CN104386671B - A kind of pollution-free low cost prepares the technique of single-layer graphene oxide - Google Patents
A kind of pollution-free low cost prepares the technique of single-layer graphene oxide Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002356 single layer Substances 0.000 title claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 45
- 239000010439 graphite Substances 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010790 dilution Methods 0.000 claims abstract description 12
- 239000012895 dilution Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 7
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
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- 238000004108 freeze drying Methods 0.000 claims description 7
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- 238000006243 chemical reaction Methods 0.000 abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004880 explosion Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000013049 sediment Substances 0.000 description 12
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
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- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
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- 150000007513 acids Chemical class 0.000 description 2
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- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明涉及纳米材料领域，特别是一种无污染低成本制备单层氧化石墨烯的工艺。 The invention relates to the field of nanometer materials, in particular to a process for preparing single-layer graphene oxide with no pollution and low cost.
背景技术 Background technique
自2004年起，石墨烯的优异的力学性质、电学性质、热学性质、光学性质相继被发现。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。 Since 2004, the excellent mechanical properties, electrical properties, thermal properties, and optical properties of graphene have been discovered one after another. Graphene has a large theoretical specific surface area, coupled with the excellent performance of the monolithic structure, carbon-based materials with graphene as the source material have been greatly developed and applied.
氧化石墨烯是石墨烯的氧化物，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。其表面具有丰富的官能团，可溶解于强极性溶剂中，也可以进行改性，另外其具有超大的尺度及比表面积等。目前已经实现的宏观组装材料纤维、薄膜、气凝胶、石墨烯基催化剂等都是依托于氧化石墨烯来制备的。 Graphene oxide is the oxide of graphene, an important precursor of graphene, and the most important intermediate for the macroscopic assembly and modification of graphene materials. Its surface has abundant functional groups, can be dissolved in strong polar solvents, and can also be modified. In addition, it has a super large scale and specific surface area. The macro-assembled material fibers, films, aerogels, and graphene-based catalysts that have been realized so far are all based 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modifiedHummers。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爆炸，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。 The existing methods for preparing graphene oxide mainly include Brodie, Staudenmaier, Hofmann, Hummers and modified Hummers. These methods are generally divided into two types according to the oxidizing agent used, the Brodie method based on potassium chlorate and the Hummers method based on potassium permanganate. However, these two oxidants are not only easy to explode, but also have a slow reaction rate. Potassium chlorate is easy to release toxic gas, and potassium permanganate will produce heavy metal ion pollution. All of these methods fall under the theme of the times that are not in line with green environmental protection.
由于强酸的存在，其清洗过程繁复复杂，耗时耗力，成本高。另外由于污染性物质的存在，其污染性废水需要特殊的处理：首先处理其污染性物质，然后将其废液中的废酸中和掉。此过程也有很高的成本。为此氧化石墨烯的低成本无污染制备问题的到了人们越来越多的重视。 Due to the presence of strong acid, the cleaning process is complicated, time-consuming and labor-intensive, and the cost is high. In addition, due to the existence of polluting substances, its polluting wastewater needs special treatment: firstly, its polluting substances are treated, and then the waste acid in its waste liquid is neutralized. This process also has a high cost. For this reason, the low-cost and pollution-free preparation of graphene oxide has attracted more and more attention.
发明内容 Contents of the invention
本发明的目的是克服现有技术的不足，提供一种简便的无污染低成本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，溶解性好；反应过程时间段，安全无污染，所有物质及原料都得到了充分的利用，极大地降低了成本。 The purpose of the present invention is to overcome the deficiencies in the prior art, provide a kind of easy pollution-free and low-cost method for preparing single-layer graphene oxide, the graphene oxide sheet monolayer of this method preparation is uniformly dispersed, and solubility is good; Reaction process time Section, safe and pollution-free, all substances and raw materials have been fully utilized, which greatly reduces the cost.
无污染低成本制备氧化石墨烯的工艺的步骤如下： The steps of the process for preparing graphene oxide with no pollution and low cost are as follows:
1)将石墨与强酸在0-40oC下搅拌混合浸润5min-30min，加入强氧化剂，并持续搅拌1-8h，以氧化剥离石墨片层； 1) Mix and soak graphite and strong acid at 0-40 o C for 5min-30min, add a strong oxidant, and keep stirring for 1-8h to oxidize and peel off the graphite sheet;
2)离心分离，回收上层清液作为强酸用于下一次反应，并将泥状产物缓慢倒入去离子水中稀释，搅拌，用1mol/L的稀盐酸洗涤后用去离子水反复清洗离心，得到单层氧化石墨烯水溶液； 2) Centrifugal separation, reclaim the supernatant as a strong acid for the next reaction, slowly pour the muddy product into deionized water for dilution, stir, wash with 1mol/L dilute hydrochloric acid, and then repeatedly wash and centrifuge with deionized water to obtain Monolayer graphene oxide aqueous solution;
3)在步骤2)产生的废水中通入氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料； 3) Ammonia gas is introduced into the waste water generated in step 2) until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements;
4)将步骤2)得到的氧化石墨烯水溶液浓缩后经过冻干/喷雾干燥/超临界干燥技术，得到高密度高比表面积的石墨烯粉体。 4) After concentrating the graphene oxide aqueous solution obtained in step 2), go through freeze-drying/spray drying/supercritical drying technology to obtain graphene powder with high density and high specific surface area.
所述的强酸与石墨体积质量比为：40-100ml：1g。所述的强氧化剂与石墨的质量比为：4-10g：1g。所述的石墨的粒度为0.5um-3mm。所述的强酸为质量百分比浓度为50%-98%的硫酸、磷酸或者它们的混合酸，以及它们的离心回收产物。所述的强氧化剂为高铁酸钾或高铁酸钠。 The volume-to-mass ratio of the strong acid to graphite is: 40-100ml: 1g. The mass ratio of the strong oxidizing agent to graphite is: 4-10g:1g. The particle size of the graphite is 0.5um-3mm. The strong acid is sulfuric acid, phosphoric acid or their mixed acids with a concentration of 50%-98% by mass, and their centrifuged recovery products. The strong oxidizing agent is potassium ferrate or sodium ferrate.
本发明制备过程简单安全可控，耗时耗能少，没有爆炸危险，没有污染。其中浓硫酸的循环使用，所有原料成肥过程，使得所有原料以及元素都得到了充分的利用。极大地降低了氧化石墨烯制备成本。 The preparation process of the invention is simple, safe and controllable, consumes less time and energy, has no danger of explosion and no pollution. Among them, the recycling of concentrated sulfuric acid and the fertilizer process of all raw materials make full use of all raw materials and elements. The cost of graphene oxide preparation is greatly reduced.
附图说明 Description of drawings
图1为氧化石墨烯溶液（6mg/mL）； Figure 1 is graphene oxide solution (6mg/mL);
图2为氧化石墨烯溶液的偏光液晶图片（3mg/mL）； Figure 2 is a polarized liquid crystal picture of graphene oxide solution (3mg/mL);
图3为氧化石墨烯的扫描图片； Fig. 3 is the scanning picture of graphene oxide;
图4为氧化石墨烯的原子力图片； Fig. 4 is the atomic force picture of graphene oxide;
图5为氧化石墨烯的粉体SEM图片。 Figure 5 is a powder SEM picture of graphene oxide.
具体实施方式 detailed description
无污染低成本制备氧化石墨烯的工艺的步骤如下： The steps of the process for preparing graphene oxide with no pollution and low cost are as follows:
1)将石墨与强酸在0-40oC下搅拌混合浸润5min-30min，加入强氧化剂，并持续搅拌1-8h，以氧化剥离石墨片层； 1) Mix and soak graphite and strong acid at 0-40 o C for 5min-30min, add a strong oxidant, and keep stirring for 1-8h to oxidize and peel off the graphite sheet;
2)离心分离，回收上层清液作为强酸用于下一次反应，并将泥状产物缓慢倒入去离子水中稀释，搅拌，用1mol/L的稀盐酸洗涤后用去离子水反复清洗离心，得到单层氧化石墨烯水溶液； 2) Centrifugal separation, reclaim the supernatant as a strong acid for the next reaction, slowly pour the muddy product into deionized water for dilution, stir, wash with 1mol/L dilute hydrochloric acid, and then repeatedly wash and centrifuge with deionized water to obtain Monolayer graphene oxide aqueous solution;
3)在步骤2)产生的废水中通入氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料； 3) Ammonia gas is introduced into the waste water generated in step 2) until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements;
4)将步骤2)得到的氧化石墨烯水溶液浓缩后经过冻干/喷雾干燥/超临界干燥技术，得到高密度高比表面积的石墨烯粉体。 4) After concentrating the graphene oxide aqueous solution obtained in step 2), go through freeze-drying/spray drying/supercritical drying technology to obtain graphene powder with high density and high specific surface area.
所述的强酸与石墨体积质量比为：40-100ml：1g。所述的强氧化剂与石墨的质量比为：4-10g：1g。所述的石墨的粒度为0.5um-3mm。所述的强酸为质量百分比浓度为50%-98%的硫酸、磷酸或者它们的混合酸，以及它们的离心回收产物。所述的强氧化剂为高铁酸钾或高铁酸钠。 The volume-to-mass ratio of the strong acid to graphite is: 40-100ml: 1g. The mass ratio of the strong oxidizing agent to graphite is: 4-10g:1g. The particle size of the graphite is 0.5um-3mm. The strong acid is sulfuric acid, phosphoric acid or their mixed acids with a concentration of 50%-98% by mass, and their centrifuged recovery products. The strong oxidizing agent is potassium ferrate or sodium ferrate.
实施例1 Example 1
将石墨与强酸在0oC下搅拌混合浸润5min，加入强氧化剂，并持续搅拌1h，以氧化剥离石墨片层；离心分离，回收上层清液作为强酸用于下一次反应，并将泥状产物缓慢倒入去离子水中稀释，搅拌，用1mol/L的稀盐酸洗涤后用去离子水反复清洗离心，得到单层氧化石墨烯水溶液；在步骤2)产生的废水中通入氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料；将步骤2)得到的氧化石墨烯水溶液浓缩后经过冻干/喷雾干燥/超临界干燥技术，得到高密度高比表面积的石墨烯粉体。所述的强酸与石墨体积质量比为：40ml：1g。所述的强氧化剂与石墨的质量比为：4g：1g。所述的石墨的粒度为0.5um。所述的强酸为质量百分比浓度为50%的硫酸。所述的强氧化剂为高铁酸钾。 Mix graphite and strong acid at 0 o C for 5 minutes, add a strong oxidant, and continue stirring for 1 hour to oxidize and peel off the graphite sheet; centrifuge, recover the supernatant as a strong acid for the next reaction, and remove the muddy product Slowly pour into deionized water for dilution, stir, wash with 1mol/L dilute hydrochloric acid and then repeatedly wash and centrifuge with deionized water to obtain a single-layer graphene oxide aqueous solution; pass ammonia gas into the waste water generated in step 2) to reach the pH value 7, to obtain an inorganic fertilizer containing nitrogen, potassium, and iron elements; the graphene oxide aqueous solution obtained in step 2) is concentrated and then subjected to freeze-drying/spray drying/supercritical drying technology to obtain graphene powder with high density and high specific surface area . The volume-to-mass ratio of the strong acid to graphite is: 40ml:1g. The mass ratio of the strong oxidizing agent to graphite is: 4g:1g. The particle size of the graphite is 0.5um. Described strong acid is the sulfuric acid that mass percent concentration is 50%. Described strong oxidizing agent is potassium ferrate.
实施例2 Example 2
将石墨与强酸在40oC下搅拌混合浸润30min，加入强氧化剂，并持续搅拌8h，以氧化剥离石墨片层；离心分离，回收上层清液作为强酸用于下一次反应，并将泥状产物缓慢倒入去离子水中稀释，搅拌，用1mol/L的稀盐酸洗涤后用去离子水反复清洗离心，得到单层氧化石墨烯水溶液；在步骤2)产生的废水中通入氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料；将步骤2)得到的氧化石墨烯水溶液浓缩后经过冻干/喷雾干燥/超临界干燥技术，得到高密度高比表面积的石墨烯粉体。所述的强酸与石墨体积质量比为：100ml：1g。所述的强氧化剂与石墨的质量比为：10g：1g。所述的石墨的粒度为3mm。所述的强酸为质量百分比浓度为98%的离心回收产物。所述的强氧化剂为高铁酸钠。 Stir and mix graphite and strong acid at 40 o C for 30 minutes, add a strong oxidant, and continue to stir for 8 hours to oxidize and peel off the graphite sheet; centrifuge, recover the supernatant as a strong acid for the next reaction, and remove the muddy product Slowly pour into deionized water for dilution, stir, wash with 1mol/L dilute hydrochloric acid and then repeatedly wash and centrifuge with deionized water to obtain a single-layer graphene oxide aqueous solution; pass ammonia gas into the waste water generated in step 2) to reach the pH value 7, to obtain an inorganic fertilizer containing nitrogen, potassium, and iron elements; the graphene oxide aqueous solution obtained in step 2) is concentrated and then subjected to freeze-drying/spray drying/supercritical drying technology to obtain graphene powder with high density and high specific surface area . The volume-to-mass ratio of the strong acid to graphite is: 100ml: 1g. The mass ratio of the strong oxidizing agent to graphite is: 10g:1g. The particle size of the graphite is 3mm. The strong acid is a product recovered by centrifugation with a concentration of 98% by mass. Described strong oxidizing agent is sodium ferrate.
实施例3 Example 3
将粒度在0.5μm的石墨与浓硫酸在0℃下搅拌混合浸润0.5h，加入高铁酸钾和过硫酸钾。随后将反应液升至室温反应1h。反应完毕后，将反应液离心以回收强酸。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。将其产生的废液用氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料。反应过程中，强酸与石墨的比例为40ml：1g，高铁酸钾和石墨的比例为4g：1g。所制得的氧化石墨烯溶液经过喷雾干燥法制备成密度在30mg/mL的土黄色氧化石墨烯粉体。 Graphite with a particle size of 0.5 μm and concentrated sulfuric acid were stirred, mixed and infiltrated at 0°C for 0.5 h, and potassium ferrate and potassium persulfate were added. Then the reaction solution was raised to room temperature for 1 h. After the reaction, the reaction solution was centrifuged to recover the strong acid. Slowly pour the bottom sediment into iced deionized water for dilution, let it stand for a period of time, wash the sediment repeatedly with 1mol/L dilute hydrochloric acid and deionized water, and centrifuge to obtain single-layer graphene oxide. The generated waste liquid is treated with ammonia gas until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements. During the reaction, the ratio of strong acid to graphite is 40ml:1g, and the ratio of potassium ferrate to graphite is 4g:1g. The prepared graphene oxide solution was spray-dried to prepare a khaki graphene oxide powder with a density of 30 mg/mL.
实施例4 Example 4
将粒度在40μm的石墨与硫酸（50%）在10℃下搅拌混合浸润10min，加入高铁酸钠。随后将反应液升至室温反应3h。反应完毕后，将反应液离心以回收强酸。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。将其产生的废液用氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料。反应过程中，强酸与石墨的比例为50ml：1g，高铁酸钾和石墨的比例为6g：1g。所制得的氧化石墨烯溶液经过喷雾干燥法制备成密度在70mg/mL的土黄色氧化石墨烯粉体。 Stir, mix and infiltrate graphite with a particle size of 40 μm and sulfuric acid (50%) at 10°C for 10 minutes, and add sodium ferrate. Then the reaction solution was raised to room temperature for 3 h. After the reaction, the reaction solution was centrifuged to recover the strong acid. Slowly pour the bottom sediment into iced deionized water for dilution, let it stand for a period of time, wash the sediment repeatedly with 1mol/L dilute hydrochloric acid and deionized water, and centrifuge to obtain single-layer graphene oxide. The generated waste liquid is treated with ammonia gas until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements. During the reaction, the ratio of strong acid to graphite is 50ml:1g, and the ratio of potassium ferrate to graphite is 6g:1g. The prepared graphene oxide solution was spray-dried to prepare a khaki graphene oxide powder with a density of 70 mg/mL.
由附图1，制备的氧化石墨烯具有良好的溶解性。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；附图4，为氧化石墨烯粉体，密度为70mg/mL。 By accompanying drawing 1, the graphene oxide prepared has good solubility. It can be seen from the accompanying drawing 2 and the SEM picture that the thickness distribution of the prepared graphene oxide is uniform, and the wrinkled part shows that the sheet has a certain flexibility; it can be seen from the accompanying drawing 3 by AFM that the thickness of the prepared graphene oxide is about 1.1nm , which is a single layer; Figure 4 is a graphene oxide powder with a density of 70mg/mL.
实施例5 Example 5
将粒度在40μm的石墨与硫酸（80%）在18℃下搅拌混合浸润20min，加入高铁酸钾。随后将反应液升至室温反应3h。反应完毕后，将反应液离心以回收强酸。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。将其产生的废液用氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料。反应过程中，强酸与石墨的比例为50ml：1g，高铁酸钾和石墨的比例为5g：1g。所制得的氧化石墨烯溶液经过喷雾干燥法制备成密度在100mg/mL的土黄色氧化石墨烯粉体。 Stir, mix and infiltrate graphite with a particle size of 40 μm and sulfuric acid (80%) at 18°C for 20 minutes, and add potassium ferrate. Then the reaction solution was raised to room temperature for 3 h. After the reaction, the reaction solution was centrifuged to recover the strong acid. Slowly pour the bottom sediment into iced deionized water for dilution, let it stand for a period of time, wash the sediment repeatedly with 1mol/L dilute hydrochloric acid and deionized water, and centrifuge to obtain single-layer graphene oxide. The generated waste liquid is treated with ammonia gas until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements. During the reaction, the ratio of strong acid to graphite is 50ml:1g, and the ratio of potassium ferrate to graphite is 5g:1g. The prepared graphene oxide solution was prepared into a khaki graphene oxide powder with a density of 100 mg/mL through a spray drying method.
实施例6 Example 6
将粒度在100μm的石墨与浓磷酸在30℃下搅拌混合浸润30min，加入高铁酸钾。随后将反应液升至室温反应6h。反应完毕后，将反应液离心以回收强酸。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。将其产生的废液用氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料。反应过程中，强酸与石墨的比例为60ml：1g，高铁酸钾和石墨的比例为8g：1g。所制得的氧化石墨烯溶液经过冻干法制备成密度在10mg/mL的氧化石墨烯固体。 Graphite with a particle size of 100 μm and concentrated phosphoric acid were stirred, mixed and infiltrated at 30°C for 30 minutes, and potassium ferrate was added. Then the reaction solution was raised to room temperature for 6 h. After the reaction, the reaction solution was centrifuged to recover the strong acid. Slowly pour the bottom sediment into iced deionized water for dilution, let it stand for a period of time, wash the sediment repeatedly with 1mol/L dilute hydrochloric acid and deionized water, and centrifuge to obtain single-layer graphene oxide. The generated waste liquid is treated with ammonia gas until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements. During the reaction, the ratio of strong acid to graphite is 60ml:1g, and the ratio of potassium ferrate to graphite is 8g:1g. The prepared graphene oxide solution was prepared into a graphene oxide solid with a density of 10 mg/mL through a freeze-drying method.
实施例7 Example 7
将粒度在300μm的石墨与浓硫酸以及浓磷酸在20℃下搅拌混合浸润25min，加入高铁酸钠。随后将反应液升至室温反应7h。反应完毕后，将反应液离心以回收强酸。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。将其产生的废液用氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料。反应过程中，浓硫酸、浓磷酸与石墨的比例为80ml：20ml：1g，高铁酸钠和石墨的比例为7g：1g。所制得的氧化石墨烯溶液经过冻干法制备成密度在30mg/mL的氧化石墨烯固体。 Stir, mix and infiltrate graphite with a particle size of 300 μm, concentrated sulfuric acid and concentrated phosphoric acid at 20°C for 25 minutes, and add sodium ferrate. Then the reaction solution was raised to room temperature for 7 h. After the reaction, the reaction solution was centrifuged to recover the strong acid. Slowly pour the bottom sediment into iced deionized water for dilution, let it stand for a period of time, wash the sediment repeatedly with 1mol/L dilute hydrochloric acid and deionized water, and centrifuge to obtain single-layer graphene oxide. The generated waste liquid is treated with ammonia gas until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements. During the reaction, the ratio of concentrated sulfuric acid, concentrated phosphoric acid and graphite is 80ml:20ml:1g, and the ratio of sodium ferrate and graphite is 7g:1g. The prepared graphene oxide solution was prepared into a graphene oxide solid with a density of 30 mg/mL through a freeze-drying method.
实施例8 Example 8
将粒度在500μm的石墨与硫酸（60%）以及浓磷酸混合酸的回收酸在20℃下搅拌混合浸润30min，加入高铁酸钠。随后将反应液升至室温反应8h。反应完毕后，将反应液离心以回收强酸。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。将其产生的废液用氨气至pH值为7，得到含有氮、钾、铁元素的无机肥料。反应过程中，硫酸（60%）以及浓磷酸与石墨的比例为60ml：30ml：1g，高铁酸钠和石墨的比例为9g：1g。所制得的氧化石墨烯溶液经过超临界干燥制备成密度在80mg/mL的氧化石墨烯固体。 Graphite with a particle size of 500 μm, sulfuric acid (60%) and concentrated phosphoric acid mixed acid were mixed and infiltrated at 20°C for 30 minutes, and sodium ferrate was added. Then the reaction solution was raised to room temperature for 8 h. After the reaction, the reaction solution was centrifuged to recover the strong acid. Slowly pour the bottom sediment into iced deionized water for dilution, let it stand for a period of time, wash the sediment repeatedly with 1mol/L dilute hydrochloric acid and deionized water, and centrifuge to obtain single-layer graphene oxide. The generated waste liquid is treated with ammonia gas until the pH value is 7 to obtain an inorganic fertilizer containing nitrogen, potassium and iron elements. During the reaction, the ratio of sulfuric acid (60%) and concentrated phosphoric acid to graphite is 60ml:30ml:1g, and the ratio of sodium ferrate to graphite is 9g:1g. The prepared graphene oxide solution was prepared by supercritical drying into a graphene oxide solid with a density of 80 mg/mL.
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 used to illustrate the present invention, rather than to limit the present invention. Within the spirit of the present invention and the protection scope of the claims, any modification and change made to the present invention will fall into the protection scope of the present invention.
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