Chen Duhong, Lin Zhen, Sartin Matthew M, Huang Teng-Xiang, Liu Jia, Zhang Qiugen, Han Lianhuan, Li Jian-Feng, Tian Zhong-Qun, Zhan Dongping
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering; Department of Mechanical and Electrical Engineering, School of Aerospace Engineering; and Graphene Industry and Engineering Research Institute, Xiamen University, Xiamen 361005, China.
J Am Chem Soc. 2020 Apr 8;142(14):6516-6520. doi: 10.1021/jacs.0c02158. Epub 2020 Mar 30.
Here we propose a strategy of radical oxidation reaction for the high-efficiency production of graphene oxide (GO). GO plays important roles in the sustainable development of energy and the environment, taking advantages of oxygen-containing functional groups for good dispersibility and assembly. Compared with Hummers' method, electrochemical exfoliation of graphite is considered facile and green, although the oxidation is fairly low. To synthesize GO with better crystallinity and higher oxidation degree, we present a photosynergetic electrochemical method. By using oxalate anions as the intercalation ions and co-reactant, the interfacial concentration of hydroxyl radicals generated during electrochemical exfoliation was promoted, and the oxidation degree was comparable with that of GO prepared by Hummers' method. In addition, the crystallinity was improved with fewer layers and larger size. Moreover, the aniline coassembled GO membrane was selectively permeable to water molecules by the hydrogen-bond interaction, but it was impermeable to Na, K, and Mg, due to the electrostatic interactions. Thus, it has a prospective application to water desalination and purification. This work opens a novel approach to the direct functionalization of graphene during the electroexfoliation processes and to the subsequent assembly of the functionalized graphene.
在此,我们提出一种用于高效生产氧化石墨烯(GO)的自由基氧化反应策略。GO凭借其含有的含氧官能团所具备的良好分散性和组装性,在能源与环境的可持续发展中发挥着重要作用。与Hummers法相比,石墨的电化学剥离法虽氧化程度较低,但被认为简便且绿色环保。为了合成具有更好结晶度和更高氧化程度的GO,我们提出了一种光协同电化学方法。通过使用草酸根阴离子作为嵌入离子和共反应物,促进了电化学剥离过程中产生的羟基自由基的界面浓度,其氧化程度与用Hummers法制备的GO相当。此外,结晶度得到提高,层数减少且尺寸增大。而且,苯胺共组装的GO膜通过氢键相互作用对水分子具有选择性渗透性,但由于静电相互作用,对Na、K和Mg不渗透。因此,它在水脱盐和净化方面具有潜在应用前景。这项工作为在电剥离过程中对石墨烯进行直接功能化以及随后对功能化石墨烯进行组装开辟了一条新途径。