WO2016054877A1 - Rapid and environmentally-friendly method for preparing single-layer graphene oxide - Google Patents

Rapid and environmentally-friendly method for preparing single-layer graphene oxide Download PDF

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WO2016054877A1
WO2016054877A1 PCT/CN2015/070511 CN2015070511W WO2016054877A1 WO 2016054877 A1 WO2016054877 A1 WO 2016054877A1 CN 2015070511 W CN2015070511 W CN 2015070511W WO 2016054877 A1 WO2016054877 A1 WO 2016054877A1
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acid
graphene oxide
graphite
strong
deionized water
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PCT/CN2015/070511
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French (fr)
Chinese (zh)
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高超
彭蠡
郑耀臣
魏杨扬
许震
孙海燕
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浙江碳谷上希材料科技有限公司
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    • 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
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides

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  • the invention relates to the field of nano materials, in particular to a method for rapidly preparing green single-layer graphene oxide.
  • the preparation of graphene by redox method is considered to be the most important method to realize the industrial preparation of graphene.
  • Its intermediate graphene oxide is an important precursor of graphene, and it is the most important intermediate for the macroscopic assembly and modification of graphene materials.
  • the macroscopic assembly materials, films, aerogels, and the like which have been realized so far are all prepared by relying on graphene oxide.
  • the object of the present invention is to overcome the deficiencies of the prior art and provide a simple method for preparing a single layer of graphene oxide by a fast green two-step method.
  • the graphene oxide sheet prepared by the method is uniformly dispersed and has a small metal ion content. During the reaction process, the pollution is less and the operation is safe.
  • a method for rapidly preparing a single layer of graphene oxide in green is as follows:
  • the volume ratio of the strong acid to the graphite is: 40-100 ml: 1 g.
  • the mass ratio of the strong oxidizing agent, the stabilizer and the graphite is 4-10 g: 0.001-1:1 g.
  • the graphite has a particle size of 0.5 um to 3 mm.
  • the strong acid is sulfuric acid (50% - 98%), fuming sulfuric acid, chlorosulfonic acid, concentrated phosphoric acid, concentrated nitric acid, fluorosulfonic acid, trifluoromethanesulfonic acid or a mixed acid thereof.
  • the strong oxidant is ferrate.
  • the stabilizer is periodic acid, periodate, persulfate, zinc salt, aluminum salt, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate , orthophosphoric acid, orthophosphate, metaphosphoric acid, metaphosphate, and more Phosphoric acid, polyphosphate, boric acid, borate, phosphoric anhydride, orthophosphoric anhydride, metaphosphoric anhydride, polyphosphoric anhydride, boric anhydride, and combinations thereof.
  • the preparation process of the invention is simple, safe and controllable, and consumes less time and energy, and is converted into a single layer of graphene oxide by directly converting graphite. Most importantly, the method for preparing graphene oxide does not cause any pollution, the raw material is most fully utilized, and the prepared graphene oxide has less polluting heavy metal ions.
  • Figure 1 is a graphene oxide solution (6 mg / mL);
  • Figure 3 is an atomic force picture of graphene oxide.
  • a method for rapidly preparing a single layer of graphene oxide in green is as follows:
  • the volume ratio of the strong acid to the graphite is: 40-100 ml: 1 g.
  • the mass ratio of the strong oxidizing agent, the stabilizer and the graphite is 4-10 g: 0.001-1:1 g.
  • the graphite has a particle size of 0.5 to 3 mm.
  • the strong acid is sulfuric acid, sulfuric acid (50%-98%), fuming sulfuric acid, chlorosulfonic acid, concentrated phosphoric acid, concentrated nitric acid, fluorosulfonic acid, trifluoromethanesulfonic acid or a mixed acid thereof.
  • the strong oxidant is ferrate.
  • the stabilizer is periodic acid, periodate, persulfate, zinc salt, aluminum salt, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate , orthophosphoric acid, orthophosphate, metaphosphoric acid, metaphosphate, polyphosphoric acid, polyphosphate, boric acid, borate, phosphoric anhydride, orthophosphoric anhydride, metaphosphoric anhydride, polyphosphoric anhydride, boric anhydride, and combinations thereof .
  • the graphite having a particle size of 0.5 ⁇ m was mixed with fuming concentrated sulfuric acid at -10 ° C for 0.5 h, and potassium ferrate and potassium persulfate were added.
  • the reaction solution was then raised to 0 ° C for 1 h.
  • the reaction solution was centrifuged to discard the strong acid.
  • the bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of strong acid to graphite was 40 ml: 1 g
  • the ratio of potassium ferrate, potassium persulfate and graphite was 4 g: 0.01 g: 1 g.
  • the graphite having a particle size of 40 ⁇ m was mixed with sulfuric acid (50%) at -10 ° C for 0.5 h with stirring, and potassium ferrate and periodic acid were added.
  • the reaction solution was then raised to 0 ° C for 1 h.
  • the reaction solution was centrifuged to discard the strong acid. Slow the bottom sediment It was diluted into deionized water of ice and allowed to stand for a while.
  • the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of strong acid to graphite was 50 ml: 1 g
  • the ratio of potassium ferrate, periodate to graphite was 6 g: 0.001 g: 1 g.
  • the graphene oxide prepared by the drawing of Fig. 1 has good solubility and forms a liquid crystal. 2, the SEM picture shows that the prepared graphene oxide has a uniform thickness distribution, and the pleated portion indicates that the sheet layer has a certain flexibility; as can be seen from FIG. 3 by AFM, the thickness of the prepared graphene oxide is about 1.1 nm. , that is, a single layer.
  • the graphite having a particle size of 40 ⁇ m was mixed with sulfuric acid (98%) at -10 ° C for 0.5 h with stirring, and potassium ferrate and periodic acid were added.
  • the reaction solution was then raised to 0 ° C for 1 h.
  • the reaction solution was centrifuged to discard the strong acid.
  • the bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of strong acid to graphite was 50 ml: 1 g
  • the ratio of potassium ferrate, periodate to graphite was 6 g: 0.001 g: 1 g.
  • the graphite having a particle size of 40 ⁇ m was mixed with concentrated phosphoric acid at 0 ° C for 1 h with stirring, and potassium ferrate and boric acid were added.
  • the reaction solution was then raised to 20 ° C for 2 h.
  • the reaction solution was centrifuged to discard the strong acid.
  • the bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of strong acid to graphite was 60 ml: 1 g
  • the ratio of potassium ferrate, potassium persulfate and boric acid was 10 g: 0.1 g: 1 g.
  • Graphite having a particle size of 100 ⁇ m was mixed with concentrated sulfuric acid and concentrated phosphoric acid at 20 ° C for 0.1 h, and potassium ferrate and zinc chloride were added. The reaction solution was then raised to 40 ° C for 4 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of concentrated sulfuric acid, concentrated phosphoric acid and graphite was 80 ml: 20 ml: 1 g, and the ratio of potassium ferrate, zinc chloride and graphite was 7 g: 0.4 g: 1 g.
  • the graphite having a particle size of 500 ⁇ m was mixed with fuming sulfuric acid and concentrated phosphoric acid at 20 ° C for 0.1 h, and potassium ferrate and perchloric acid were added. The reaction solution was then raised to 40 ° C for 4 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 90 ml: 1 g, potassium ferrate, and the ratio of perchloric acid to graphite was 9 g: 1 g: 1 g.
  • the graphite having a particle size of 1 mm and the fuming sulfuric acid were mixed and infiltrated at 20 ° C for 0.5 h, and potassium ferrate and sodium hypochlorite were added.
  • the reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid.
  • the bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of strong acid to graphite was 100 ml: 1 g
  • the ratio of potassium ferrate, sodium perchlorate and graphite was 10 g: 1 g: 1 g.
  • the graphite having a particle size of 2 mm and the concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and phosphoric anhydride were added.
  • the reaction solution was then raised to 60 ° C for 6 h.
  • the reaction solution was centrifuged to discard the strong acid.
  • the bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of strong acid to graphite was 100 ml: 1 g
  • the ratio of potassium ferrate, metaphosphoric anhydride and graphite was 10 g: 0.3 g: 1 g.
  • the graphite having a particle size of 3 mm and the concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and sodium chlorate were added.
  • the reaction solution was then raised to 60 ° C for 6 h.
  • the reaction solution was centrifuged to discard the strong acid.
  • the bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide.
  • the ratio of strong acid to graphite was 100 ml: 1 g
  • the ratio of potassium ferrate, sodium chlorate and graphite was 8 g: 0.6 g: 1 g.
  • Graphite having a particle size of 3 mm and concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and phosphoric anhydride were added. The reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 100 ml: 1 g, and the ratio of potassium ferrate, potassium metaphosphate and graphite was 6 g: 1 g: 1 g.
  • Graphite having a particle size of 3 mm and concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and phosphoric anhydride were added. The reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 100 ml: 1 g, and the ratio of potassium ferrate, potassium borate, sodium phosphate and graphite was 10 g: 0.4 g: 0.2 g: 1 g.

Abstract

Provided is a rapid and environmentally-friendly method for preparing a large amount of single-layer graphene oxide, comprising: 1) mixing, stirring and soaking graphite and a strong acid, adding a strong oxidant (ferrate) and a stabilizer, slowly heating and continuously stirring to oxidize and exfoliate graphite sheets; 2) performing centrifugal separation on the reaction liquid, removing the strong acid, slowly pouring the mud-like product into icy deionized water to dilute, leaving the same to stand, repeatedly washing the precipitate with diluted hydrochloric acid and deionized water, and obtaining single-layer graphene oxide by means of centrifugal separation. The method is simple, safe, and energy efficient, and does not use a polluting halogen or heavy metal oxidizing agent.

Description

一种快速绿色制备单层氧化石墨烯的方法Method for preparing single layer graphene oxide by rapid green color 技术领域Technical field
本发明涉及纳米材料领域，特别是一种一种快速绿色制备单层氧化石墨烯的方法。The invention relates to the field of nano materials, in particular to a method for rapidly preparing green single-layer graphene oxide.
背景技术Background technique
2004年,英国曼彻斯特大学A.K.Geim教授课题组运用机械剥离法成功制备石墨烯,推翻了完美二维晶体结构无法在非绝对零度下稳定存在的这一论断。接着石墨烯优异的力学性质、电学性质、热学性质、光学性质被相继发现。石墨烯具有超大的理论比表面积,加之单片层结构所具有的优异性能，以石墨烯作为源头材料的碳基材料得到了长足的发展和应用。In 2004, Professor A.K. Geim of the University of Manchester in the United Kingdom successfully used the mechanical stripping method to successfully prepare graphene, overturning the assertion that the perfect two-dimensional crystal structure could not exist stably at non-absolute zero degrees. Then, the excellent mechanical properties, electrical properties, thermal properties, and optical properties of graphene were successively discovered. Graphene has a large theoretical specific surface area, combined with the excellent performance of the monolithic structure, and the carbon-based material with graphene as the source material has been greatly developed and applied.
氧化还原法制备石墨烯被认为是最可能实现石墨烯产业化制备的重要方法。而其中间体氧化石墨烯则是石墨烯的重要前驱体，是石墨烯材料实现宏观组装和改性的最重要的中间体。目前已经实现的宏观组装材料纤维、薄膜、气凝胶等都是依托于氧化石墨烯来制备的。The preparation of graphene by redox method is considered to be the most important method to realize the industrial preparation of graphene. Its intermediate graphene oxide is an important precursor of graphene, and it is the most important intermediate for the macroscopic assembly and modification of graphene materials. The macroscopic assembly materials, films, aerogels, and the like which have been realized so far are all prepared by relying on graphene oxide.
现有的制备氧化石墨烯的方法主要有Brodie、Staudenmaier、Hofmann、Hummers以及modified Hummers。这些方法一般根据所用氧化剂一般分为两种，基于氯酸钾的Brodie法和基于高锰酸钾的Hummers。然而这两种氧化剂不仅都容易***，而且反应速率慢。氯酸钾容易释放有毒气体，高锰酸钾会产生重金属离子污染。所有这些方法都属于不符合绿色环保的时代主题，因此氧化石墨烯的绿色安全快速生产问题的到了人们越来越多的重视。Existing methods for preparing graphene oxide include Brodie, Staudenmaier, Hofmann, Hummers, and modified Hummers. These methods are generally classified into two types depending on the oxidizing agent used, a Brodie method based on potassium chlorate and a Hummers based on potassium permanganate. However, both oxidants are not only easy to explode, but also have a slow reaction rate. Potassium chlorate tends to release toxic gases, and potassium permanganate can cause heavy metal ion contamination. All of these methods belong to the era of environmental protection, so the green safety and rapid production of graphene oxide has attracted more and more attention.
发明内容Summary of the invention
本发明的目的是克服现有技术的不足，提供一种简便的一种快速绿色两步法制备单层氧化石墨烯的方法，该方法制备的氧化石墨烯片单层均一分散，金属离子含量少；反应过程时间段，污染少，操作安全。The object of the present invention is to overcome the deficiencies of the prior art and provide a simple method for preparing a single layer of graphene oxide by a fast green two-step method. The graphene oxide sheet prepared by the method is uniformly dispersed and has a small metal ion content. During the reaction process, the pollution is less and the operation is safe.
一种快速绿色制备单层氧化石墨烯的方法的步骤如下：A method for rapidly preparing a single layer of graphene oxide in green is as follows:
1)将石墨与强酸在-10-20℃下搅拌混合浸润5min-1h，加入强氧化剂高铁酸盐以及其稳定剂，缓慢升温至-10-80℃并持续搅拌0.5-24h，以氧化剥离石墨片层；1) Mix and infiltrate graphite and strong acid at -10-20 °C for 5 min-1 h, add strong oxidant ferrate and its stabilizer, slowly heat up to -10-80 °C and continue stirring for 0.5-24 h to oxidize and strip graphite. Slice
2)将反应液离心，弃去强酸，并将泥状产物缓慢倒入冰的去离子水中稀释，静止，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。2) Centrifuge the reaction solution, discard the strong acid, and slowly pour the product into ice deionized water, stand still, and wash the precipitate repeatedly with 1 mol/L dilute hydrochloric acid and deionized water, and separate into a single layer by centrifugation. Graphene oxide.
所述的强酸与石墨体积质量比为：40-100ml：1g。所述的强氧化剂、稳定剂与石墨的质量比为：4-10g：0.001-1：1g。所述的石墨的粒度为0.5um-3mm。所述的强酸为硫酸(50％-98％)、发烟硫酸、氯磺酸、浓磷酸、浓硝酸、氟磺酸、三氟甲磺酸或者它们的混合酸。所述的强氧化剂为高铁酸盐。所述的稳定剂为高碘酸、高碘酸盐盐、过硫酸盐、锌盐、铝盐、次氯酸、次氯酸盐、氯酸、氯酸盐、高氯酸、高氯酸盐、正磷酸、正磷酸盐、偏磷酸、偏磷酸盐、多 磷酸、多磷酸盐、硼酸、硼酸盐、磷酸酐、正磷酸酐、偏磷酸酐、多磷酸酐、硼酸酐及其它们的组合。The volume ratio of the strong acid to the graphite is: 40-100 ml: 1 g. The mass ratio of the strong oxidizing agent, the stabilizer and the graphite is 4-10 g: 0.001-1:1 g. The graphite has a particle size of 0.5 um to 3 mm. The strong acid is sulfuric acid (50% - 98%), fuming sulfuric acid, chlorosulfonic acid, concentrated phosphoric acid, concentrated nitric acid, fluorosulfonic acid, trifluoromethanesulfonic acid or a mixed acid thereof. The strong oxidant is ferrate. The stabilizer is periodic acid, periodate, persulfate, zinc salt, aluminum salt, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate , orthophosphoric acid, orthophosphate, metaphosphoric acid, metaphosphate, and more Phosphoric acid, polyphosphate, boric acid, borate, phosphoric anhydride, orthophosphoric anhydride, metaphosphoric anhydride, polyphosphoric anhydride, boric anhydride, and combinations thereof.
本发明制备过程简单安全可控，耗时耗能少，通过一种直接将石墨转化为单层的氧化石墨烯。最重要的是，本方法制备氧化石墨烯不产生任何污染，原料得到最充分的利用，并且制备的氧化石墨烯污染性重金属离子含量少。The preparation process of the invention is simple, safe and controllable, and consumes less time and energy, and is converted into a single layer of graphene oxide by directly converting graphite. Most importantly, the method for preparing graphene oxide does not cause any pollution, the raw material is most fully utilized, and the prepared graphene oxide has less polluting heavy metal ions.
附图说明DRAWINGS
图1为氧化石墨烯溶液(6mg/mL)；Figure 1 is a graphene oxide solution (6 mg / mL);
图2为氧化石墨烯的扫描图片；2 is a scanned image of graphene oxide;
图3为氧化石墨烯的原子力图片。Figure 3 is an atomic force picture of graphene oxide.
具体实施方式detailed description
一种快速绿色制备单层氧化石墨烯的方法的步骤如下：A method for rapidly preparing a single layer of graphene oxide in green is as follows:
1)将石墨与强酸在-10-20℃下搅拌混合浸润5min-1h，加入强氧化剂高铁酸盐以及其稳定剂，缓慢升温至-10-80℃并持续搅拌0.5-24h，以氧化剥离石墨片层；1) Mix and infiltrate graphite and strong acid at -10-20 °C for 5 min-1 h, add strong oxidant ferrate and its stabilizer, slowly heat up to -10-80 °C and continue stirring for 0.5-24 h to oxidize and strip graphite. Slice
2)将反应液离心，弃去强酸，并将泥状产物缓慢倒入冰的去离子水中稀释，静止，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。2) Centrifuge the reaction solution, discard the strong acid, and slowly pour the product into ice deionized water, stand still, and wash the precipitate repeatedly with 1 mol/L dilute hydrochloric acid and deionized water, and separate into a single layer by centrifugation. Graphene oxide.
所述的强酸与石墨体积质量比为：40-100ml：1g。所述的强氧化剂、稳定剂与石墨的质量比为：4-10g：0.001-1：1g。所述的石墨的粒度为0.5-3mm。所述的强酸为硫酸、硫酸(50％-98％)、发烟硫酸、氯磺酸、浓磷酸、浓硝酸、氟磺酸、三氟甲磺酸或者它们的混合酸。所述的强氧化剂为高铁酸盐。所述的稳定剂为高碘酸、高碘酸盐盐、过硫酸盐、锌盐、铝盐、次氯酸、次氯酸盐、氯酸、氯酸盐、高氯酸、高氯酸盐、正磷酸、正磷酸盐、偏磷酸、偏磷酸盐、多磷酸、多磷酸盐、硼酸、硼酸盐、磷酸酐、正磷酸酐、偏磷酸酐、多磷酸酐、硼酸酐及其它们的组合。The volume ratio of the strong acid to the graphite is: 40-100 ml: 1 g. The mass ratio of the strong oxidizing agent, the stabilizer and the graphite is 4-10 g: 0.001-1:1 g. The graphite has a particle size of 0.5 to 3 mm. The strong acid is sulfuric acid, sulfuric acid (50%-98%), fuming sulfuric acid, chlorosulfonic acid, concentrated phosphoric acid, concentrated nitric acid, fluorosulfonic acid, trifluoromethanesulfonic acid or a mixed acid thereof. The strong oxidant is ferrate. The stabilizer is periodic acid, periodate, persulfate, zinc salt, aluminum salt, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate , orthophosphoric acid, orthophosphate, metaphosphoric acid, metaphosphate, polyphosphoric acid, polyphosphate, boric acid, borate, phosphoric anhydride, orthophosphoric anhydride, metaphosphoric anhydride, polyphosphoric anhydride, boric anhydride, and combinations thereof .
实施例1Example 1
将粒度在0.5μm的石墨与发烟浓硫酸在-10℃下搅拌混合浸润0.5h，加入高铁酸钾和过硫酸钾。随后将反应液升至0℃反应1h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为40ml：1g，高铁酸钾，过硫酸钾和石墨的比例为4g：0.01g：1g。The graphite having a particle size of 0.5 μm was mixed with fuming concentrated sulfuric acid at -10 ° C for 0.5 h, and potassium ferrate and potassium persulfate were added. The reaction solution was then raised to 0 ° C for 1 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 40 ml: 1 g, and the ratio of potassium ferrate, potassium persulfate and graphite was 4 g: 0.01 g: 1 g.
实施例2Example 2
将粒度在40μm的石墨与硫酸(50％)在-10℃下搅拌混合浸润0.5h，加入高铁酸钾和高碘酸。随后将反应液升至0℃反应1h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢 倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为50ml：1g，高铁酸钾，高碘酸和石墨的比例为6g：0.001g：1g。The graphite having a particle size of 40 μm was mixed with sulfuric acid (50%) at -10 ° C for 0.5 h with stirring, and potassium ferrate and periodic acid were added. The reaction solution was then raised to 0 ° C for 1 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. Slow the bottom sediment It was diluted into deionized water of ice and allowed to stand for a while. The precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 50 ml: 1 g, and the ratio of potassium ferrate, periodate to graphite was 6 g: 0.001 g: 1 g.
由附图1，制备的氧化石墨烯具有良好的溶解性，并形成了液晶。由附图2，SEM图片可以看出，所制备氧化石墨烯厚度分布均匀，褶皱部分说明片层具有一定的柔性；由附图3由AFM可以看出，所制备氧化石墨烯厚度在1.1nm左右，也就是单层。The graphene oxide prepared by the drawing of Fig. 1 has good solubility and forms a liquid crystal. 2, the SEM picture shows that the prepared graphene oxide has a uniform thickness distribution, and the pleated portion indicates that the sheet layer has a certain flexibility; as can be seen from FIG. 3 by AFM, the thickness of the prepared graphene oxide is about 1.1 nm. , that is, a single layer.
实施例3Example 3
将粒度在40μm的石墨与硫酸(98％)在-10℃下搅拌混合浸润0.5h，加入高铁酸钾和高碘酸。随后将反应液升至0℃反应1h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为50ml：1g，高铁酸钾，高碘酸和石墨的比例为6g：0.001g：1g。The graphite having a particle size of 40 μm was mixed with sulfuric acid (98%) at -10 ° C for 0.5 h with stirring, and potassium ferrate and periodic acid were added. The reaction solution was then raised to 0 ° C for 1 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 50 ml: 1 g, and the ratio of potassium ferrate, periodate to graphite was 6 g: 0.001 g: 1 g.
实施例4Example 4
将粒度在40μm的石墨与浓磷酸在0℃下搅拌混合浸润1h，加入高铁酸钾和硼酸。随后将反应液升至20℃反应2h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为60ml：1g，高铁酸钾，过硫酸钾和硼酸的比例为10g：0.1g：1g。The graphite having a particle size of 40 μm was mixed with concentrated phosphoric acid at 0 ° C for 1 h with stirring, and potassium ferrate and boric acid were added. The reaction solution was then raised to 20 ° C for 2 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 60 ml: 1 g, and the ratio of potassium ferrate, potassium persulfate and boric acid was 10 g: 0.1 g: 1 g.
实施例5Example 5
将粒度在100μm的石墨与浓硫酸以及浓磷酸在20℃下搅拌混合浸润0.1h，加入高铁酸钾和氯化锌。随后将反应液升至40℃反应4h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，浓硫酸、浓磷酸与石墨的比例为80ml：20ml：1g，高铁酸钾，氯化锌和石墨的比例为7g：0.4g：1g。Graphite having a particle size of 100 μm was mixed with concentrated sulfuric acid and concentrated phosphoric acid at 20 ° C for 0.1 h, and potassium ferrate and zinc chloride were added. The reaction solution was then raised to 40 ° C for 4 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of concentrated sulfuric acid, concentrated phosphoric acid and graphite was 80 ml: 20 ml: 1 g, and the ratio of potassium ferrate, zinc chloride and graphite was 7 g: 0.4 g: 1 g.
实施例6Example 6
将粒度在500μm的石墨与发烟硫酸以及浓磷酸在20℃下搅拌混合浸润0.1h，加入高铁酸钾和高氯酸。随后将反应液升至40℃反应4h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为90ml：1g，高铁酸钾，高氯酸和石墨的比例为9g：1g：1g。The graphite having a particle size of 500 μm was mixed with fuming sulfuric acid and concentrated phosphoric acid at 20 ° C for 0.1 h, and potassium ferrate and perchloric acid were added. The reaction solution was then raised to 40 ° C for 4 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 90 ml: 1 g, potassium ferrate, and the ratio of perchloric acid to graphite was 9 g: 1 g: 1 g.
实施例7 Example 7
将粒度在1mm的石墨与发烟硫酸在20℃下搅拌混合浸润0.5h，加入高铁酸钾和次氯酸钠。随后将反应液升至60℃反应6h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为100ml：1g，高铁酸钾，高氯酸钠和石墨的比例为10g：1g：1g。The graphite having a particle size of 1 mm and the fuming sulfuric acid were mixed and infiltrated at 20 ° C for 0.5 h, and potassium ferrate and sodium hypochlorite were added. The reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 100 ml: 1 g, and the ratio of potassium ferrate, sodium perchlorate and graphite was 10 g: 1 g: 1 g.
实施例8Example 8
将粒度在2mm的石墨与浓硫酸在20℃下搅拌混合浸润1h，加入高铁酸钾和偏磷酸酐。随后将反应液升至60℃反应6h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为100ml：1g，高铁酸钾，偏磷酸酐和石墨的比例为10g：0.3g：1g。The graphite having a particle size of 2 mm and the concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and phosphoric anhydride were added. The reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 100 ml: 1 g, and the ratio of potassium ferrate, metaphosphoric anhydride and graphite was 10 g: 0.3 g: 1 g.
实施例9Example 9
将粒度在3mm的石墨与浓硫酸在20℃下搅拌混合浸润1h，加入高铁酸钾和氯酸钠。随后将反应液升至60℃反应6h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为100ml：1g，高铁酸钾，氯酸钠和石墨的比例为8g：0.6g：1g。The graphite having a particle size of 3 mm and the concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and sodium chlorate were added. The reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 100 ml: 1 g, and the ratio of potassium ferrate, sodium chlorate and graphite was 8 g: 0.6 g: 1 g.
实施例10Example 10
将粒度在3mm的石墨与浓硫酸在20℃下搅拌混合浸润1h，加入高铁酸钾和偏磷酸酐。随后将反应液升至60℃反应6h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为100ml：1g，高铁酸钾，偏磷酸钾和石墨的比例为6g：1g：1g。Graphite having a particle size of 3 mm and concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and phosphoric anhydride were added. The reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 100 ml: 1 g, and the ratio of potassium ferrate, potassium metaphosphate and graphite was 6 g: 1 g: 1 g.
实施例11Example 11
将粒度在3mm的石墨与浓硫酸在20℃下搅拌混合浸润1h，加入高铁酸钾和偏磷酸酐。随后将反应液升至60℃反应6h。反应完毕后，将反应液离心以弃去强酸。将底层沉淀物缓慢倒入冰的去离子水中稀释，静止一段时间，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。反应过程中，强酸与石墨的比例为100ml：1g，高铁酸钾，硼酸钾，磷酸钠和石墨的比例为10g：0.4g：0.2g：1g。Graphite having a particle size of 3 mm and concentrated sulfuric acid were mixed and infiltrated at 20 ° C for 1 h, and potassium ferrate and phosphoric anhydride were added. The reaction solution was then raised to 60 ° C for 6 h. After the reaction was completed, the reaction solution was centrifuged to discard the strong acid. The bottom layer precipitate was slowly poured into iced deionized water and diluted for a while, and the precipitate was repeatedly washed with 1 mol/L of dilute hydrochloric acid and deionized water, and centrifuged to obtain a single layer of graphene oxide. During the reaction, the ratio of strong acid to graphite was 100 ml: 1 g, and the ratio of potassium ferrate, potassium borate, sodium phosphate and graphite was 10 g: 0.4 g: 0.2 g: 1 g.
上述实施例用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都落入本发明的保护范围。 The above-mentioned embodiments are intended to be illustrative of the present invention and are not intended to limit the scope of the invention, and the modifications and variations of the invention are intended to be included within the scope of the invention.

Claims (7)

  1. 一种快速绿色制备单层氧化石墨烯的方法，其特征在于：它的步骤如下：A method for rapidly preparing a single layer of graphene oxide, characterized in that the steps are as follows:
    1)将石墨与强酸在-10-20℃下搅拌混合浸润5min-1h，加入强氧化剂高铁酸盐以及其稳定剂，缓慢升温至-10-80℃并持续搅拌0.5-24h，以氧化剥离石墨片层；1) Mix and infiltrate graphite and strong acid at -10-20 °C for 5 min-1 h, add strong oxidant ferrate and its stabilizer, slowly heat up to -10-80 °C and continue stirring for 0.5-24 h to oxidize and strip graphite. Slice
    2)将反应液离心，弃去强酸，并将泥状产物缓慢倒入冰的去离子水中稀释，静止，将沉淀物用1mol/L的稀盐酸和去离子水反复清洗，离心分离得到单层氧化石墨烯。2) Centrifuge the reaction solution, discard the strong acid, and slowly pour the product into ice deionized water, stand still, and wash the precipitate repeatedly with 1 mol/L dilute hydrochloric acid and deionized water, and separate into a single layer by centrifugation. Graphene oxide.
  2. 如权利要求1所述的一种快速绿色制备单层氧化石墨烯的方法，其特征在于：所述的强酸与石墨体积质量比为：40-100ml：1g。The method for rapidly preparing a single layer of graphene oxide according to claim 1, wherein the volume ratio of the strong acid to the graphite is 40-100 ml: 1 g.
  3. 如权利要求1所述的一种快速绿色制备单层氧化石墨烯的方法，其特征在于：所述的强氧化剂、稳定剂与石墨的质量比为：4-10g：0.001-1：1g。The method for rapidly preparing green single-layer graphene oxide according to claim 1, wherein the mass ratio of the strong oxidizing agent, the stabilizer and the graphite is 4-10 g: 0.001-1:1 g.
  4. 根据权利要求1所述的一种快速绿色制备单层氧化石墨烯的方法，其特征在于，所述的石墨的粒度为0.5um-3mm。The method for rapidly preparing a single layer of graphene oxide according to claim 1, wherein the graphite has a particle size of 0.5 um to 3 mm.
  5. 根据权利要求1所述的一种快速绿色制备单层氧化石墨烯的方法，其特征在于，所述的强酸为硫酸、硫酸(50％-98％)、发烟硫酸、氯磺酸、浓磷酸、浓硝酸、氟磺酸、三氟甲磺酸或者它们的混合酸。The method for rapidly preparing green single-layer graphene oxide according to claim 1, wherein the strong acid is sulfuric acid, sulfuric acid (50%-98%), fuming sulfuric acid, chlorosulfonic acid, concentrated phosphoric acid. Concentrated nitric acid, fluorosulfonic acid, trifluoromethanesulfonic acid or a mixed acid thereof.
  6. 根据权利要求1所述的一种快速绿色制备单层氧化石墨烯的方法，其特征在于，所述的强氧化剂为高铁酸盐。A method for rapidly preparing a single layer of graphene oxide according to claim 1, wherein the strong oxidizing agent is ferrate.
  7. 根据权利要求1所述的一种快速绿色制备单层氧化石墨烯的方法，其特征在于，所述的稳定剂为高碘酸、高碘酸盐盐、过硫酸盐、锌盐、铝盐、次氯酸、次氯酸盐、氯酸、氯酸盐、高氯酸、高氯酸盐、正磷酸、正磷酸盐、偏磷酸、偏磷酸盐、多磷酸、多磷酸盐、硼酸、硼酸盐、磷酸酐、正磷酸酐、偏磷酸酐、多磷酸酐、硼酸酐及其它们的组合。 The method for rapidly preparing green single-layer graphene oxide according to claim 1, wherein the stabilizer is periodic acid, periodate salt, persulfate salt, zinc salt, aluminum salt, Hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, orthophosphoric acid, orthophosphate, metaphosphoric acid, metaphosphate, polyphosphoric acid, polyphosphate, boric acid, boric acid Salts, phosphoric anhydrides, orthophosphoric anhydrides, metaphosphoric anhydrides, polyphosphoric anhydrides, boric anhydrides, and combinations thereof.
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