分段取样法研究改进Hummers法制备GO结构特性及其机理

doi:10.16085/j.issn.1000-6613.2022-1275

摘要/Abstract

摘要：

氧化石墨烯（GO）制备过程调控及机理研究对其性能及其功能化改性具有重要意义。本文基于改进Hummers法制备GO，采用分段取样法提取主要阶段的中间产物；利用SEM、Raman光谱以及XRD、FTIR、XPS等检测手段表征分析各阶段产物的微观形貌、结构和成分，以探究GO制备机理，并采用TEM对最终制备的GO进行形貌表征观察，探究各阶段反应对GO制备的影响规律，以实现对GO氧化程度和结构的调控。研究结果表明：在浓H₂SO₄/KMnO₄混合体系中，使用单一的浓H₂SO₄无法对石墨进行插层与氧化，KMnO₄是石墨氧化的必要条件；氧化阶段会形成大量的含氧官能团，导致石墨层间距进一步扩大。GO-1到GO-5阶段，氧化石墨的C/O从7.23降到2.03，氧化石墨片层间距从原始石墨的0.344nm增加到0.815nm，研究成果为GO的进一步改性与应用提供数据及理论支持。

关键词: 氧化石墨烯, 改进Hummers法, 氧化

Abstract:

The research on the regulation and mechanism of graphene oxide (GO) preparation is of great significance for its properties and functional modification. In this paper, the synthesis Hummers method was used to prepare GO, and the segmented sampling method was employed to extract the intermediates of the main stages. SEM, Raman spectroscopy, XRD, FTIR, XPS and other detection methods were used to characterize and analyze the micromorphology, structure and composition of the products at each stage to explore the preparation mechanism of GO. TEM was used to characterize and observe the morphology of the final prepared GO to explore the influence rule of each stage reaction on GO preparation and to realize the regulation of GO oxidation degree and structure. The results displayed that in the mixed system of concentrated H₂SO₄/KMnO₄, the intercalation and oxidation of graphite could not be carried out by using a single concentrated H₂SO₄, while KMnO₄ was the necessary condition for graphite oxidation. In the oxidation phase, a large number of oxygen-containing functional groups was formed, leading to further expansion of graphite layer spacing. In the GO-1 to GO-5 stage, the C/O ratio of graphite oxide decreased from 7.23 to 2.03 and the laminar spacing of graphite oxide increased from 0.344nm to 0.815nm. The research results provided distinct data and theoretical support for further modification and application of GO products.

Key words: gaphene oxide, improved Hummers method, oxidation

中图分类号:

TQ23

张浩月, 李春丽, 徐博, 李筱贺, 仝铃, 邱广明. 分段取样法研究改进Hummers法制备GO结构特性及其机理[J]. 化工进展, 2023, 42(5): 2606-2615.

ZHANG Haoyue, LI Chunli, XU Bo, LI Xiaohe, TONG Ling, QIU Guangming. Structural characteristics and mechanism of GO prepared via improved Hummers method based on segmental sampling[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2606-2615.

图/表 10

图1 制备方法和取样节点示意图

图2 GO样品的SEM图

图3 石墨样品的Raman谱图

图4 各阶段样品的XRD谱图

图5 不同取样点石墨样品的FTIR谱图

图6 样品的XPS全谱扫描

图7 样品的XPS C1s 谱图

表1 C 1s XPS光谱和样品元素组成拟合结果

样品	C1峰的组成（原子分数）/%				元素的原子分数/%				C/O
样品	C $̿$ C（sp²）	C—C（sp³）	C—O	COOH	C	O	S	Mn	C/O
GO-1	85.99	14.01	—	—	85.72	11.85	2.43	—	7.23
GO-2	43.04	23.5	19.27	14.19	68.06	25.92	2.51	3.51	2.62
GO-3	36.04	20.35	35.50	8.11	42.81	45.36	10.05	1.77	0.94
GO-4	22.26	25.43	36.51	15.08	59.57	36.02	4.01	0.30	1.66
GO-5	23.33	31.33	36.71	8.63	65.26	32.15	4.29	0.18	2.03

表1 C 1s XPS光谱和样品元素组成拟合结果

样品	C1峰的组成（原子分数）/%				元素的原子分数/%				C/O
样品	C $̿$ C（sp²）	C—C（sp³）	C—O	COOH	C	O	S	Mn	C/O
GO-1	85.99	14.01	—	—	85.72	11.85	2.43	—	7.23
GO-2	43.04	23.5	19.27	14.19	68.06	25.92	2.51	3.51	2.62
GO-3	36.04	20.35	35.50	8.11	42.81	45.36	10.05	1.77	0.94
GO-4	22.26	25.43	36.51	15.08	59.57	36.02	4.01	0.30	1.66
GO-5	23.33	31.33	36.71	8.63	65.26	32.15	4.29	0.18	2.03

图8 放大不同倍数下的GO TEM图

图9 不同取样点溶液状态及制得样品形貌

参考文献 34

1	ZHANG Z H, SCHNIEPP H C, ADAMSON D H. Characterization of graphene oxide: Variations in reported approaches[J]. Carbon, 2019, 154: 510-521.
2	BORINI Stefano, WHITE Richard, WEI Di, et al. Ultrafast graphene oxide humidity sensors[J]. ACS Nano, 2013, 7(12): 11166-11173.
3	MENG Chunfeng, HU Pinfei, CHEN Hantao, et al. 2D conductive MOFs with sufficient redox sites: Reduced graphene oxide/Cu-benzenehexathiolate composites as high capacity anode materials for lithium-ion batteries[J]. Nanoscale, 2021, 13(16): 7751-7760.
4	STENGL V, BAKARDJIEVA S, GRYGAR T M, et al. TiO₂-graphene oxide nanocomposite as advanced photocatalytic materials[J]. Chemistry Central Journal, 2013, 7(1): 41.
5	LI D, MÜLLER M B, GILJE S, et al. Processable aqueous dispersions of graphene nanosheets[J]. Nature Nanotechnology, 2008, 3(2): 101-105.
6	MARCANO D C, KOSYNKIN D V, BERLIN J M, et al. Improved synthesis of graphene oxide[J]. ACS Nano, 2010, 4(8): 4806-4814.
7	CHEN Ji, YAO Bowen, LI Chun, et al. An improved Hummers method for eco-friendly synthesis of graphene oxide[J]. Carbon, 2013, 64: 225-229.
8	陈骥. 氧化石墨烯的制备及结构控制[D]. 北京: 清华大学, 2016.
	CHEN Ji. Synthesis and structural control of graphene oxide[D]. Beijing: Tsinghua University, 2016.
9	HOU Yonggang, Shenghua LYU, LIU Leipeng, et al. High-quality preparation of graphene oxide via the Hummers’ method: Understanding the roles of the intercalator, oxidant, and graphite particle size[J]. Ceramics International, 2020, 46(2): 2392-2402.
10	徐博, 李春丽, 张浩月, 等. 改进Hummers法制备氧化石墨烯的机理研究[J]. 膜科学与技术, 2021, 41(6): 18-26.
	XU Bo, LI Chunli, ZHANG Haoyue, et al. Study on the mechanism of preparation of graphene oxide bimroved Hummers method[J]. Membrane Science and Technology, 2021, 41(6): 18-26.
11	GUERRERO-CONTRERAS J, CABALLERO-BRIONES F. Graphene oxide powders with different oxidation degree, prepared by synthesis variations of the Hummers method[J]. Materials Chemistry and Physics, 2015, 153: 209-220.
12	ALKHOUZAAM Abedalkader, QIBLAWEY Hazim, KHRAISHEH Majeda, et al. Synthesis of graphene oxides particle of high oxidation degree using a modified Hummers method[J]. Ceramics International, 2020,46(15): 23997-24007.
13	QIAN Zhe, CHEN Liang, LI Deyuan, et al. Preparation of graphene oxides with different sheet sizes by temperature control[J]. Chinese Physics B, 2017, 26(10): 106101.
14	AL-GAASHANI R, ZAKARIA Y, LEE O S, et al. Effects of preparation temperature on production of graphene oxide by novel chemical processing[J]. Ceramics International, 2021, 47(7): 10113-10122.
15	AL-GAASHANI R, NAJJAR A, ZAKARIA Y, et al. XPS and structural studies of high quality graphene oxide and reduced graphene oxide prepared by different chemical oxidation methods[J]. Ceramics International, 2019, 45(11): 14439-14448.
16	赖奇, 罗学萍. 氧化石墨烯的制备和定性定量分析[J]. 材料研究学报, 2015, 29(2): 155-160.
	LAI Qi, LUO Xueping. Qreparation and qualitative and analysis of graphene oxides by UV spectroscopy[J]. Chinese Journal of Materials Research, 2015, 29(2):155-160.
17	KRISHNAMOORTHY Karthikeyan, VEERAPANDIAN Murugan, YUN Kyusik, et al. The chemical and structural analysis of graphene oxide with different degrees of oxidation[J]. Carbon, 2013, 53: 38-49.
18	董艳丽. GIC的制备及其阻燃PE的研究[D]. 哈尔滨: 哈尔滨理工大学, 2012.
	DONG Yanli. Study on the preparation of GIC and its flame retardant PE[D]. Harbin: Harbin University of Science and Technology, 2012.
19	XING Xiaohan, ZHANG Xiaohua, ZHANG Kang, et al. Preparation of large-sized graphene from needle coke and the adsorption for malachite green with its graphene oxide[J]. Fullerenes, Nanotubes and Carbon Nanostructures, 2019, 27(2): 97-105.
20	CHUA C K, SOFER Z, PUMERA M. Graphite oxides: Effects of permanganate and chlorate oxidants on the oxygen composition[J]. Chemistry, 2012, 18(42): 13453-13459.
21	Ondřej JANKOVSKÝ, Michal NOVÁČEK, LUXA Jan, et al. Concentration of nitric acid strongly influences chemical composition of graphite oxide[J]. Chemistry, 2017, 23(26): 6432-6440.
22	MANAKHOV Anton, Miroslav MICHLÍČEK, FELTEN Alexandre, et al. XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach[J]. Applied Surface Science, 2017, 394: 578-585.
23	DRESSELHAUS M S, DRESSELHAUS G. Intercalation compounds of graphite[J]. Advances in Physics, 2002, 51(1): 1-186.
24	KANG J H, KIM T, CHOI J, et al. Hidden second oxidation step of hummers method[J]. Chemistry of Materials, 2016, 28(3): 756-764.
25	SHAMAILA S, SAJJAD A K, IQBAL A. Modifications in development of graphene oxide synthetic routes[J]. Chemical Engineering Journal, 2016, 294: 458-477.
26	PARK J, KIM Y S, SUNG S J, et al. Highly dispersible edge-selectively oxidized graphene with improved electrical performance[J]. Nanoscale, 2017, 9(4): 1699-1708.
27	汪波涛. 氧化石墨烯改性双马来酰亚胺复合材料的制备与性能[D]. 哈尔滨: 哈尔滨理工大学, 2018.
	WANG Botao. Preparation and properties of bismaleimide composite modified by graphene oxide[D]. Harbin: Harbin University of Science and Technology, 2018.
28	HONTORIA-LUCAS C, LÓPEZ-PEINADO A J, LÓPEZ-GONZÁLEZ J D, et al. Study of oxygen-containing groups in a series of graphite oxides: Physical and chemical characterization[J]. Carbon, 1995, 33(11): 1585-1592.
29	STORM M M, JOHNSEN R E, NORBY P. In situ X-ray powder diffraction studies of the synthesis of graphene oxide and formation of reduced graphene oxide[J]. Journal of Solid State Chemistry, 2016, 240: 49-54.
30	CHEN C H, HU S, SHIH J F, et al. Effective synthesis of highly oxidized graphene oxide that enables wafer-scale nanopatterning: Preformed acidic oxidizing medium approach[J]. Scientific Reports, 2017, 7: 3908.
31	DIMIEV A M, BACHILO S M, SAITO R, et al. Reversible formation of ammonium persulfate/sulfuric acid graphite intercalation compounds and their peculiar Raman spectra[J]. ACS Nano, 2012, 6(9): 7842-7849.
32	EKLUND P C, OLK C H, HOLLER F J, et al. Raman scattering study of the staging kinetics in the c-face skin of pyrolytic graphite-H₂SO₄ [J]. Journal of Materials Research, 1986, 1(2): 361-367.
33	傅玲. 氧化石墨和聚吡咯/氧化石墨纳米复合材料的制备、表征及应用研究[D]. 长沙: 湖南大学, 2005.
	FU Ling. The research on synthesis, characterization and application of graphite oxide and polypyrrole/graphite oxide nanocomposites[D]. Changsha: Hunan University, 2005.
34	DIMIEV A, KOSYNKIN D V, ALEMANY L B, et al. Pristine graphite oxide[J]. Journal of the American Chemical Society, 2012, 134(5): 2815-2822.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[7]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[8]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[9]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[10]	杨寒月, 孔令真, 陈家庆, 孙欢, 宋家恺, 王思诚, 孔标. 微气泡型下向流管式气液接触器脱碳性能[J]. 化工进展, 2023, 42(S1): 197-204.
[11]	杨建平. 降低HPPO装置反应系统原料消耗的PSE[J]. 化工进展, 2023, 42(S1): 21-32.
[12]	王福安. 300kt/a环氧丙烷工艺反应器降耗减排分析[J]. 化工进展, 2023, 42(S1): 213-218.
[13]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[14]	赖诗妮, 江丽霞, 李军, 黄宏宇, 小林敬幸. 含碳掺氨燃料的研究进展[J]. 化工进展, 2023, 42(9): 4603-4615.
[15]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.