Shiyanova Kseniya A, Gudkov Maksim V, Rabchinskii Maxim K, Sokura Liliia A, Stolyarova Dina Y, Baidakova Marina V, Shashkin Dmitriy P, Trofimuk Andrei D, Smirnov Dmitry A, Komarov Ivan A, Timofeeva Victoria A, Melnikov Valery P
N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 119991 Moscow, Russia.
Ioffe Institute, 194021 Saint Petersburg, Russia.
Nanomaterials (Basel). 2021 Apr 3;11(4):915. doi: 10.3390/nano11040915.
In this paper, we propose a facile approach to the management of graphene oxide (GO) chemistry via its synthesis using KMnO/KCrO oxidizing agents at different ratios. Using Fourier Transformed Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, and X-ray Absorption Spectroscopy, we show that the number of basal-plane and edge-located oxygenic groups can be controllably tuned by altering the KMnO/KCrO ratio. The linear two-fold reduction in the number of the hydroxyls and epoxides with the simultaneous three-fold rise in the content of carbonyls and carboxyls is indicated upon the transition from KMnO to KCrO as a predominant oxidizing agent. The effect of the oxidation mixture's composition on the structure of the synthesized GOs is also comprehensively studied by means of X-ray diffraction, Raman spectroscopy, transmission electron microscopy, atomic-force microscopy, optical microscopy, and the laser diffraction method. The nanoscale corrugation of the GO platelets with the increase of the KCrO content is signified, whereas the 10-100 μm lateral size, lamellar, and defect-free structure is demonstrated for all of the synthesized GOs regardless of the KMnO/KCrO ratio. The proposed method for the synthesis of GO with the desired chemistry opens up new horizons for the development of graphene-based materials with tunable functional properties.
在本文中,我们提出了一种简便的方法来管理氧化石墨烯(GO)的化学性质,即通过使用不同比例的KMnO/KCrO氧化剂合成GO。利用傅里叶变换红外光谱、X射线光电子能谱和X射线吸收光谱,我们表明,通过改变KMnO/KCrO的比例,可以可控地调节基面和边缘位置含氧基团的数量。当从以KMnO为主的氧化剂转变为以KCrO为主的氧化剂时,羟基和环氧化物的数量呈线性两倍减少,同时羰基和羧基的含量则呈三倍增加。还通过X射线衍射、拉曼光谱、透射电子显微镜、原子力显微镜、光学显微镜和激光衍射法全面研究了氧化混合物的组成对合成的GO结构的影响。结果表明,随着KCrO含量的增加,GO片层的纳米级波纹增大,而无论KMnO/KCrO比例如何,所有合成的GO均呈现出10 - 100μm的横向尺寸、层状且无缺陷的结构。所提出的合成具有所需化学性质的GO的方法为开发具有可调功能特性的石墨烯基材料开辟了新的前景。