WO2016155396A1 - 一种多孔石墨烯和石墨烯量子点及其绿色制备方法 - Google Patents

一种多孔石墨烯和石墨烯量子点及其绿色制备方法 Download PDF

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WO2016155396A1
WO2016155396A1 PCT/CN2015/100021 CN2015100021W WO2016155396A1 WO 2016155396 A1 WO2016155396 A1 WO 2016155396A1 CN 2015100021 W CN2015100021 W CN 2015100021W WO 2016155396 A1 WO2016155396 A1 WO 2016155396A1
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graphene
quantum dots
graphene quantum
porous graphene
acetic acid
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PCT/CN2015/100021
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English (en)
French (fr)
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王小英
李晓云
孙润仓
叶伟杰
陈伟敏
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华南理工大学
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Priority claimed from CN201510150669.3A external-priority patent/CN104843677B/zh
Priority claimed from CN201510915456.5A external-priority patent/CN105502352A/zh
Application filed by 华南理工大学 filed Critical 华南理工大学
Priority to US15/563,406 priority Critical patent/US10005957B2/en
Publication of WO2016155396A1 publication Critical patent/WO2016155396A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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  • the invention belongs to the field of nanotechnology and new material technology, and particularly relates to a porous graphene and graphene quantum dots and a green preparation method thereof.
  • the graphene material is a nano-scale graphite material composed of a single layer of graphite.
  • the porous graphene is formed by physically or chemically forming a hole having a nanometer size in a sheet of graphene, and the porous structure makes the graphene in energy, catalysis or There are great advantages in adsorbing materials.
  • a graphene material having a porous structure there are mainly the following methods for preparing a graphene material having a porous structure: (1) The multi-layered graphene and the surfactant are hydrothermally reacted in a strong aqueous alkali solution, but this method introduces a lot of functional groups in the graphene sheet layer due to the addition of the surfactant; (2) Heating a carbon material such as graphene and a transition metal simultaneously to obtain porous graphene, but this method uses an expensive transition metal; (3) The chemical deposition method obtains a graphene sheet layer, and then forms a porous graphene by etching, but the method is complicated in process and high in cost; (4) After the graphite is mixed with the nano metal particles, the porous graphene material is obtained by acid treatment, and the cost of the reaction is increased due to the introduction of the nano metal.
  • the graphene quantum dots are obtained by preparing the porous graphene by one-step ultrasonication, the method is simple and easy, the cost is low, and high graphitization is obtained. Porous graphene having a small number of layers and a large lateral dimension of the sheet.
  • graphene quantum dots exhibit a series of new properties due to quantum confinement effects and boundary effects.
  • the preparation methods of graphene quantum dots are divided into two major categories, top-down and bottom-up methods.
  • the top-down method mainly includes hydrothermal method, electrochemical method and chemical stripping carbon fiber method, and the raw materials used are generally graphene oxide or reduced graphene oxide, and a strong oxidizing agent or a toxic reagent is used in the preparation process.
  • the bottom-up method mainly includes solution chemistry, ultrasonic method and microwave method, controlled pyrolysis polycyclic aromatic hydrocarbon method, and preparation of carbon quantum dots using small molecules as carbon sources. Ultrasonic etching is also a kind of top-down method. At present, there is no report on the use of graphite as a raw material for ultrasonic preparation of porous graphene and graphene quantum dots.
  • the object of the present invention is to provide a porous graphene and graphene quantum dot and a green preparation method thereof, which is simple and easy to process, and the raw material (graphite It is easy to obtain that the obtained porous graphene has a uniform pore size distribution and a large lateral dimension of the sheet; the graphene quantum dot has a good crystal form and a uniform size distribution.
  • the resulting porous graphene can be used as a carrier for reverse gene transfection, and graphene quantum dots can be used for cell imaging.
  • a green preparation method of porous graphene and graphene quantum dots the preparation steps are as follows:
  • the mass ratio of the chitosan to the graphite is 1:10 to 10:1.
  • the chitosan of the step 1) has a weight average molecular weight of 5.0 ⁇ 10 3 to 1.0 ⁇ 10 6 and a degree of deacetylation of 40% to 95%.
  • step 1) the volume concentration of acetic acid in the aqueous acetic acid solution is 0.5% to 4%.
  • the mass concentration of the chitosan aqueous acetic acid solution is 0.1 to 0.5 mg/mL.
  • step 3 the temperature of the ultrasonic treatment is 10 to 75 ° C; and the power of the ultrasonic treatment is 420 to 600 W.
  • the time for sonication is 0.5 ⁇ 24 hours.
  • step 4) is centrifuged at 1000 to 2000 rpm for 5 to 10 minutes.
  • step 4) the product after centrifugation is further carried out using an aqueous solution of acetic acid having a volume concentration of acetic acid of 0.5% to 4%. Centrifuge and wash at 15000 ⁇ 20000 rpm for 1.5 ⁇ 3 hours, and centrifuge to obtain porous graphene.
  • step 4 the supernatant after centrifugation uses a molecular weight cutoff of 3000 to 10000.
  • the dialysis bag was dialyzed, and the dialyzed material was graphene quantum dots.
  • porous graphene prepared by the above preparation method, the porous graphene sheet having a thickness of 0.5 to 2 nm and a lateral dimension of 1 to 30 micrometers; porous graphene has a uniform pore surface with a pore size of 10 nm to 500 nm.
  • the present invention has the following advantages:
  • the porous graphene prepared by the method of the invention has high degree of graphitization, The pore size distribution is uniform, the thickness of the sheet is 0.5 ⁇ 2 nm, the lateral dimension of the sheet is large, 1 ⁇ 30 microns, and the diameter of the sheet hole is 10 ⁇ 500 nm.
  • the resulting graphene quantum dots The crystal form is good, the size distribution is uniform, the thickness is 0.5 ⁇ 1.5 nm, and the particle size is 3 ⁇ 7 nm.
  • Figure 1 (a) ⁇ (e) are graphene sonicated for 0.5 hours, 2 hours, 8 hours, 16 Atomic force microscopy of porous graphene obtained in hours and 24 hours; (f) in Figure 1 is an atomic force micrograph and height map of large-sized porous graphene obtained by sonication for 8 hours.
  • Fig. 3 is a luminescence spectrum of the graphene quantum dots prepared in Example 3 excited under different wavelengths of light.
  • Figure 4 (a) is a TEM image of the graphene quantum dots prepared in Example 3; (b), (c in Figure 4) Atomic force microscopy and height maps of graphene quantum dots prepared in Example 3, respectively.
  • a 0.5% acetic acid aqueous solution of acetic acid was prepared, and a chitosan having a weight average molecular weight of 5.0 ⁇ 10 3 and a deacetylation degree of 40% was dissolved in an aqueous acetic acid solution to obtain a chitosan having a mass concentration of 0.1 mg/mL.
  • Sugar solution stir well;
  • the above mixture was placed in an ultrasonic cleaner for sonication at a temperature of 75 ° C for 0.5 hours, and the ultrasonic power was 600W.
  • the above ultrasonic solution was centrifuged at 1000 rpm for 10 minutes, and the volume concentration was 0.5% after centrifugation.
  • the aqueous acetic acid solution was centrifuged at 15,000 rpm for 0.5 hour.
  • the precipitate obtained by centrifugation is porous graphene; the centrifugation supernatant has a molecular weight cut off of 10,000 After dialysis bag dialysis, the dialyzed material is graphene quantum dots.
  • Formulated acetate concentration of 2% by volume aqueous acetic acid the weight average molecular weight was 2.0 ⁇ 10 4, the degree of deacetylation of the chitosan was dissolved in 53% aqueous acetic acid to obtain the concentration of 0.2mg / mL of chitosan Sugar solution, stir well;
  • the above mixture was placed in an ultrasonic cleaner for sonication at a temperature of 60 ° C for 2 hours and the ultrasonic power was 540 W. .
  • the above sonicated solution was centrifuged at 2000 rpm for 10 minutes, centrifuged, and then subjected to a 2% by volume aqueous solution of acetic acid. Centrifugal washing at 20000 rpm for 1 hour.
  • the precipitate obtained by centrifugation is porous graphene; the centrifugation supernatant has a molecular weight cut off of 5000.
  • the dialyzed material is graphene quantum dots.
  • a 4% acetic acid aqueous solution of acetic acid was prepared, and a chitosan having a weight average molecular weight of 1.5 ⁇ 10 5 and a degree of deacetylation of 60% was dissolved in an aqueous acetic acid solution to obtain a chitosan having a mass concentration of 0.5 mg/mL.
  • Sugar solution stir well;
  • the above mixture was placed in an ultrasonic cleaner for sonication at a temperature of 30 ° C for 8 hours and the ultrasonic power was 480 W. .
  • the above sonicated solution was centrifuged at 2000 rpm for 5 minutes, centrifuged, and then subjected to a 4% by volume aqueous solution of acetic acid. Centrifugal washing at 16000 rpm for 1.5 hours.
  • the precipitate obtained by centrifugation is porous graphene; the centrifugation supernatant has a molecular weight cutoff of 3000 After dialysis bag dialysis, the dialyzed material is graphene quantum dots.
  • Formulated acetate concentration of 0.5% by volume aqueous acetic acid the weight average molecular weight was 4.5 ⁇ 10 5, deacetylation degree of the chitosan was dissolved in 80% aqueous acetic acid to obtain the concentration of 0.2mg / mL of chitosan Sugar solution, stir well;
  • the above mixture was placed in an ultrasonic cleaner for sonication at a temperature of 10 ° C for 16 hours and the ultrasonic power was 420 W. .
  • the above ultrasonic solution was centrifuged at 1000 rpm for 10 minutes, and the volume concentration was 0.5% after centrifugation.
  • the aqueous acetic acid solution was centrifuged at 18,000 rpm for 2 hours.
  • the precipitate obtained by centrifugation is porous graphene; the centrifugation supernatant has a molecular weight cut off of 10,000 After dialysis bag dialysis, the dialyzed material is graphene quantum dots.
  • a 0.5% acetic acid aqueous solution of acetic acid was prepared, and a chitosan having a weight average molecular weight of 1.0 ⁇ 10 6 and a degree of deacetylation of 95% was dissolved in an aqueous acetic acid solution to obtain a chitosan having a mass concentration of 0.2 mg/mL.
  • Sugar solution stir well;
  • the above mixture was placed in an ultrasonic cleaner for sonication at a temperature of 30 ° C for 24 hours and ultrasonic power of 600 W. .
  • the above ultrasonic solution was centrifuged at 2000 rpm for 10 minutes, and the volume concentration was 0.5% after centrifugation.
  • the aqueous acetic acid solution was centrifuged at 15,000 rpm for 3 hours.
  • the precipitate obtained by centrifugation is porous graphene; the centrifugation supernatant has a molecular weight cut off of 10,000 After dialysis bag dialysis, the dialyzed material is graphene quantum dots.
  • Figure 1 shows the change in the pore structure of graphene as a function of ultrasonic time, where (a) ⁇ (e) ) sonicated for 0.5 hours, 2 hours, 8 hours, 16 hours and 24 Atomic force microscopy of porous graphene obtained in hours. It was found that as the ultrasonic time prolonged, the pore structure became larger and smaller, ranging from 10 nm to 500 nm.
  • Figure 1 (f ) and its illustrations are atomic force microscopy and height maps of large-sized porous graphene obtained by ultrasonic treatment for 8 hours. From the marked lines in Figure f, the transverse dimension of the graphene sheets is 30 ⁇ m. The graph curve shows a graphene layer thickness of 0.9 nm.
  • Figure 3 shows Example 3
  • the luminescence spectra of the obtained graphene quantum dots at different excitation wavelengths can be seen from the figure, as the excitation wavelength changes, the emission peak positions of the obtained graphene quantum dots remain basically unchanged.
  • the graphene quantum dots emit strong fluorescence, and the fluorescence spectrum peak is at 546 nm.
  • Figure 4 shows the TEM of the graphene quantum dots prepared in Example 3. Photographs, as can be seen from the figure, the graphene quantum dots have a particle size between 3 and 7 nanometers. The crystallinity of the graphene quantum dots is good, and obvious lattice fringes can be observed. (b) in Fig. 4 is the embodiment 3 The atomic force microscopy of the obtained graphene quantum dots, (c) in Fig. 4 is the height map corresponding to the underlined part in (b), and the height of the graphene quantum dots is 0.9. Nanographs, TEM photographs and atomic force microscopy images and height maps of graphene quantum dots prepared in other examples are basically the same as those in Example 3.

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Abstract

一种多孔石墨烯和石墨烯量子点及其制备方法，所述方法为：将石墨原料加入壳聚糖的醋酸水溶液中，以壳聚糖作为剥离剂，经过超声处理，离心沉淀得多孔石墨烯，离心上清液透析后得石墨烯量子点。得到的多孔石墨烯层数较少且片层横向尺寸较大；得到的石墨烯量子点分散性好且粒径分布均一。制备方法简单易行，制备的多孔石墨烯和石墨烯量子点的石墨化程度高。得到的多孔石墨烯可以作为反向基因转染的载体，石墨烯量子点可以用于细胞成像。

Description

一种多孔石墨烯和石墨烯量子点及其绿色制备方法
技术领域
本发明属于纳米技术领域与新材料技术领域，具体涉及一种 多孔石墨烯和石墨烯量子点及其绿色制备方法 。
背景技术
石墨烯材料是由单层石墨组成的纳米级石墨材料，多孔石墨烯是在石墨烯的片层中通过物理或者化学的方法制造一些具有纳米尺寸的孔洞，多孔结构使得石墨烯在能源、催化或者吸附材料方面有很大的优势。
目前关于具有多孔结构的石墨烯材料的制备主要有以下方法：（ 1 ）将多层的石墨烯与表面活性剂在强碱水溶液中进行水热反应，但是这种方法由于表面活性剂的加入在石墨烯片层中引入了很多的官能团；（ 2 ）将石墨烯等碳材料和过渡金属同时加热得到多孔石墨烯，但是这种方法使用了价格昂贵的过渡金属；（ 3 ）化学沉积法得到石墨烯片层，然后通过刻蚀形成多孔石墨烯，但是这种方法工艺复杂，成本较高；（ 4 ）将石墨与纳米金属颗粒混合后，通过酸处理溶解得到多孔石墨烯材料，由于纳米金属的引入提高了反应的成本。本发明中通过一步超声在制备多孔石墨烯的同时得到了石墨烯量子点，方法简单易行，成本低，而且获得了高度石墨化、 层数较少和片层横向尺寸较大的多孔石墨烯。
石墨烯量子点除了具有石墨烯的优异性能，还因量子限域效应和边界效应而展现出一系列新的特性。石墨烯量子点的制备方法分为两大类，自上而下和自下而上的方法。自上而下的方法主要包括水热法、电化学法和化学剥离碳纤维法，使用的原料一般为氧化石墨烯或者还原氧化石墨烯，制备过程中使用了强氧化剂或者有毒的试剂。自下而上的方法主要包括溶液化学法、超声波法和微波法、可控热解多环芳烃法，使用小分子作为碳源制备碳量子点。超声刻蚀法也是一种自上而下方法的一种，目前没有采用石墨作为原料一步超声制备多孔石墨烯和石墨烯量子点的报道。
发明内容
本发明目的是提出一种 多孔石墨烯和石墨烯量子点及其绿色制备方法，该方法简单易行，原料（ 石墨 ）易得，所得多孔石墨烯的孔径分布均匀、片层横向尺寸较大；石墨烯量子点晶型好、尺寸分布均匀。所得到的多孔石墨烯可以作为反向基因转染的载体，石墨烯量子点可以用于细胞成像。
本发明具体通过以下技术方案实现：
一种多孔石墨烯和石墨烯量子点的绿色制备方法，制备步骤如下：
1 ）将壳聚糖溶解在醋酸水溶液中，得到壳聚糖的醋酸水溶液；
2 ）在壳聚糖的醋酸水溶液中加入石墨，搅拌至混合均匀得混合液；
3 ）将混合液放入超声清洗器中，进行超声处理；
4 ）将超声后的混合液离心沉淀，得到多孔石墨烯；离心上清液透析后得到石墨烯量子点。
进一步地，所述壳聚糖与所述石墨的质量比为 1:10~10:1 。
进一步地，步骤 1 ）所述壳聚糖的重均分子量为 5.0 × 103~1.0 × 106 ，脱乙酰度为 40%~95% 。
进一步地，步骤 1 ）所述醋酸水溶液中醋酸的体积浓度为 0.5%~4% ；所述壳聚糖的醋酸水溶液的质量浓度为 0.1~0.5mg/mL 。
进一步地，步骤 3 ）所述超声处理的温度为 10~75℃；超声处理的功率为420~600W ；超声处理的时间为 0.5~24 小时。
更进一步地，步骤 4 ）所述混合液经过 1000~2000 rpm 离心 5~10 分钟。
进一步地，步骤 4 ）离心后的产物再使用醋酸体积浓度为 0.5%~4% 的醋酸水溶液进行 15000~20000 rpm 离心清洗 1.5~3 小时，离心沉淀得到多孔石墨烯。
进一步地，步骤 4 ）离心后的上清液使用截留分子量为 3000~10000 的透析袋透析，透析出来的物质为石墨烯量子点。
由上述制备方法制备得到的 一种多孔石墨烯，该多孔石墨烯片层厚度为 0.5 ～ 2 纳米，横向尺寸 1 ～ 30 微米；多孔石墨烯表面孔均匀分布，孔径为 10 纳米～ 500 纳米。
由上述制备方法 制备得到的一种石墨烯量子点，该石墨烯量子点厚度为 0.5~1.5 纳米，粒径为 3~7 纳米。
与现有技术相比，本发明具有以下优点：
由于本发明中只使用了超声处理，制备方法简单易行， 原料易得 。 用本发明方法制备的多孔石墨烯石墨化度高， 孔径分布均匀， 片层的厚度为0.5~2 纳米，片层横向尺寸较大， 1~30 微米，片层孔的直径为 10~500 纳米。所得到的石墨烯量子点 晶型好、尺寸分布均匀，厚度为 0.5~1.5 纳米，粒径为 3~7 纳米。
附图说明
图 1 中（ a ）～（ e ）分别为石墨烯经过超声处理 0.5 小时， 2 小时， 8 小时， 16 小时和 24 小时得到的多孔石墨烯的 原子力显微镜图；图 1 中（ f ）为超声处理 8 小时得到的大尺寸多孔石墨烯的原子力显微镜图与高度图。
图 2 中的（ a ）、（ b ）为石墨与实施例 3 制得的多孔石墨烯的 X 射线光电子能谱图。
图 3 为实施例 3 制得的石墨烯量子点在不同波长光下激发的发光光谱图。
图 4 中（ a ）为实施例 3 制得的石墨烯量子点的 TEM 照片；图 4 中（ b ）、（ c ）分别为实施例 3 制得的石墨烯量子点的原子力显微镜图与高度图。
具体实施方式
下面结合具体实施例对本发明作进一步说明，但不限于此，需指出的是，以下若有未特别详细说明之处，均是本领域技术人员可参照现有技术实现的。
实施例 1 ：
配制醋酸的体积浓度为 0.5% 的醋酸水溶液，将重均分子量为 5.0 × 103 ，脱乙酰度为 40% 的壳聚糖溶于醋酸水溶液中，制得质量浓度为 0.1mg/mL 的壳聚糖溶液，搅拌均匀；
将 500mg 的石墨加入到上述壳聚糖溶液中，得混合液；控制壳聚糖与石墨的质量比为 1:10 ；
将上述混合液放入超声清洗器中进行超声处理，温度为 75 ℃ ，时间为 0.5 小时，超声的功率为 600W 。
将上述超声后的溶液经过 1000rpm 离心 10 分钟，离心后使用体积浓度为 0.5% 的醋酸水溶液进行 15000rpm 离心清洗，离心的时间为 0.5 小时。离心得到的沉淀为多孔石墨烯；离心上清液用截留分子量为 10000 的透析袋透析后，透析出来的物质为石墨烯量子点。
实施例 2 ：
配制醋酸的体积浓度为 2% 的醋酸水溶液，将重均分子量为 2.0 × 104 ，脱乙酰度为 53% 的壳聚糖溶于醋酸水溶液中，制得质量浓度为 0.2mg/mL 的壳聚糖溶液，搅拌均匀；
将 200mg 的石墨加入到上述壳聚糖溶液中，得混合液；控制壳聚糖与石墨的质量比为 1:5 ；
将上述混合液放入超声清洗器中进行超声处理，温度为 60 ℃ ，时间为 2 小时，超声的功率为 540W 。
将上述超声后的溶液经过 2000rpm 离心 10 分钟，离心后使用体积浓度为 2% 的醋酸水溶液进行 20000rpm 离心清洗，离心的时间为 1 小时。离心得到的沉淀为多孔石墨烯；离心上清液用截留分子量为 5000 的透析袋透析后，透析出来的物质为石墨烯量子点。
实施例 3 ：
配制醋酸的体积浓度为 4% 的醋酸水溶液，将重均分子量为 1.5 × 105 ，脱乙酰度为 60% 的壳聚糖溶于醋酸水溶液中，制得质量浓度为 0.5mg/mL 的壳聚糖溶液，搅拌均匀；
将 100mg 的石墨加入到上述壳聚糖溶液中，得混合液；控制壳聚糖与石墨的质量比为 1:1 ；
将上述混合液放入超声清洗器中进行超声处理，温度为 30 ℃ ，时间为 8 小时，超声的功率为 480W 。
将上述超声后的溶液经过 2000rpm 离心 5 分钟，离心后使用体积浓度为 4% 的醋酸水溶液进行 16000rpm 离心清洗，离心的时间为 1.5 小时。离心得到的沉淀为多孔石墨烯；离心上清液用截留分子量为 3000 的透析袋透析后，透析出来的物质为石墨烯量子点。
实施例 4 ：
配制醋酸的体积浓度为 0.5% 的醋酸水溶液，将重均分子量为 4.5 × 105 ，脱乙酰度为 80% 的壳聚糖溶于醋酸水溶液中，制得质量浓度为 0.2mg/mL 的壳聚糖溶液，搅拌均匀；
将 100mg 的石墨加入到上述壳聚糖溶液中，得混合液；控制壳聚糖与石墨的质量比为 5:1 ；
将上述混合液放入超声清洗器中进行超声处理，温度为 10 ℃ ，时间为 16 小时，超声的功率为 420W 。
将上述超声后的溶液经过 1000rpm 离心 10 分钟，离心后使用体积浓度为 0.5% 的醋酸水溶液进行 18000rpm 离心清洗，离心的时间为 2 小时。离心得到的沉淀为多孔石墨烯；离心上清液用截留分子量为 10000 的透析袋透析后，透析出来的物质为石墨烯量子点。
实施例 5 ：
配制醋酸的体积浓度为 0.5% 的醋酸水溶液，将重均分子量为 1.0 × 106 ，脱乙酰度为 95% 的壳聚糖溶于醋酸水溶液中，制得质量浓度为 0.2mg/mL 的壳聚糖溶液，搅拌均匀；
将 50mg 的石墨加入到上述壳聚糖溶液中，得混合液；控制壳聚糖与石墨的质量比为 10:1 ；
将上述混合液放入超声清洗器中进行超声处理，温度为 30 ℃ ，时间为 24 小时，超声的功率为 600W 。
将上述超声后的溶液经过 2000rpm 离心 10 分钟，离心后使用体积浓度为 0.5% 的醋酸水溶液进行 15000rpm 离心清洗，离心的时间为 3 小时。离心得到的沉淀为多孔石墨烯；离心上清液用截留分子量为 10000 的透析袋透析后，透析出来的物质为石墨烯量子点。
图 1 给出了随着超声时间的变化石墨烯的孔结构的大小的变化，其中，图 1 中的（ a ）～（ e ）分别为经过超声处理 0.5 小时， 2 小时， 8 小时， 16 小时和 24 小时得到的多孔石墨烯的原子力显微镜图。对比发现，随着超声时间的延长，孔结构从小变大，尺寸从 10 纳米到 500 纳米。图 1 中的（ f ）及其插图为超声处理 8 小时得到的大尺寸多孔石墨烯的原子力显微镜图与高度图，从图 f 中的标示线条可以看到石墨烯片层的横向尺寸达到了 30 微米，从图 f 的插图曲线中看到石墨烯片层的厚度为 0.9 纳米。
图 2 中的（ a ）、（ b ）给出了石墨与实施例 3 制得的多孔石墨烯的 X 射线光电子能谱图，从图中可以知道，本发明实施例 3 制得的多孔石墨烯的含氧官能团较少，石墨化度高。其它实施例制得的多孔石墨烯的 X 射线光电子能谱图与实施例 3 的基本一致。
图 3 给出了实施例 3 制得的石墨烯量子点在不同激发波长下的发光光谱，从图中可以看到随着激发波长的改变，得到的石墨烯量子点的发射峰位置基本保持不变。在 380 纳米的激发波长下，石墨烯量子点发射强的荧光，荧光光谱峰位在 546 纳米。
图 4 中的（ a ）出了实施例 3 制得的石墨烯量子点的 TEM 照片，从图中可以得知，石墨烯量子点的粒径在 3~7 纳米之间。石墨烯量子点的晶度好，可以观察到明显的晶格条纹。图 4 中的（ b ）为实施例 3 制得的石墨烯量子点的原子力显微镜图，图 4 中的（ c ）为图（ b ）中划线部分对应的高度图，可以看到石墨烯量子点的高度为 0.9 纳米，其它实施例制得的石墨烯量子点的 TEM 照片和原子力显微镜图与及其高度图与实施例 3 的基本一致。

Claims (10)

  1. 一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，制备步骤如下：
    1 ）将壳聚糖溶解在醋酸水溶液中，得到壳聚糖的醋酸水溶液；
    2 ）在壳聚糖的醋酸水溶液中加入石墨，搅拌至混合均匀得混合液；
    3 ）将混合液放入超声清洗器中，进行超声处理；
    4 ）将超声后的混合液离心沉淀，得到多孔石墨烯；离心上清液透析后得到石墨烯量子点。
  2. 根据权利要求1所述的一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，所述壳聚糖与所述石墨的质量比为1:10~10:1。
  3. 根据权利要求1所述的一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，步骤1）所述壳聚糖的重均分子量为5.0×103~1.0×106，脱乙酰度为40%~95%。
  4. 根据权利要求1所述的一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，步骤1）所述醋酸水溶液中醋酸的体积浓度为0.5%~4%；所述壳聚糖的醋酸水溶液的质量浓度为0.1~0.5mg/mL。
  5. 根据权利要求1所述的一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，步骤3）所述超声处理的温度为10~75℃；超声处理的功率为420~600W；超声处理的时间为0.5~24小时。
  6. 根据权利要求1所述的一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，步骤4）所述混合液经过1000~2000 rpm离心5~10分钟。
  7. 根据权利要求1所述的一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，步骤4）离心后的产物再使用醋酸体积浓度为0.5%~4%的醋酸水溶液进行15000~20000 rpm离心清洗1.5~3小时，离心沉淀得到多孔石墨烯。
  8. 根据权利要求1所述的一种多孔石墨烯和石墨烯量子点的绿色制备方法，其特征在于，步骤4）离心后的上清液使用截留分子量为3000~10000的透析袋透析，透析出来的物质为石墨烯量子点。
  9. 由权利要求1所述制备方法制备得到的一种多孔石墨烯，其特征是：该多孔石墨烯片层厚度为0.5～2纳米，横向尺寸1～30微米；多孔石墨烯表面孔均匀分布，孔径为10纳米～500纳米。
  10. 由权利要求1所述制备方法制备得到的一种石墨烯量子点，其特征是：该石墨烯量子点厚度为0.5~1.5纳米，粒径为3~7纳米。
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