CN106006620A - Graphene oxide aerogel and graphene aerogel, as well as preparation methods and environmental application of graphene oxide aerogel and graphene aerogel - Google Patents

Graphene oxide aerogel and graphene aerogel, as well as preparation methods and environmental application of graphene oxide aerogel and graphene aerogel Download PDF

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CN106006620A
CN106006620A CN201610361186.2A CN201610361186A CN106006620A CN 106006620 A CN106006620 A CN 106006620A CN 201610361186 A CN201610361186 A CN 201610361186A CN 106006620 A CN106006620 A CN 106006620A
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付明来
陈建炜
杨佳诚
苑宝玲
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Abstract

本发明涉及石墨烯氧化物和石墨烯气凝胶及其制备方法与环境应用。石墨烯氧化物(GO)和石墨烯(G)气凝胶分别是GO和G基本单元构成的两类具有大量孔隙、类似海绵状结构的碳固体;具有极低密度、极强亲疏水性、较强弹性及防火性等特性。气凝胶制备工艺包括:(1)制备氧化石墨前驱体,(2)控制氧化石墨性质如官能团种类和数量、分散性、浓度、尺寸结构等,(3)水热/溶剂热GO(或G)溶液,(4)干燥(干燥和还原)处理后,即可获得性能优异的GO(或G)气凝胶。该制备工艺可操作性强、易于扩大,所制备的气凝胶在吸附去除废水中染料和废油方面具有广阔应用前景。The invention relates to graphene oxide and graphene airgel, their preparation method and environmental application. Graphene oxide (GO) and graphene (G) airgel are two types of carbon solids with a large number of pores and a sponge-like structure composed of GO and G basic units respectively; they have extremely low density, strong hydrophilicity and hydrophobicity, and relatively Strong elasticity and fire resistance and other characteristics. The airgel preparation process includes: (1) preparation of graphite oxide precursor, (2) control of graphite oxide properties such as functional group type and quantity, dispersion, concentration, size structure, etc., (3) hydrothermal/solvothermal GO (or G ) solution, (4) after drying (drying and reduction) treatment, GO (or G) airgel with excellent performance can be obtained. The preparation process has strong operability and is easy to expand, and the prepared airgel has broad application prospects in the adsorption and removal of dyes and waste oils in wastewater.

Description

石墨烯氧化物和石墨烯气凝胶及其制备方法与环境应用 Graphene oxide and graphene airgel, preparation method and environmental application thereof

技术领域 technical field

本发明属于高效功能材料,具体地说是石墨烯氧化物和石墨烯气凝胶及其制备方法与环境应用,两种气凝胶在材料化学、环境、电子和能源等领域具有广阔的应用前景。 The invention belongs to high-efficiency functional materials, specifically graphene oxide and graphene airgel and their preparation methods and environmental applications. The two aerogels have broad application prospects in the fields of material chemistry, environment, electronics and energy. .

背景技术 Background technique

气凝胶(aerogel),又称为干凝胶,是经过化学溶液反应,形成溶胶,再凝胶化获得的凝胶。除去凝胶中的大部分溶剂,获得的一种空间网状结构中充满气体,外表呈固体状密度极低的(接近空气密度)多孔材料。气凝胶具有密度低、孔隙率高、比表面积大、热导率低和化学性能稳定等性质,由这些基本性质可以衍生出其它性能,诸如隔热、隔音、防震、亲/疏水等。气凝胶分为四类,第一类为无机气凝胶(氧化物、氟化物、碳化物、混合氧化物),第二类为有机气凝胶(醛系、脲衍生物、聚合物、碳类),第三类为混合气凝胶(有机+无机),第四类为复合气凝胶(纤维增强气凝胶、其它复合气凝胶)。常见的气凝胶有硅气凝胶、碳气凝胶和二氧化硅气凝胶。石墨烯氧化物和石墨烯气凝胶是最新发展的气凝胶,属于碳气凝胶。 Aerogel, also known as xerogel, is a gel obtained by reacting with a chemical solution to form a sol and then gel. Most of the solvent in the gel is removed, and the obtained space network structure is filled with gas, and the appearance is solid-like porous material with extremely low density (close to air density). Airgel has the properties of low density, high porosity, large specific surface area, low thermal conductivity and stable chemical properties. From these basic properties, other properties can be derived, such as heat insulation, sound insulation, shock resistance, hydrophilic/hydrophobic, etc. Airgel is divided into four categories, the first category is inorganic aerogels (oxides, fluorides, carbides, mixed oxides), the second category is organic aerogels (aldehydes, urea derivatives, polymers, carbon), the third type is hybrid aerogels (organic + inorganic), and the fourth type is composite aerogels (fiber-reinforced aerogels, other composite aerogels). Common aerogels are silica aerogel, carbon aerogel and silica aerogel. Graphene oxide and graphene aerogels are the latest developed aerogels, belonging to carbon aerogels.

碳是自然界分布最普遍的元素之一,也是构成地球上一切生命体最重要的元素。以碳元素为主要构成的有机高分子材料,包括塑料、橡胶和纤维等,已发展成为材料学三个主要学科方向之一。而以碳元素本身,通过不同结构、组合,能形成一个独特的无机非金属材料世界。碳原子间不仅能够以sp3杂化轨道形成单键,还能以sp2及sp杂化轨道形成稳定的双键和叁键,因此,除了自然界存在多种同素异形体的碳材料外,科学家们通过实验还合成了众多结构和性质完全不同的碳材料,如人们熟悉的金刚石和石墨,以及以C60为代表的富勒烯以及碳纳米粉体、管材、线材等,这些碳纳米材料始终是纳米材料和纳米科学研究的重点。最近新型碳纳米材料石墨烯的发现以及其潜在的应用,更是推动这类新型碳纳米材料的研究与应用。这些新型碳材料的特性几乎可涵盖地球上所有物质的性质甚至相对立的两种性质,如从最硬到极软、全吸光-全透光、绝缘体-半导体-高导体、绝热-良导热、高铁磁体、高临界温度的超导体等。因此,碳材料作为一种重要的材料,开展碳材料的研究与产业化应用,重点关注石墨烯为基础的新型碳纳米材料研究,是发展高新材料的一个重要的方向。 Carbon is one of the most widely distributed elements in nature and the most important element that constitutes all life on earth. Organic polymer materials mainly composed of carbon, including plastics, rubber and fibers, have developed into one of the three main disciplines of materials science. And carbon itself, through different structures and combinations, can form a unique world of inorganic non-metallic materials. Carbon atoms can not only form single bonds with sp 3 hybrid orbitals, but also form stable double bonds and triple bonds with sp 2 and sp hybrid orbitals. Therefore, in addition to carbon materials with various allotropes in nature, Scientists have also synthesized many carbon materials with completely different structures and properties through experiments, such as familiar diamond and graphite, and fullerene represented by C60, as well as carbon nanopowders, pipes, wires, etc. These carbon nanomaterials are always It is the focus of nanomaterials and nanoscience research. The recent discovery of graphene, a new type of carbon nanomaterial, and its potential applications have promoted the research and application of this type of new type of carbon nanomaterial. The characteristics of these new carbon materials can almost cover the properties of all substances on the earth and even two opposite properties, such as from the hardest to the softest, full light absorption-full light transmission, insulator-semiconductor-high conductor, heat insulation-good thermal conductivity, High ferromagnets, high critical temperature superconductors, etc. Therefore, as an important material, carbon materials are an important direction for the development of high-tech materials to carry out the research and industrial application of carbon materials, focusing on the research of new carbon nanomaterials based on graphene.

2004年,英国曼切斯特大学物理学家安德烈•海姆和康斯坦丁•诺沃肖洛夫,成功地在实验中从石墨中分离出石墨烯(graphene, GR),证实石墨烯可以稳定存在。仅仅6年之后,两人便因此共同获得了2010年诺贝尔物理学奖。一个成果从完成到获诺贝尔奖,仅仅间隔6年时间,是十分罕见的。石墨烯是碳原子以sp2轨道杂化组成六角形蜂巢状晶格的二维(2D)晶体,可以看作是所有碳纳米材料的基础结构。石墨烯可以曲翘成零维(0D)的富勒烯(fullerence);卷曲成一维(1D)的碳纳米管(carbon nanotube, CNT)或堆叠成三维(3D)的石墨(graphite)。由于石墨烯具有超高的强度和韧性、不透水、不透气、耐强酸碱、既能导电又高度透明等一系列奇特性质,多个国家和研究结构对它的研发投入了极大兴趣。有科学家甚至预言,石墨烯将“彻底改变21世纪”。 In 2004, Andre Heim and Konstantin Novoselov, physicists at the University of Manchester, UK, successfully separated graphene (GR) from graphite in experiments, confirming that graphene can exist stably. Only six years later, the two jointly won the 2010 Nobel Prize in Physics. It is very rare that there is only 6 years between the completion of a result and the Nobel Prize. Graphene is a two-dimensional (2D) crystal in which carbon atoms are hybridized in sp2 orbitals to form a hexagonal honeycomb lattice, which can be regarded as the basic structure of all carbon nanomaterials. Graphene can be warped into zero-dimensional (0D) fullerene (fullerence); curled into one-dimensional (1D) carbon nanotube (carbon nanotube, CNT) or stacked into three-dimensional (3D) graphite (graphite). Because graphene has a series of unique properties such as ultra-high strength and toughness, impermeability, airtightness, strong acid and alkali resistance, electrical conductivity and high transparency, many countries and research institutions have invested great interest in its research and development. Some scientists even predict that graphene will "completely change the 21st century".

气凝胶是前驱体经过化学溶液反应形成溶胶,溶胶聚合凝胶化得到凝胶,通过干燥(通常是超临界干燥和冷冻干燥)除去溶胶中的大部分溶剂即可获得具有空间网状结构并充满气体的固体气凝胶。石墨烯氧化物和石墨烯气凝胶以氧化石墨为前驱体,通过超声分散得到石墨烯氧化物胶体溶液,经过水热/溶剂热过程得到凝胶,凝胶干燥后便可获得气凝胶。对石墨烯氧化物胶体溶液(官能团种类及数量、分散性及浓度、尺寸、结构完整性等)、水热/溶剂热过程(溶剂类型、反应条件)、干燥工艺及后续处理(还原)等进行详细系统的研究,可以获得具有优异性能的石墨烯氧化物和石墨烯气凝胶。气凝胶的应用非常广泛,包括热学领域、电学领域、声学领域、光学领域、过滤与催化领域、吸附领域、分形特性及捕获高速粒子等,以热学应用领域为例,气凝胶在化工工业、建筑工业、石油工业、运输工业、原油泄漏、航空航天、国防、鞋子和其它民用行业上均有涉猎。石墨烯氧化物和石墨烯气凝胶的应用同样遍及各行各业,它们在环境领域的应用得到了极大的关注,特别是在污染物吸附去除方面,净化环境的潜力无限,主要得益于它们的三维多孔结构,结构中包含了无数的大孔、中孔、介孔、微孔,这就赋予石墨烯氧化物和石墨烯气凝胶巨大的比表面、孔容,再加上巨大的π共轭结构,无疑是作为吸附材料的最佳选择。 Airgel is a precursor that reacts with a chemical solution to form a sol, and the sol is polymerized and gelled to obtain a gel, and most of the solvent in the sol can be removed by drying (usually supercritical drying and freeze drying) to obtain a space network structure and Solid aerogels filled with gas. Graphene oxide and graphene airgel use graphite oxide as a precursor, obtain a graphene oxide colloidal solution by ultrasonic dispersion, and obtain a gel through a hydrothermal/solvothermal process, and then obtain an aerogel after the gel is dried. Graphene oxide colloidal solution (type and quantity of functional groups, dispersion and concentration, size, structural integrity, etc.), hydrothermal/solvothermal process (solvent type, reaction conditions), drying process and subsequent treatment (reduction), etc. With detailed and systematic research, graphene oxides and graphene aerogels with excellent properties can be obtained. Airgel has a wide range of applications, including thermal fields, electrical fields, acoustic fields, optical fields, filtration and catalysis fields, adsorption fields, fractal characteristics, and capturing high-speed particles, etc. Taking thermal applications as an example, airgel plays an important role in the chemical industry , construction industry, petroleum industry, transportation industry, crude oil spills, aerospace, defense, shoes and other civilian industries are involved. Graphene oxide and graphene aerogels are also used in all walks of life, and their application in the environmental field has received great attention, especially in the adsorption and removal of pollutants. The potential for purifying the environment is unlimited, mainly due to Their three-dimensional porous structure contains numerous macropores, mesopores, mesopores, and micropores, which endow graphene oxide and graphene airgel with a huge specific surface area and pore volume, plus a huge The π-conjugated structure is undoubtedly the best choice as an adsorption material.

发明内容 Contents of the invention

本发明的目的在于提供石墨烯氧化物和石墨烯气凝胶及其制备方法与环境应用。石墨烯氧化物(GO)和石墨烯(G)气凝胶分别是GO和G基本单元构成的两类具有大量孔隙、类似海绵状结构的碳固体。GO密度为0.3~2.0 mg/cm3、接触角在30~80 °、孔径为1 nm~5 μm、孔隙率为65~99%、比表面积为100~1700 m2/g并具有较强弹性及防火性;G密度为0.25~1.8 mg/cm3、接触角在95~150 °、孔径为1 nm~3.5 μm、孔隙率为80~99%、比表面积为300~2000 m2/g并具有较强弹性及防火性。 The object of the present invention is to provide graphene oxide and graphene airgel and preparation method thereof and environmental application. Graphene oxide (GO) and graphene (G) aerogels are two types of carbon solids with a large number of pores and a sponge-like structure composed of GO and G basic units, respectively. GO has a density of 0.3~2.0 mg/cm 3 , a contact angle of 30~80°, a pore size of 1 nm~5 μm, a porosity of 65~99%, a specific surface area of 100~1700 m 2 /g and strong elasticity. and fire resistance; G density is 0.25~1.8 mg/cm 3 , contact angle is 95~150 °, pore diameter is 1 nm~3.5 μm, porosity is 80~99%, specific surface area is 300~2000 m 2 /g and It has strong elasticity and fire resistance.

本发明的另一目的是提供所述GO和G气凝胶的可控制备方法,制备方法包括:(1)制备氧化石墨前驱体,(2)控制氧化石墨性质如官能团种类和数量、分散性、浓度、尺寸结构等,(3)水热/溶剂热GO(或G)溶液,(4)干燥(或干燥和还原)处理后,即可获得性能优异的GO(或G)气凝胶。本发明的目的通过以下技术路线实现。 Another object of the present invention is to provide a controllable preparation method of the GO and G aerogels, the preparation method includes: (1) preparing graphite oxide precursor, (2) controlling the properties of graphite oxide such as the type and quantity of functional groups, and dispersibility , concentration, size structure, etc., (3) hydrothermal/solvothermal GO (or G) solution, (4) after drying (or drying and reduction) treatment, GO (or G) airgel with excellent performance can be obtained. The object of the present invention is achieved through the following technical routes.

1. 氧化石墨的制备: 1. Preparation of graphite oxide:

所述氧化石墨溶液采用改进的Hummer法合成。 The graphite oxide solution is synthesized by an improved Hummer method.

(1)取100~500 mL浓硫酸、1.0~5.0 g石墨粉和5.0~30.0 g高锰酸钾在冰水浴下搅拌分散0.5~3.0 h。 (1) Take 100~500 mL concentrated sulfuric acid, 1.0~5.0 g graphite powder and 5.0~30.0 g potassium permanganate and stir and disperse 0.5~3.0 g under ice water bath h.

(2)将步骤(1)得到的混合物在25~50 ℃下保持1~12 h。 (2) Keep the mixture obtained in step (1) at 25-50 °C for 1-12 h.

(3)往步骤(2)得到的产物中加入100~300 mL去离子水,待反应体系冷却降温到90~105 ℃时滴加2~10 mL过氧化氢直至反应溶液没有颜色变化。 (3) Add 100-300 mL of deionized water to the product obtained in step (2), and when the reaction system cools down to 90-105 °C, add 2-10 mL of hydrogen peroxide dropwise until the reaction solution has no color change.

(4)将步骤(3)的产物依次用250~1500 mL、体积分数为20%~50%的盐酸溶液和1500~7500 mL去离子水进行洗涤产物。 (4) Wash the product of step (3) with 250-1500 mL of hydrochloric acid solution with a volume fraction of 20%-50% and 1500-7500 mL of deionized water in sequence.

(5)将上一步骤得到的产物配制成浓度为0.3~15 mg/mL氧化石墨水溶液。所得氧化石墨具有丰富的含氧官能团、碎片少结构较完整、尺寸在0.5~45 μm、分散性极好。 (5) Prepare the product obtained in the previous step to a concentration of 0.3~15 mg/mL graphite oxide aqueous solution. The obtained graphite oxide has abundant oxygen-containing functional groups, fewer fragments and relatively complete structure, with a size of 0.5-45 μm and excellent dispersibility.

2. GO气凝胶的制备: 2. Preparation of GO airgel:

石墨经过预氧化和性能处理后,所述GO气凝胶优选通过溶剂热和冷冻干燥两个过程合成。 After pre-oxidation and performance treatment of graphite, the GO airgel is preferably synthesized by two processes of solvothermal and freeze-drying.

(1)取2~30 mL浓度为0.3~15.0 mg/mL的氧化石墨水溶液并加入0~118 mL去离子水或乙醇或乙二醇,对新配制的氧化石墨溶液进行功率为40~200 W、频率为8~40 KHZ超声分散5~120 min得到GO胶体溶液。 (1) Take 2~30 mL of graphite oxide aqueous solution with a concentration of 0.3~15.0 mg/mL and add 0~118 mL of deionized water or ethanol or ethylene glycol, and perform a power of 40~200 on the newly prepared graphite oxide solution. W, frequency 8~40 KHZ ultrasonic dispersion 5~120 min to get GO colloidal solution.

(2)将步骤(1)得到的GO胶体溶液转移到内衬聚四氟乙烯反应釜中,为了增强所得石墨烯氧化物气凝胶的机械性能,可在反应釜中加入0.1~1.0 wt%的高聚物(PEG、PAN和PVDF),在100~200 ℃下反应6~24 h。 (2) Transfer the GO colloidal solution obtained in step (1) to a polytetrafluoroethylene-lined reactor. In order to enhance the mechanical properties of the obtained graphene oxide airgel, 0.1~1.0 wt% The polymers (PEG, PAN and PVDF) were reacted at 100-200 °C for 6-24 h.

(3)将步骤(2)得到的GO凝胶反复用去离子水洗涤6~24 次,在冷冻温度为-5~-65 ℃,真空度为15~60000 Pa的条件下干燥1~72 h即可获得GO气凝胶。 (3) The GO gel obtained in step (2) was repeatedly washed with deionized water for 6 to 24 times, and dried at a freezing temperature of -5 to -65 °C and a vacuum of 15 to 60,000 Pa for 1 to 72 h GO airgel can be obtained.

3. G气凝胶的制备: 3. Preparation of G airgel:

石墨经过预氧化和性能处理后,所述G气凝胶优选通过溶剂热、冷冻干燥及还原处理三个过程合成。 After pre-oxidation and performance treatment of graphite, the G airgel is preferably synthesized through three processes of solvothermal, freeze-drying and reduction treatment.

(1)取2~30 mL浓度为0.3~15.0 mg/mL的氧化石墨水溶液,利用等密度差速离心对氧化石墨水溶液的溶剂水进行乙醇或乙二醇的置换,转速设定为12000~18000 转/分钟,氧化石墨水溶液首次离心后每次都加入乙醇或乙二醇进行高速离心3~30 次以完成乙醇或乙二醇对水的置换配制氧化石墨的乙醇或乙二醇溶液,为了得到具有不同性质的G气凝胶,可以通过加入10~40 mL去离子水到氧化石墨的乙醇或乙二醇溶液中配制氧化石墨乙醇与水的混合液或乙二醇与水的混合液。对新配制的氧化石墨溶液进行功率为40~200 W、频率为8~40 KHZ超声分散5~120 min得到GO胶体溶液。 (1) Take 2~30 mL of graphite oxide aqueous solution with a concentration of 0.3~15.0 mg/mL, use isopycnic differential centrifugation to replace the solvent water of graphite oxide aqueous solution with ethanol or ethylene glycol, and set the speed at 12000~18000 rpm, after the first centrifugation of the graphite oxide aqueous solution, ethanol or ethylene glycol was added each time to carry out high-speed centrifugation for 3 to 30 times to complete the replacement of water by ethanol or ethylene glycol to prepare the ethanol or ethylene glycol solution of graphite oxide, in order to obtain For G aerogels with different properties, a mixture of graphite oxide ethanol and water or a mixture of ethylene glycol and water can be prepared by adding 10-40 mL of deionized water to the ethanol or ethylene glycol solution of graphite oxide. The power of the newly prepared graphite oxide solution is 40~200 W, frequency 8~40 KHZ ultrasonic dispersion 5~120 min to get GO colloidal solution.

(2)将步骤(1)得到的GO胶体溶液转移到内衬聚四氟乙烯反应釜中,为了增强所得G气凝胶的机械性能和提高还原程度,可在反应釜中加入0.1~1.0 wt%的添加剂(1H,1H,2H,2H-全弗葵基硫醇、多巴胺、葡萄糖、蔗糖等)。 (2) Transfer the GO colloid solution obtained in step (1) to a polytetrafluoroethylene-lined reactor. In order to enhance the mechanical properties of the obtained G airgel and increase the degree of reduction, 0.1–1.0 wt. % of additives (1H,1H,2H,2H-full fudecyl mercaptan, dopamine, glucose, sucrose, etc.).

(3)将步骤(2)得到的石墨烯(氧化物)凝胶反复用去离子水洗涤6~24 次,在冷冻温度为-5~-65 ℃,真空度为15~60000 Pa的条件下干燥1~72 h即可获得石墨烯(氧化物)气凝胶。 (3) Wash the graphene (oxide) gel obtained in step (2) repeatedly with deionized water for 6 to 24 times, at a freezing temperature of -5 to -65 ℃, drying under the condition of vacuum degree of 15-60000 Pa for 1-72 h can obtain graphene (oxide) airgel.

(4)将步骤(3)得到的石墨烯(氧化物)气凝胶做进一步还原处理,处理方法包括在氩气氛下以300~1000 ℃/h的升温速率,1600~2800 ℃高温处理30~240 min、40~80 ℃的10~40%的氢碘酸溶液浸渍3~24 h后在25~60 ℃条件下真空干燥12~48 h、40~80 ℃的10~25%的氨水溶液浸渍3~24 h后在25~60 ℃条件下真空干燥12~48 h和0.5~5 g/L的硼氢化钠溶液中浸渍3~24 h后在25~60 ℃条件下真空干燥12~48 h。 (4) The graphene (oxide) airgel obtained in step (3) is further reduced, and the treatment method includes 300~1000 ℃/h heating rate, 1600~2800 ℃ high temperature treatment for 30~240 min, 40~80 10~40% hydroiodic acid solution at ℃ for 3~24 After h, vacuum dry at 25~60°C for 12~48 h. Immerse in 10-25% ammonia solution at 40-80 °C for 3-24 h, then vacuum dry at 25-60 °C for 12-48 h and immerse in 0.5-5 g/L sodium borohydride solution for 3-24 h. After 25~60 h Vacuum drying at ℃ for 12-48 h.

所述利用GO和G气凝胶用以环境中污染物的吸附去除。 The GO and G aerogels are used for adsorption and removal of pollutants in the environment.

本发明与现有技术相比具有以下优点 Compared with the prior art, the present invention has the following advantages .

(1)本发明所述石墨烯氧化物和石墨烯气凝胶具有优异的特性及性能,低密度、高孔隙率(无数互相连接的大孔、中孔、介孔和微孔)、大比表面、低热导率、可调接触角和化学性质稳定等,由这些基本特性衍生出隔热、隔音、防震、亲/疏水、导电、弹性及防火性等。 (1) The graphene oxide and graphene airgel of the present invention have excellent characteristics and performance, low density, high porosity (numerous interconnected macropores, mesopores, mesopores and micropores), large specific Surface, low thermal conductivity, adjustable contact angle, and stable chemical properties, etc., are derived from these basic properties for heat insulation, sound insulation, shock resistance, hydrophilic/hydrophobic, electrical conductivity, elasticity, and fire resistance.

(2)本发明所提供的石墨烯氧化物和石墨烯气凝胶制备方法系统、工艺简单并易于扩大。气凝胶的制备以氧化石墨为前驱体,通过控制氧化石墨的性质(官能团种类及数量、分散性及浓度、尺寸、结构完整性等)、水热/溶剂热过程(溶剂类型、反应条件)、干燥工艺及后续处理(还原),可以获得具有特定形貌、尺寸和优异性能的石墨烯氧化物和石墨烯气凝胶。 (2) The graphene oxide and graphene airgel preparation method system provided by the present invention is simple in process and easy to expand. The preparation of airgel uses graphite oxide as a precursor, by controlling the properties of graphite oxide (type and quantity of functional groups, dispersion and concentration, size, structural integrity, etc.), hydrothermal/solvothermal process (solvent type, reaction conditions) , drying process and subsequent treatment (reduction), graphene oxide and graphene airgel with specific morphology, size and excellent properties can be obtained.

(3)本发明提供的石墨烯氧化物和石墨烯气凝胶是具有大孔容和比表面的三维碳材料,因此这两类气凝胶可以作为优异的吸附材料应用在环境净化中,可重复利用且再生性能高,经济环保。石墨烯气凝胶由于具有优越的导电性致使其在电子领域的应用潜力巨大,另外,具备优异特性及性能的石墨烯氧化物和石墨烯气凝胶在材料、化学、能源等领域的应用前景也非常广阔。 (3) The graphene oxide and graphene airgel provided by the present invention are three-dimensional carbon materials with large pore volume and specific surface area, so these two types of airgel can be used as excellent adsorption materials in environmental purification, and can Reusable and high regeneration performance, economical and environmentally friendly. Due to its superior electrical conductivity, graphene airgel has great application potential in the field of electronics. In addition, graphene oxide and graphene aerogel with excellent characteristics and performance have application prospects in the fields of materials, chemistry, and energy. Also very expansive.

附图说明 Description of drawings

图1为氧化石墨粉末的宏观形貌。 Figure 1 is the macroscopic morphology of graphite oxide powder.

图2为本发明制备的石墨烯氧化物气凝胶1的宏观形貌。 Fig. 2 is the macroscopic morphology of the graphene oxide airgel 1 prepared in the present invention.

图3为本发明制备的石墨烯氧化物气凝胶2的宏观形貌。 Fig. 3 is the macroscopic morphology of the graphene oxide airgel 2 prepared in the present invention.

图4为本发明制备的石墨烯氧化物气凝胶3的弹性测试实验。 Fig. 4 is the elasticity test experiment of the graphene oxide airgel 3 prepared by the present invention.

图5为本发明制备的石墨烯氧化物气凝胶4的水接触角测试实验。 Fig. 5 is the water contact angle test experiment of the graphene oxide airgel 4 prepared by the present invention.

图6为本发明制备的石墨烯氧化物气凝胶5吸附罗丹明B的效果图。 Fig. 6 is an effect diagram of adsorption of rhodamine B by graphene oxide airgel 5 prepared in the present invention.

图7为本发明制备的石墨烯气凝胶1的宏观形貌。 Fig. 7 is the macroscopic morphology of the graphene airgel 1 prepared in the present invention.

图8为本发明制备的石墨烯气凝胶2的宏观形貌。 Fig. 8 is the macroscopic morphology of the graphene airgel 2 prepared in the present invention.

图9为本发明制备的石墨烯气凝胶3的防火性测试实验。 Fig. 9 is a flame test experiment of the graphene airgel 3 prepared by the present invention.

图10为本发明制备的石墨烯气凝胶4的水接触角测试实验。 Fig. 10 is a test experiment of the water contact angle of the graphene airgel 4 prepared by the present invention.

图11为本发明制备的石墨烯气凝胶5吸附炼油厂废油液的效果图。 Fig. 11 is an effect diagram of graphene airgel 5 prepared by the present invention adsorbing refinery waste oil.

图12为本发明制备的石墨烯气凝胶6的宏观形貌。 Fig. 12 is the macroscopic morphology of the graphene airgel 6 prepared by the present invention.

具体实施方式 detailed description

下面结合实施例和附图对本发明作进一步详细说明,但本发明保护范围不局限于所述内容。 The present invention will be described in further detail below in conjunction with the embodiments and accompanying drawings, but the protection scope of the present invention is not limited to the content described.

实施例 1 Embodiment 1 :

按照本发明提出的合成方法制备氧化石墨。 Graphite oxide is prepared according to the synthesis method proposed by the present invention.

将105 mL浓硫酸、1.0 g石墨和6.5 g高锰酸钾在冰水浴下搅拌分散2.0 h,;然后把混合物转移至油浴锅中,在36 ℃下保持5 h;过程结束后将反应容器从油浴锅中转移出来并迅速加入300 mL去离子水,加入的同时剧烈搅拌,待反应体系冷却降温到98 ℃时逐滴滴加5.0 mL过氧化氢直至反应溶液没有颜色变化和气体产生;依次用300 mL体积分数为20%盐酸溶液4500 mL去离子水洗涤样品至中性后,将氧化石墨配制成浓度为0.3~15 mg/mL的氧化石墨水溶液。所制氧化石墨具有丰富的含氧官能团、碎片少结构较完整、尺寸在0.5~45 μm、分散性极好。取适量氧化石墨水溶液在40 ℃条件下真空干燥60 h得到如图1所示的氧化石墨粉末。 Stir and disperse 105 mL of concentrated sulfuric acid, 1.0 g of graphite and 6.5 g of potassium permanganate in an ice-water bath for 2.0 h; then transfer the mixture to an oil bath and keep it at 36 °C for 5 h; Transfer it from the oil bath and quickly add 300 mL of deionized water. Stir vigorously while adding. When the reaction system cools down to 98 °C, add 5.0 mL of hydrogen peroxide drop by drop until the reaction solution has no color change and gas generation; Wash the sample with 300 mL of 20% hydrochloric acid solution and 4500 mL of deionized water to neutrality, and prepare graphite oxide at a concentration of 0.3-15 mg/mL graphite oxide aqueous solution. The prepared graphite oxide has abundant oxygen-containing functional groups, less fragments and relatively complete structure, with a size of 0.5-45 μm and excellent dispersion. An appropriate amount of graphite oxide aqueous solution was vacuum-dried at 40 °C for 60 h to obtain graphite oxide powder as shown in Figure 1.

实施例Example 22 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶1。 Graphene oxide airgel 1 was prepared according to the synthesis method proposed in the present invention.

量取30 mL浓度为1.0 mg/mL的氧化石墨(尺寸为0.5~3 μm)水溶液进行功率为200 W、频率为40 KHZ的超声分散40 min得到石墨烯氧化物的胶体溶液;将石墨烯氧化物胶体溶液转移到内衬聚四氟乙烯反应釜中,在180 ℃下反应12 h;把水热反应得到的石墨烯氧化物凝胶用去离子水洗涤12 次,在冷冻温度为-55 ℃,真空度为1000 Pa的条件下干燥24 h获得石墨烯氧化物气凝胶1,其比表面积为299 m2/g,宏观形貌如图2所示。 Measure 30 mL of graphite oxide (0.5-3 μm in size) aqueous solution with a concentration of 1.0 mg/mL and perform ultrasonic dispersion with a power of 200 W and a frequency of 40 KHZ for 40 min to obtain a colloidal solution of graphene oxide; The colloid solution was transferred to a polytetrafluoroethylene-lined reactor, and reacted at 180 °C for 12 h; the graphene oxide gel obtained by the hydrothermal reaction was washed 12 times with deionized water, and the freezing temperature was -55 °C. , and dried for 24 h under the condition of vacuum degree of 1000 Pa to obtain graphene oxide airgel 1 with a specific surface area of 299 m 2 /g, and the macroscopic morphology is shown in Fig. 2 .

实施例Example 33 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶2。 Graphene oxide airgel 2 was prepared according to the synthesis method proposed in the present invention.

量取20 mL浓度为1.0 mg/mL的氧化石墨(尺寸为0.5~3 μm)水溶液并加入10 mL乙醇配制氧化石墨乙醇和水混合溶液进行功率为200 W、频率为40 KHZ超声分散30 min得到石墨烯氧化物的胶体溶液;将石墨烯氧化物胶体溶液转移到内衬聚四氟乙烯反应釜中,在170 ℃下反应15 h;把溶剂热反应得到的石墨烯氧化物凝胶用去离子水洗涤24 次,在冷冻温度为-60 ℃,真空度为1000 Pa的条件下干燥20 h获得石墨烯氧化物气凝胶2,经测定,石墨烯氧化物气凝胶2的的密度为0.95 mg/cm3,其宏观形貌如图3所示。 Measure 20 mL of graphite oxide (0.5-3 μm in size) aqueous solution with a concentration of 1.0 mg/mL and add 10 mL of ethanol to prepare a mixed solution of graphite oxide ethanol and water, and perform ultrasonic dispersion at 200 W and 40 KHZ for 30 min to obtain Colloidal solution of graphene oxide; transfer the graphene oxide colloidal solution to a polytetrafluoroethylene-lined reactor and react at 170 °C for 15 h; After washing with water for 24 times, drying for 20 h at a freezing temperature of -60 °C and a vacuum of 1000 Pa to obtain graphene oxide airgel 2, the density of graphene oxide airgel 2 was determined to be 0.95 mg/cm 3 , and its macroscopic morphology is shown in Fig. 3 .

实施例Example 44 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶3。 Graphene oxide airgel 3 was prepared according to the synthesis method proposed in the present invention.

量取10 mL浓度为3.0 mg/mL的氧化石墨(尺寸为30~45 μm)水溶液并加入20 mL乙二醇配制氧化石墨乙二醇和水混合溶液进行功率为80 W、频率为16 KHZ超声分散10 min得到石墨烯氧化物的胶体溶液;将石墨烯氧化物胶体溶液转移到内衬聚四氟乙烯反应釜中,在反应釜中加入0.5%的PEG,在180 ℃下反应24 h;把溶剂热反应得到的石墨烯氧化物凝胶用去离子水洗涤24 次,在冷冻温度为-65 ℃,真空度为5000 Pa的条件下干燥48 h获得石墨烯氧化物气凝胶3,石墨烯氧化物气凝胶3的弹性测试实验如图4所示。 Measure 10 mL of graphite oxide (30-45 μm in size) aqueous solution with a concentration of 3.0 mg/mL and add 20 mL of ethylene glycol to prepare a mixed solution of graphite oxide ethylene glycol and water. The power is 80 W and the frequency is 16 KHZ ultrasonic dispersion for 10 min to obtain a colloidal solution of graphene oxide; transfer the graphene oxide colloidal solution to a polytetrafluoroethylene-lined reactor, add 0.5% PEG to the reactor, and react at 180 °C for 24 h ; The graphene oxide gel obtained by the solvothermal reaction was washed 24 times with deionized water, and dried for 48 h at a freezing temperature of -65 °C and a vacuum of 5000 Pa to obtain graphene oxide airgel 3, The elastic test experiment of graphene oxide airgel 3 is shown in Figure 4.

实施例 5 Embodiment 5 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶4。 Graphene oxide airgel 4 was prepared according to the synthesis method proposed in the present invention.

本实施例与实施例2相比,除了改变氧化石墨的浓度(1.5 mg/mL)外,其他均与实施例2完全相同。得到的石墨烯氧化物气凝胶4的接触角为46 °(图5)。 Compared with Example 2, this example is exactly the same as Example 2 except for changing the concentration of graphite oxide (1.5 mg/mL). The obtained graphene oxide airgel 4 has a contact angle of 46° (Fig. 5).

实施例 6 Embodiment 6 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶5。 Graphene oxide airgel 5 was prepared according to the synthesis method proposed in the present invention.

本实施例与实施例4相比,除了改变氧化石墨乙二醇和水混合溶液为氧化石墨水溶液,其他均与实施例4完全相同。以所制备的石墨烯氧化物气凝胶5(质量为27 mg)作为滤芯制作滤柱,配制10 mg/L的罗丹明B溶液,往过滤柱注射10 mL罗丹明B溶液,溶液在重力作用下滤出,5 个循环的罗丹明B去除率均为100%(图6)。 Compared with Example 4, this example is identical to Example 4 except that the mixed solution of graphite oxide ethylene glycol and water is changed to an aqueous solution of graphite oxide. The prepared graphene oxide airgel 5 (mass 27 mg) was used as a filter element to make a filter column, and a 10 mg/L Rhodamine B solution was prepared, and 10 mL of Rhodamine B solution was injected into the filter column, and the solution was The removal rate of rhodamine B in the five cycles was 100% (Fig. 6).

实施例 7 Embodiment 7 :

按照本发明提出的合成方法制备石墨烯气凝胶1。 Graphene airgel 1 was prepared according to the synthesis method proposed in the present invention.

量取2 mL浓度为15.0 mg/mL的氧化石墨(尺寸为30~45 μm)水溶液,利用等密度差速离心对氧化石墨水溶液的溶剂水进行乙醇的置换,转速设定为18000 转/分钟,氧化石墨水溶液首次离心后每次都加入乙醇进行高速离心20 次以完成乙醇对水的置换配制氧化石墨乙醇溶液(定容到30 mL),对新配制的氧化石墨乙醇溶液搅拌分散2 h后进行功率为80 W、频率为16 KHZ超声分散10 min得到石墨烯氧化物胶体乙醇溶液;将石墨烯氧化物胶体乙醇溶液转移到内衬聚四氟乙烯反应釜中,在反应釜中加入0.5%的1H,1H,2H,2H-全弗葵基硫醇和0.5%的多巴胺,在180 ℃下反应12 h;把溶剂热反应得到的石墨烯(氧化物)凝胶反复用去离子水洗涤12 次,在冷冻温度为-60 ℃,真空度为1000 Pa的条件下干燥36 h获得石墨烯(氧化物)气凝胶1;所制石墨烯(氧化物)气凝胶进一步在氩气氛下以900 ℃/h的升温速率,1600 ℃高温处理120 min即可得到石墨烯气凝胶1,其比表面积为341 m2/g,宏观形貌如图7所示。 Measure 2 mL of graphite oxide (30-45 μm in size) aqueous solution with a concentration of 15.0 mg/mL, and use isopycnic differential centrifugation to replace the solvent water of the graphite oxide aqueous solution with ethanol, with the speed set at 18,000 rpm. After the graphite oxide aqueous solution was centrifuged for the first time, ethanol was added each time for high-speed centrifugation 20 times to complete the replacement of ethanol with water. Prepare graphite oxide ethanol solution (constant volume to 30 mL), and stir and disperse the newly prepared graphite oxide ethanol solution for 2 h. The power is 80 W and the frequency is 16 KHZ ultrasonic dispersion for 10 min to obtain the graphene oxide colloid ethanol solution; the graphene oxide colloid ethanol solution is transferred to a polytetrafluoroethylene lined reactor, and 0.5% 1H, 1H, 2H, 2H-full fudecyl mercaptan and 0.5% dopamine were reacted at 180 °C for 12 h; the graphene (oxide) gel obtained by the solvothermal reaction was washed 12 times with deionized water repeatedly, Graphene (oxide) airgel 1 was obtained by drying at a freezing temperature of -60 °C and a vacuum of 1000 Pa for 36 h; the prepared graphene (oxide) airgel was further heated at 900 °C The graphene airgel 1 can be obtained by heating at a heating rate of 1600 °C for 120 min at a heating rate of 1600 °C. Its specific surface area is 341 m 2 /g, and its macroscopic morphology is shown in Figure 7.

实施例 8 Embodiment 8 :

按照本发明提出的合成方法制备石墨烯气凝胶2。 Graphene airgel 2 was prepared according to the synthesis method proposed in the present invention.

量取10 mL浓度为2.7 mg/mL的氧化石墨(尺寸为10~20 μm)水溶液并加入20 mL乙醇配制氧化石墨乙醇和水混合溶液,对新配制的氧化石墨乙醇和水混合溶液搅拌分散1 h后进行功率为100 W、频率为20 KHZ超声分散20 min得到石墨烯氧化物胶体的乙醇和水混合溶液;将石墨烯氧化物胶体的乙醇和水混合溶液转移到内衬聚四氟乙烯反应釜中,在反应釜中加入1%的蔗糖,在160 ℃下反应24 h;把溶剂热反应得到的石墨烯(氧化物)凝胶反复用去离子水洗涤24 次,在冷冻温度为-58 ℃,真空度为100 Pa的条件下干燥24 h获得石墨烯(氧化物)气凝胶2;所制石墨烯(氧化物)气凝胶进一步在80 ℃的25%的氨水溶液中浸渍3 h后在40 ℃条件下真空干燥24 h即可得到石墨烯气凝胶2,经测定,石墨烯气凝胶2的密度为0.83 mg/cm3,其宏观形貌如图8所示。 Measure 10 mL of graphite oxide (10-20 μm in size) aqueous solution with a concentration of 2.7 mg/mL and add 20 mL of ethanol to prepare graphite oxide ethanol and water mixed solution, stir and disperse the newly prepared graphite oxide ethanol and water mixed solution for 1 After h, the power is 100 W, the frequency is 20 KHZ ultrasonic dispersion for 20 min to obtain the ethanol and water mixed solution of graphene oxide colloid; the ethanol and water mixed solution of graphene oxide colloid is transferred to the liner polytetrafluoroethylene reaction Add 1% sucrose to the reactor and react at 160 °C for 24 h; wash the graphene (oxide) gel obtained by the solvothermal reaction with deionized water for 24 times, and freeze it at -58 ℃, dried at a vacuum of 100 Pa for 24 h to obtain graphene (oxide) airgel 2; the prepared graphene (oxide) aerogel was further immersed in 25% ammonia solution at 80 °C for 3 h Afterwards, the graphene airgel 2 was obtained by vacuum drying at 40°C for 24 hours. The density of the graphene airgel 2 was determined to be 0.83 mg/cm 3 , and its macroscopic morphology is shown in Figure 8.

实施例 9 Embodiment 9 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶3。 Graphene oxide airgel 3 was prepared according to the synthesis method proposed in the present invention.

本实施例与实施例7相比,除了改变石墨烯(氧化物)气凝胶的还原处理方法为80 ℃的40%的氢碘酸溶液浸渍8 h后在50 ℃条件下真空干燥48 h外,其他均与实施例7完全相同。石墨烯气凝胶3的防火性测试实验如图9所示。 Compared with Example 7 in this example, except that the reduction treatment method of the graphene (oxide) airgel was changed to immerse in 40% hydroiodic acid solution at 80 °C for 8 h and then vacuum-dried at 50 °C for 48 h. , others are identical with embodiment 7. The fire resistance test experiment of graphene airgel 3 is shown in Figure 9.

实施例 10 Embodiment 10 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶4。 Graphene oxide airgel 4 was prepared according to the synthesis method proposed in the present invention.

量取20 mL浓度为1.75 mg/mL的氧化石墨(尺寸为30~45 μm)水溶液,利用等密度差速离心对氧化石墨水溶液的溶剂水进行乙二醇的置换,转速设定为16000 转/分钟,氧化石墨水溶液首次离心后每次都加入乙二醇进行高速离心20 次以完成乙醇对水的置换配制氧化石墨乙二醇溶液(定容到35 mL),对新配制的氧化石墨乙二醇溶液搅拌分散2 h后进行功率为80 W、频率为16 KHZ超声分散10 min得到石墨烯氧化物胶体乙二醇溶液;将石墨烯氧化物胶体乙二醇溶液转移到内衬聚四氟乙烯反应釜中,在反应釜中加入1%的葡萄糖,在190 ℃下反应15 h;把溶剂热反应得到的石墨烯(氧化物)凝胶反复用去离子水洗涤12 次,在冷冻温度为-58 ℃,真空度为1500 Pa的条件下干燥48 h获得石墨烯(氧化物)气凝胶4;所制石墨烯(氧化物)气凝胶进一步在1 g/L的硼氢化钠溶液中浸渍5 h后在50 ℃条件下真空干燥36 h。得到的石墨烯气凝胶4的接触角为122 °(图10)。 Measure 20 mL of graphite oxide (30-45 μm in size) aqueous solution with a concentration of 1.75 mg/mL, and use isopycnic differential centrifugation to replace the solvent water of graphite oxide aqueous solution with ethylene glycol, and set the speed at 16000 rpm After the graphite oxide aqueous solution was centrifuged for the first time, ethylene glycol was added for high-speed centrifugation 20 times each time to complete the replacement of ethanol with water to prepare graphite oxide ethylene glycol solution (fixed volume to 35 mL), and the newly prepared graphite oxide ethylene glycol solution was After the alcohol solution was stirred and dispersed for 2 hours, ultrasonic dispersion was performed at a power of 80 W and a frequency of 16 KHZ for 10 minutes to obtain a graphene oxide colloidal glycol solution; the graphene oxide colloidal glycol solution was transferred to a polytetrafluoroethylene-lined In the reaction kettle, add 1% glucose to the reaction kettle and react at 190 °C for 15 h; wash the graphene (oxide) gel obtained by the solvothermal reaction with deionized water for 12 times, and freeze it at - Graphene (oxide) aerogel 4 was obtained by drying at 58 °C and a vacuum of 1500 Pa for 48 h; the prepared graphene (oxide) aerogel was further impregnated in 1 g/L sodium borohydride solution After 5 h, it was dried under vacuum at 50 °C for 36 h. The contact angle of the obtained graphene airgel 4 is 122° (Fig. 10).

实施例 11 Embodiment 11 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶5。 Graphene oxide airgel 5 was prepared according to the synthesis method proposed in the present invention.

本实施例与实施例7相比,除了改变氧化石墨水溶液为10 mL浓度为2.7 mg/mL的氧化石墨(尺寸为30~45 μm)水溶液外,其他均与实施例7完全相同。以所制备的石墨烯气凝胶5作为吸附剂对炼油厂的废油液进行吸附,吸附容量为106 g/g,5个循环后的吸附容量为103 g/g(图11)。 Compared with Example 7, this example is exactly the same as Example 7 except that the graphite oxide aqueous solution is changed to 10 mL graphite oxide (30-45 μm in size) aqueous solution with a concentration of 2.7 mg/mL. The prepared graphene airgel 5 was used as an adsorbent to adsorb waste oil from refineries. The adsorption capacity was 106 g/g, and the adsorption capacity after 5 cycles was 103 g/g (Fig. 11).

实施例 12 Embodiment 12 :

按照本发明提出的合成方法制备石墨烯氧化物气凝胶6。 Graphene oxide airgel 6 was prepared according to the synthesis method proposed in the present invention.

本实施例与实施例7相比,除了扩大氧化石墨水溶液的用量为实施例7的4倍(溶剂热反应的溶剂体积为120 mL)外,其他均与实施例7完全相同。所制石墨烯气凝胶6的宏观形貌如图12所示。 Compared with Example 7, this example is exactly the same as Example 7 except that the amount of the graphite oxide aqueous solution is increased to 4 times that of Example 7 (solvothermal reaction solvent volume is 120 mL). The macroscopic morphology of the prepared graphene airgel 6 is shown in FIG. 12 .

Claims (9)

1. graphene oxide (GO) and Graphene (G) aeroge and preparation method thereof and environmental applications, prepared aeroge is the carbon solid that two classes that GO with G elementary cell is constituted have a large amount of hole, similar spongiosis respectively, its preparation method includes: (1) prepares graphite oxide presoma, (2) graphite oxide character such as functional group's kind and quantity, dispersibility, concentration, dimensional structure etc. are controlled, (3) hot GO(or G of hydrothermal/solvent) solution, (4) after being dried (or being dried and reduction) process, GO(or G that i.e. availability is excellent) aeroge.
2. GO and the G aeroge described in claim 1, its preparation method is characterised by: graphite oxide solution used is the Hummer method synthesis to improve, the graphite oxide solution concentration of ultrasonic wave added preparation is 0.3 ~ 15 mg/mL, and its ultrasonic power, frequency and time are respectively 40 ~ 200 W, 8 ~ 40 KHZ and 5 ~ 120 min.
3. GO and the G aeroge described in claim 1, its preparation method is characterised by: the hot temperature and time of GO and G aeroge solvent/water is 100 ~ 200 respectively DEG C and 6 ~ 24 h, solvent/water hot afterproduct deionized water all washs 6 ~ 24 times;Lyophilization temperature, vacuum and time are-5 ~-65 DEG C, 15 ~ 60000 Pa and 1 ~ 72 h respectively.
4. the GO aeroge described in claim 1, its preparation method is characterised by: solution used is graphite oxide aqueous solution, the ethanol mixed liquor (ethanol is 0.02 ~ 2 with the volume ratio of water) with water or the mixed liquor (ethylene glycol is 0.02 ~ 2 with the volume ratio of water) of ethylene glycol and water;During GO solvent thermal, high polymer PEG, PAN and PVDF addition is 0.1 ~ 1.0 wt%.
5. the GO aeroge described in claim 4, it is characterised in that: described GO aeroge density is 0.3 ~ 2.0 mg/cm3, contact angle 30 ~ 80 °, aperture be 1 nm ~ 5 μm, porosity be 65 ~ 99%, specific surface area be 100 ~ 1700 m2/ g, GO aeroge has stronger elasticity and fire line.
6. the G aeroge described in claim 1, its preparation method is characterised by: solution used is graphite oxide ethanol solution, ethylene glycol solution, the ethanol mixed liquor (ethanol is 2 ~ 14 with the volume ratio of water) with water or the mixed liquor (ethylene glycol is 2 ~ 14 with the volume ratio of water) of ethylene glycol and water;1H in G solvent thermal process, 1H, 2H, 2H-the most not certain herbaceous plants with big flowers base mercaptan, dopamine, glucose, sucrose additive addition are 0.1 ~ 1.0 wt%;G aeroge method of reducing includes: 1) under argon shield gas 1600 ~ 2800 High-temperature process 30 ~ 240 at DEG C 300 ~ 1000 DEG C/h of min(heating rate), 2) volume ratio of 40 ~ 80 DEG C be 10 ~ 40% hydroiodic acid solution in impregnate 3 ~ 24 h, 3) volume ratio of 40 ~ 80 DEG C be 10 ~ 25% ammonia spirit in impregnate 3 ~ 24 h, or 4) sodium borohydride solution of 0.5 ~ 5 g/L impregnates under room temperature 3 ~ 24 h.
7. the G aeroge described in claim 6, it is characterised in that: described G aeroge density is 0.25 ~ 1.8 mg/cm3, contact angle 95 ~ 150 °, aperture be 1 nm ~ 3.5 μm, porosity be 80 ~ 99%, specific surface area be 300 ~ 2000 m2/ g, G aeroge has stronger elasticity and fire line.
8. the GO aeroge described in claim 1, it is characterised by environmental applications: prepared GO aeroge is used for Adsorption hydrophilic pollutant, and with prepared GO aeroge, (quality is 10 ~ 60 Mg) processing the rhodamine B solution that 5 ~ 50 mL concentration are 1 ~ 50 mg/L, rhodamine B can be by complete Adsorption;After circulating 10 times, rhodamine B clearance is still 100%.
9. the G aeroge described in claim 1, it is characterised by environmental applications: prepared G aeroge is used for Adsorption hydrophobic contaminant, and with prepared G aeroge, (quality is 10 ~ 60 Mg) adsorbing waste oil liquid in oil plant, its adsorption capacity is up to 80 g/g;After circulating 10 times, its adsorption capacity > 60 g/g.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102239114A (en) * 2008-12-04 2011-11-09 泰科电子公司 Graphene and graphene oxide aerogels
CN102887508A (en) * 2012-09-28 2013-01-23 上海理工大学 Method for preparing high-strength graphite oxide aerogel
CN104843676A (en) * 2014-12-03 2015-08-19 北汽福田汽车股份有限公司 Preparation method for graphene aerogel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102239114A (en) * 2008-12-04 2011-11-09 泰科电子公司 Graphene and graphene oxide aerogels
CN102887508A (en) * 2012-09-28 2013-01-23 上海理工大学 Method for preparing high-strength graphite oxide aerogel
CN104843676A (en) * 2014-12-03 2015-08-19 北汽福田汽车股份有限公司 Preparation method for graphene aerogel

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