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采用Hummers法将石墨氧化为氧化石墨烯的机理

Mechanism of Oxidization of Graphite to Graphene Oxide by the Hummers Method.

作者信息

Chen Xiaodong, Qu Zhan, Liu Zhe, Ren Guoyu

机构信息

School of Chemistry and Chemical Engineering, Yulin University, Yulin 719000, Shaanxi, P. R. China.

Shaanxi Key Laboratory of Clean Utilization of Low-Metamorphic Coal, Yulin 719000, Shaanxi, P. R. China.

出版信息

ACS Omega. 2022 Jun 28;7(27):23503-23510. doi: 10.1021/acsomega.2c01963. eCollection 2022 Jul 12.

Abstract

The mechanism of oxidizing reaction in the preparation of graphene oxide (GO) by a chemical oxidation method remains unclear. The main oxidant of graphite oxide has not been determined. Here, we show a new mechanism in which MnO, the main oxidant, is heated to decompose oxygen atoms and react with graphite. The whole preparation process constitutes of four distinct independent steps, different from the three steps of literature registration, and each step has its own chemical oxidation reaction. In the first step, concentrated sulfuric acid and nitric acid are intercalated between graphite layers in the form of a molecular thermal motion to produce HNO-HSO-GIC. In the second step, MnO is intercalated between graphite layers in the molecular convection-diffusion to MnO-HSO-GIC. In the third step, MnO is decomposed by heat. Oxygen atoms are generated to oxidize the defects in the graphite layer to PGO. This discovery is the latest and most important. In the fourth step, PGO is purified with deionized water, hydrogen peroxide, and hydrochloric acid to GO. Optical microscopy, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction spectrometry, and scanning electron microscopy analytical evidence was used for confirming MnO as the main oxidant and the structure of GO. This work provides a more plausible explanation for the mechanism of oxidizing reaction in the preparation of GO by a chemical oxidation method.

摘要

通过化学氧化法制备氧化石墨烯(GO)过程中的氧化反应机制仍不明确。氧化石墨的主要氧化剂尚未确定。在此,我们展示了一种新机制,即主要氧化剂MnO受热分解出氧原子并与石墨反应。整个制备过程由四个不同的独立步骤构成,不同于文献记载的三个步骤,且每个步骤都有其自身的化学氧化反应。第一步,浓硫酸和硝酸以分子热运动的形式插入石墨层间,生成HNO - HSO - GIC。第二步,MnO以分子对流扩散的方式插入石墨层间形成MnO - HSO - GIC。第三步,MnO受热分解,产生氧原子将石墨层中的缺陷氧化为PGO。这一发现是最新且最重要的。第四步,用去离子水、过氧化氢和盐酸将PGO提纯为GO。利用光学显微镜、紫外可见光谱、傅里叶变换红外光谱、X射线衍射光谱和扫描电子显微镜分析证据来确认MnO为主要氧化剂以及GO的结构。这项工作为通过化学氧化法制备GO过程中的氧化反应机制提供了更合理的解释。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d5d/9280770/453492c89979/ao2c01963_0002.jpg

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