散到液体中,仅通过溶液处理我们就能制备N - FG油墨。因此,本工作展示了N - FG油墨的“连续溶液加工”,无需复杂的后处理条件。此外,还提出了N - FG的形成机理。