WO2016037565A1 - 石墨烯水凝胶、气凝胶、其制备方法及应用 - Google Patents

石墨烯水凝胶、气凝胶、其制备方法及应用 Download PDF

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WO2016037565A1
WO2016037565A1 PCT/CN2015/089216 CN2015089216W WO2016037565A1 WO 2016037565 A1 WO2016037565 A1 WO 2016037565A1 CN 2015089216 W CN2015089216 W CN 2015089216W WO 2016037565 A1 WO2016037565 A1 WO 2016037565A1
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water
soluble
graphene
graphene oxide
reducing agent
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PCT/CN2015/089216
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English (en)
French (fr)
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李景烨
李吉豪
李林繁
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中国科学院上海应用物理研究所
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Priority claimed from CN201410461586.1A external-priority patent/CN104250005B/zh
Priority claimed from CN201510121541.4A external-priority patent/CN106032274B/zh
Priority claimed from CN201510122453.6A external-priority patent/CN106031857B/zh
Priority claimed from CN201510305992.3A external-priority patent/CN106268631B/zh
Application filed by 中国科学院上海应用物理研究所 filed Critical 中国科学院上海应用物理研究所
Publication of WO2016037565A1 publication Critical patent/WO2016037565A1/zh

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    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating

Definitions

  • the invention relates to a graphene hydrogel, an aerogel, a preparation method thereof and an application thereof.
  • Graphene is a true monoatomic layer thickness and a strict two-dimensional structure with high mechanical strength, elasticity, thermal conductivity, electrical conductivity, and quantum Hall effect. In recent years, it has attracted academia and industry. Widespread attention in the world. Since the British scientists Andre Jem and Kostyano Vosino discovered the graphene in 2010 and won the Nobel Prize, graphene research has reached an unprecedented research climax, and more and more studies have found that it is in energy storage. The special fields of electrical devices, catalysis and environmental science have great application prospects.
  • High-energy ray irradiation is a high-efficiency, low-cost, low-energy, non-polluting method.
  • the high-energy ray includes gamma ray or electron beam. It is widely used in polymer synthesis and modification, and environmental pollutant radiation. Degradation, medical and health, food processing and other fields have not been reported in the preparation of graphene aerogel. Therefore, the application of high-energy ray irradiation to the preparation of graphene aerogel is yet to be developed, which is of great significance for the application research and market-oriented production of graphene.
  • the technical problem to be solved by the present invention is to provide a graphene hydrogel, an aerogel, a preparation method thereof and an application thereof, in order to overcome the defects of high temperature and complicated process in the preparation method of the graphene aerogel in the prior art.
  • the invention adopts the irradiation method to prepare graphene hydrogel and aerogel, and has not been reported yet.
  • the preparation method is simple in operation, green and environmentally friendly, and the reaction conditions are loose; and the graphene aerogel obtained by the preparation method of the invention is Porous and macroporous structure, relatively uniform structure, can be used for adsorption of organic solvents, and has great application value.
  • the invention provides a preparation method of graphene hydrogel, which comprises the following steps:
  • the graphene oxide dispersion may be a graphene oxide dispersion prepared by a conventional method in the art, preferably obtained by the following steps: 1 pre-oxidation: graphite, concentrated sulfuric acid and nitric acid Pour into water, filter, and dry; repeat the above pre-oxidation process 2-3 times to obtain pre-oxidized graphite; 2 thermal expansion: thermal expansion of the pre-oxidized graphite of step 1 at 400-900 ° C for 10-30 s to obtain thermally expanded graphite oxide 3, the step 2 thermal expansion of graphite oxide and concentrated sulfuric acid, potassium persulfate (K 2 S 2 O 8 ) and phosphorus pentoxide mixture at 80-90 ° C, washed with water, washed, dried to obtain pre-oxidation Thermally expanded graphite; 4 The preoxidized thermally expanded graphite of step 3 is mixed with concentrated sulfuric acid at 0-5 ° C, potassium permanganate is added, the reaction is added, hydrogen peroxide is added, the mixture is
  • the content of the graphene oxide in the graphene oxide dispersion is a conventional content in the art, preferably 1 to 30 mg/mL.
  • the water-soluble reducing agent may be a water-soluble alcohol and/or an amine water-soluble reducing agent.
  • the water-soluble reducing agent when the water-soluble reducing agent is a water-soluble alcohol, the water-soluble reducing agent preferably accounts for 2 to 95% by mass, more preferably 5 to 90% by mass of the graphene oxide mixture. , optimally 10-80%.
  • the mass ratio of the graphene oxide to the water-soluble reducing agent in the graphene oxide mixture is preferably (1: 0.5)-(1:400), preferably (1:0.5)-(1:200), more preferably (1:1)-(1:150), optimally (1:5)-(1 :100).
  • the mass percentage of the water-soluble alcohol to the graphene oxide mixture is preferably 2 to 95%.
  • the quality of the reducing agent is preferably (1:0.5)-(1:200), preferably (1:0.5)-(1:100), more preferably (1:0.5)-(1:50), more Preference is given to (1:0.5)-(1:10), optimally (1:0.5)-(1:5), most preferably (1:0.5)-(1:2).
  • the water-soluble alcohol is a water-soluble alcohol conventionally used in the art, preferably methanol, ethanol, propanol, isopropanol, butanol, butanediol, isobutanol, and ethylene.
  • a water-soluble alcohol conventionally used in the art, preferably methanol, ethanol, propanol, isopropanol, butanol, butanediol, isobutanol, and ethylene.
  • the amine water-soluble reducing agent is conventional in the art, preferably a Amine, ethylenediamine, diethylamine, propylenediamine, butanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyallylamine, N,N'-di(2-aminoethyl) One or more of 1,3-propanediamine and ammonia.
  • the content of the graphene oxide in the graphene oxide mixed solution is preferably from 1 to 20 mg/mL, more preferably from 2 to 10 mg/mL.
  • inorganic nanoparticles or water-soluble precious metal compounds may be added to the graphene oxide mixture.
  • the inorganic nanoparticles may be inorganic nanoparticles conventional in the art, preferably metal nanoparticles and/or non-metal nanoparticles.
  • the metal nanoparticles are preferably one or more of silver, gold, platinum, iron, cobalt, tin, and lead.
  • the non-metallic nanoparticles are preferably one or more of metal oxide nanoparticles, non-metal oxide nanoparticles, and silicon nanoparticles, more preferably metal oxide nanoparticles.
  • the metal oxide nanoparticles are preferably one or more of titanium dioxide, ferric oxide, triiron tetroxide, manganese dioxide, tin dioxide and cobalt tetroxide; the non-metal oxide nanoparticles are more Preferably, the silica nanoparticles are included.
  • the particle size of the inorganic nanoparticles may be a particle size commonly used in the art, preferably 1-500 nm, more preferably 1-20 nm, 20-50 nm, 50-100 nm, 100-500. Nano, 100-200 nm or 10-50 nm.
  • the particle diameter of the inorganic nanoparticles is within the limits of the present invention, and the obtained composite aerogel is easily formed into a bulk structure.
  • the quality of the graphene oxide and the inorganic nanoparticles is preferably (1:0.01)-(1:5).
  • the water-soluble precious metal compound may be a conventional water-soluble precious metal compound in the art, preferably a water-soluble precious metal acid and/or a water-soluble precious metal salt.
  • the water-soluble precious metal acid is conventional in the art, preferably one or more of chloroauric acid, chloroplatinic acid, chloropalladic acid and chlorodecanoic acid.
  • the water-soluble precious metal salt is conventional in the art, preferably one or more of silver nitrate, potassium chlorate, potassium chlorate, ruthenium trichloride, ruthenium trichloride and ruthenium trichloride. .
  • the water solubility means that it can be dissolved in water at different temperatures.
  • the noble metal in the water-soluble precious metal compound is preferably gold, platinum, palladium, rhodium, silver, One or more of ⁇ and ⁇ .
  • the quality of the graphene oxide and the water-soluble precious metal compound is preferably (1:0.05)-(1:3).
  • the step (1) if the content of the water-soluble reducing agent is too small, the graphene-precious metal inorganic nanocomposite particles suspended in the tube are obtained, and the continuous wet graphene-precious metal having a certain self-supporting mechanical strength cannot be obtained.
  • Inorganic nanocomposite hydrogel if the content of water-soluble reducing agent is large, not only increases the cost but also makes the dispersion of graphene oxide and noble metal ions in solution poor, and it is not easy to obtain continuous graphene-precious metal inorganic nanoparticle composite water. gel.
  • the irradiation reaction is preferably carried out under anaerobic conditions.
  • a water-soluble alcohol is used as the water-soluble reducing agent, or an inorganic nanoparticle or a water-soluble precious metal compound is added during the preparation, the irradiation reaction can be carried out in an oxygen-free atmosphere or an aerobic atmosphere.
  • the oxygen-free atmosphere conditions are oxygen-free atmosphere conditions conventionally used in the art, preferably nitrogen and/or argon atmosphere conditions.
  • the aerobic atmosphere conditions are aerobic atmosphere conditions conventionally used in the art, generally air.
  • the high-energy ray is preferably a cobalt 60 ⁇ ray or an electron beam ray.
  • the irradiation reaction may be a routine of the irradiation process in the art.
  • the dose of the irradiation reaction is preferably from 5 to 500 kGy, more preferably from 20 to 200 kGy; and the dose rate of the irradiation reaction is preferably from 0.1 to 10 kGy/hr.
  • the dose of the irradiation reaction is preferably It is 20-800 kGy, more preferably 50-800 kGy, most preferably 110-600 kGy; the dose rate of the irradiation reaction is preferably 0.1-15 kGy/hour, more preferably 0.5-12 kGy/sm. The time is preferably 1-12 kGy/hour.
  • the present invention also provides a graphene hydrogel prepared by the above method for preparing a graphene hydrogel.
  • the invention also provides a method for preparing a graphene aerogel, which comprises the steps of: lyophilizing the above graphene hydrogel or supercritical carbon dioxide drying.
  • freeze drying described can be a routine operation in the art.
  • the graphene oxide mixture contains a water-soluble precious metal compound and when the water-soluble reducing agent is a water-soluble alcohol, the water-soluble alcohol accounts for the oxidation in order to achieve a molding effect of the graphene-precious metal inorganic nanoparticle composite aerogel.
  • the mass percentage of the graphene mixture is preferably from 5 to 90%, more preferably from 10 to 80%.
  • the quality of the graphene oxide and the amine water-soluble reducing agent is preferably (1:1)-(1:150), more preferably (1:5). )-(1:100).
  • the noble metal inorganic nanoparticles are directly blended with graphene to prepare a composite aerogel, the noble metal inorganic nanoparticles are only filled inside the porous structure of the graphene aerogel, which is unloadable on the surface of the graphene, and its agglomeration is severe and dispersed.
  • the poor properties result in its excellent catalytic and electrical properties, and its utilization efficiency is limited due to agglomeration.
  • the present invention adopts a water-soluble precious metal compound, and the obtained graphene-precious metal inorganic nanoparticle composite aerogel is completely different from the same.
  • the nanoparticles of the present invention are formed in situ on the surface of graphene by ions, which are uniformly supported on the frame structure of the graphene composite aerogel, including the outer surface and the inner porous structure, so the noble metal nanoparticles of the present invention are not only The dispersibility is better, and the adhesion is slowly formed on the graphene sheet layer, and the two are closely combined without agglomeration, so that the prepared composite aerogel is beneficial to fully exert the noble metal inorganic nanometer in the process of absorbing the organic solvent.
  • the particles themselves have good catalytic and electrical properties, and have extreme properties. Great potential application value.
  • the present invention also provides a graphene aerogel prepared by the above method for preparing a graphene aerogel.
  • the density of the graphene aerogel is preferably 4 to 9 mg/cm 3 .
  • the graphene aerogel has a pore size distribution between 10 and 100 ⁇ m, and the density is adjustable, and the density is adjustable. It is preferably 2.9 to 41 mg/cm 3 .
  • the prepared aerogel has a porous structure and a pore size distribution of 1-100 ⁇ m.
  • the prepared aerogel has a porous, macroporous structure, a relatively uniform structure, and a pore size distribution of 10-100 ⁇ m, wherein the diameter of the noble metal inorganic nanoparticle is preferably 40-80 nm.
  • the invention also provides the use of the above graphene aerogel in adsorbing an organic solvent.
  • the organic solvent may be an organic solvent conventional in the art, preferably an organic liquid solvent having a relative density of 0.63-1.59 g/cm 3 (25 ° C), which is 1 g/cm 3 relative to the density of water at 25 ° C.
  • the organic solvent may be a conventional organic solvent in the art, preferably a liquid alkane (n-decane), a liquid aromatic hydrocarbon (toluene), a liquid alcohol (n-butanol, ethanol), a liquid carboxylic acid (acrylic acid), a liquid ester ( One or more of methyl methacrylate, crude oil, edible oil (soybean oil), diesel and kerosene.
  • a liquid alkane n-decane
  • a liquid aromatic hydrocarbon toluene
  • n-butanol, ethanol a liquid carboxylic acid (acrylic acid)
  • a liquid ester One or more of methyl methacrylate, crude oil, edible oil (soybean oil), diesel and kerosene.
  • the prepared graphene aerogel is used for adsorbing n-decane when the aerogel density At 2.9 mg/cm 3 , the oil absorption performance can be as high as 250 g/g.
  • a cylindrical graphene-gold nanoparticle aerogel having a density of 3.1 mg/cm 3 was used to adsorb an organic solvent of carbon tetrachloride having a relative density of 1.59, and its adsorption capacity was up to 500 g/g.
  • the reagents and starting materials used in the present invention are commercially available.
  • the graphene hydrogel and aerogel of the present invention are directly obtained by one-step irradiation reduction and assembly by using a graphene oxide dispersion as a raw material, and are directly obtained by means of a freeze-drying method, and the irradiation reduction reaction is carried out at an ambient temperature, and the operation is simple.
  • the reaction conditions are loose and it is expected to realize industrialization of technology.
  • the raw material used in the invention is graphene oxide, the source is very wide, the cost is low, and the utilization rate is high.
  • the graphene oxide raw material used is completely gel-formed after the reaction, the aqueous solution around the gel is transparent, and the raw material has almost no loss.
  • the invention adopts water-soluble alcohol as the technical scheme of the irradiation reaction system, the preparation process is simple, does not involve harsh chemical reaction conditions, avoids complicated and difficult chemical reaction and purification process, and the prepared graphene aerogel is relatively Pure, no other elements except carbon and oxygen.
  • the shape and size of the graphene hydrogel and aerogel of the present invention are adjustable, and graphene hydrogels and aerogels of different shapes and sizes can be obtained by using irradiation reactors of different shapes and sizes.
  • the noble metal nanoparticles are distributed very uniformly and have substantially no agglomeration; the specific surface area is large, the conductivity is good, and the heat conduction performance is excellent.
  • the density of the graphene aerogel of the present invention can be adjusted, and graphene aerogels of different densities can be obtained by changing the concentration of the reactants.
  • the graphene aerogel of the invention is porous and has a large pore structure and is relatively uniform, and can be used for adsorption of an organic solvent, and has great application value.
  • the preparation method of the invention can obtain a single metal nanoparticle-graphene composite aerogel of different precious metal species, and can also obtain graphene composited with two or more precious metals. - Precious metal nanoparticle composite aerogel material.
  • the graphene sheet of graphene aerogel provides a loading site for noble metal nanoparticles, which is a precious gold
  • the in-situ formation, uniform dispersibility and applicability of the nanoparticles provide a carrier;
  • the graphene-precious metal nanoparticle composite aerogel combines the functions of graphene aerogel and noble metal nanoparticles, and graphene loaded with noble metal nanoparticles
  • the composite gel has good electrical conductivity in the process of adsorbing organic solvent, which can provide feasibility for the corresponding electrocatalytic reaction, making it suitable for the synthesis of organic reactions such as small molecule electroanalysis and electrocatalysis, and petroleum organic intermediates.
  • the synthetic field and other aspects have great potential application value.
  • Example 1 is a photograph of a macroscopic graphene aerogel obtained in Example 1 of the present invention.
  • Example 2 is a scanning electron micrograph of a graphene aerogel obtained in Example 1 of the present invention.
  • Figure 3 is a photograph of a macroscopic graphene aerogel obtained in Example 2 of the present invention.
  • Figure 4 is a photograph of a macroscopic graphene hydrogel obtained in Example 23 of the present invention.
  • Figure 5 is a photograph of a macroscopic graphene aerogel obtained in Example 23 of the present invention.
  • Figure 6 is a scanning electron micrograph of a graphene aerogel obtained in Example 23 of the present invention.
  • Example 7 is a scanning electron microscope (low magnification) diagram of a porous structure in a graphene-silver inorganic nanoparticle composite aerogel prepared in Example 40.
  • Example 8 is a scanning electron microscopy (high magnification) diagram of silver nanoparticles on a graphene sheet in a graphene-silver inorganic nanoparticle composite aerogel prepared in Example 40.
  • the evaluation criteria of the adsorption capacity are: how many grams of the organic solvent is adsorbed per gram of the graphene aerogel of the present invention.
  • the graphite used was supplied by Sigma-Aldrich.
  • the graphite used was flake graphite with an average particle size of 500 ⁇ m, and the rest of the raw materials were supplied by Sinopharm Chemical Reagent Co., Ltd.
  • thermally expanded graphite oxide 5 g was mixed with 300 ml of sulfuric acid, 5 g of K 2 S 2 O 8 , 7 g of phosphorus pentoxide in a 500 ml wide-mouthed conical flask, heated at 80 ° C for 4 hours, diluted with 2 L of water, filtered and washed, and dried in air. The day is obtained by pre-oxidizing the thermally expanded graphite.
  • the dried pre-oxidized hot-expanded graphite is mixed with 200 ml of sulfuric acid at a low temperature of 0-5 ° C, 20 g of potassium permanganate is added, slowly added, stirred at 35 ° C for 1 h, diluted with 2 L of water for 1 h, and then added with 10 ml of 30% hydrogen peroxide. After standing for 2 days, the supernatant was decanted, washed by centrifugation, and gently stirred to obtain a dispersed dispersion of graphene oxide.
  • the graphene oxide dispersion prepared in the step (1) is mixed with ethylenediamine to prepare a mixed solution of 4 mg/ml graphene oxide, wherein the mass ratio of the graphene oxide to the amine water-soluble compound is 1:50.
  • the graphene oxide mixed solution obtained in the step (2) is injected into a cylindrical irradiation reactor, and oxygen is removed by nitrogen.
  • the sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 100 kGy to form an amino-modified graphene hydrogel in the reactor.
  • the amino-modified graphene hydrogel obtained in the step (4) is freeze-dried to obtain a dry graphene aerogel.
  • the macroscopic photo of the photo shows a continuous cylindrical block structure as shown in Fig. 1.
  • the microscopic porous morphology is shown in Fig. 2 as a cross-sectional photograph of a scanning electron microscope of graphene aerogel, which can be seen from the figure.
  • the pores are macroporous structures, and the pore size is distributed between 10-100 ⁇ m, which is relatively uniform.
  • the nitrogen element content, carbon-oxygen ratio and density are shown in Table 1.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 120 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made:
  • Step (1) pre-oxidized graphite is thermally expanded at 400 ° C for 30 s to obtain thermally expanded graphite oxide
  • Step (4) The sealed irradiation reactor is irradiated with a cobalt 60 ⁇ ray source at a dose of 50 kGy to form an amino-modified graphene hydrogel in a thin tubular reactor, and dried by supercritical carbon dioxide to obtain an elongated rod-shaped graphene gas. gel.
  • the nitrogen element content, carbon-oxygen ratio and density are shown in Table 1.
  • the resulting elongated rod-shaped graphene aerogel is shown in a "king" picture as shown in Figure 3.
  • the rod-shaped graphene aerogel has good oil absorption performance and an adsorption capacity of 110 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were met: Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ -ray source at a dose of 5 kGy to form an amino-modified graphite in a cylindrical reactor. Arene hydrogel. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1. A photograph of the obtained graphene aerogel is similar to that of Example 1. The cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 112 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were met: Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ -ray source at a dose of 100 kGy to form an amino-modified graphite in a cylindrical reactor. Arene hydrogel. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1. A photograph of the obtained graphene aerogel is similar to that of Example 1. The cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 115 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were met: Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 200 kGy to form an amino-modified graphite in a cylindrical reactor. Arene hydrogel. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1. A photograph of the obtained graphene aerogel is similar to that of Example 1. The cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 120 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) was mixed with ethylenediamine to prepare a mixed solution of 1 mg/ml graphene oxide, wherein graphene oxide was obtained. The mass ratio to the amine water-soluble compound was 1:400. Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 500 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1. A photograph of the obtained graphene aerogel is similar to that of Example 1. The cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 150 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) was mixed with ethylenediamine to prepare a mixed solution of 3 mg/ml graphene oxide, wherein graphene oxide was obtained. The mass ratio to the amine water-soluble compound was 1:50. Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 50 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1. A photograph of the obtained graphene aerogel is similar to that of Example 1. The cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 130 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) was mixed with ethylenediamine to prepare a mixed solution of 5 mg/ml graphene oxide, wherein graphene oxide was obtained. The mass ratio to the amine water-soluble compound was 1:1. Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 50 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1. A photograph of the obtained graphene aerogel is similar to that of Example 1. The cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 100 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) was mixed with ethylenediamine to prepare a mixed solution of 10 mg/ml graphene oxide. The mass ratio of the graphene oxide to the amine water-soluble compound is 1:0.5. Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 50 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1. A photograph of the obtained graphene aerogel is similar to that of Example 1. The cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 90 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion obtained in the step (1) and the amino water-soluble compound (propylenediamine and diethylenetriamine in a mass ratio of 1: A mixture of 1) was mixed to prepare a mixed solution of 3 mg/ml of graphene oxide, wherein the mass ratio of graphene oxide to the amine water-soluble compound was 1:100, and the dose was 60 kGy.
  • the nitrogen element content, carbon-oxygen ratio and density of the obtained graphene aerogel are shown in Table 1.
  • a photograph of the obtained graphene aerogel is similar to that of Example 1.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 135 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) and the amino water-soluble compound (diethylamine and tetraethylenepentamine in a mass ratio of 1: The mixture of 1 was mixed to prepare a 2 mg/ml graphene oxide mixed solution in which the mass ratio of graphene oxide to the amine water-soluble compound was 1:250, and the dose was 100 kGy.
  • the nitrogen element content, carbon-oxygen ratio and density of the obtained graphene aerogel are shown in Table 1.
  • a photograph of the obtained graphene aerogel is similar to that of Example 1.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 140 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) and the amino water-soluble compound (polyallylamine and ethylenediamine in a mass ratio of 1) A mixture of: 2) was prepared by mixing a 5 mg/ml graphene oxide mixed solution in which the mass ratio of graphene oxide to the amine water-soluble compound was 1:300, and the dose was 400 kGy.
  • Graphene obtained The nitrogen element content, carbon-oxygen ratio and density of the aerogel are shown in Table 1.
  • a photograph of the obtained graphene aerogel is similar to that of Example 1.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 98 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) and the amino water-soluble compound (butanediamine and N,N'-bis(2-ammonium) were the same.
  • a mixed solution of 3 mg/ml graphene oxide was prepared by mixing ethyl)-1,3-propanediamine in a mixture of 0.5:1 by mass ratio, wherein the mass ratio of graphene oxide to amine water-soluble compound was 1:50.
  • the dose is 100kGy.
  • the nitrogen element content, carbon-oxygen ratio and density of the obtained graphene aerogel are shown in Table 1.
  • a photograph of the obtained graphene aerogel is similar to that of Example 1.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 120 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) and the amino water-soluble compound (polyallylamine and triethylenetetramine in terms of mass ratio) were A 1:2 mixture was mixed to prepare a 4 mg/ml graphene oxide mixed solution in which the mass ratio of graphene oxide to the amine water-soluble compound was 1:50.
  • Step (4) The sealed irradiation reactor was irradiated with an electron beam source at a dose of 500 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor. The nitrogen element content, carbon-oxygen ratio and density are shown in Table 1.
  • a photograph of the obtained graphene aerogel is similar to that of Example 1.
  • the graphene aerogel has good oil absorption performance and the adsorption capacity can reach 100 g/g (for example, n-decane).
  • Example 1 was repeated except that the following differences were made: the graphite oxide prepared by mixing a pure graphene oxide dispersion with an amine water-soluble compound hydrazine hydrate (NH 2 -NH 2 (H 2 O)) The mixture of olefins wherein the mass ratio of graphene oxide to the amine water-soluble compound is 1:100.
  • the graphene particles precipitated in the tube were obtained, and the continuous wet graphene hydrogel was not obtained, and the continuous dry graphene aerogel was not obtained, and the oil absorption performance was not obtained.
  • the nitrogen element content and carbon oxygen of the product are shown in Table 1.
  • Example 1 was repeated except that the following differences were made: the pure 6 mg/ml graphene oxide dispersion was placed in an irradiation tube for irradiation. As a result, continuous graphene hydrogel is not obtained, and continuous dry graphene aerogel is not obtained, and good oil absorption performance is not obtained.
  • the nitrogen element content and carbon oxygen of the product are shown in Table 1.
  • Example 1 was repeated except that the following differences were made: the graphene oxide mixture prepared by mixing a pure 2 mg/ml graphene oxide dispersion with an amine water-soluble compound propylene diamine, wherein graphene oxide The mass ratio to the amine water-soluble compound was 1:100. It was placed in the irradiation tube and allowed to stand for 12 hours without irradiation. As a result, continuous graphene hydrogels are not obtained, and good oil absorption properties are not obtained, and continuous dry graphene aerogels are not obtained. The nitrogen element content and carbon oxygen of the product are shown in Table 1.
  • the nitrogen element content, carbon-oxygen ratio, aerogel density, and oil absorption performance data of the graphene aerogel obtained in Examples 1-13 and the products obtained in Comparative Examples 1-3 were measured.
  • the nitrogen element content, the carbon element content and the oxygen element content are obtained by X-ray photoelectron spectroscopy XPS, and the carbon-to-oxygen ratio is obtained according to the ratio of the carbon element content to the oxygen element content;
  • the aerogel density is tested according to conventional means in the art, by mass Obtained from the volume ratio;
  • the oil absorption performance is tested according to the conventional means in the art, and the value is obtained from the oil absorption mass and the aerogel mass ratio, and the test results are shown in Table 1.
  • Table 1 The nitrogen content, carbon-oxygen ratio, aerogel density and oil absorption performance data of the graphene aerogel obtained in Examples 1-13 and the products obtained in Comparative Examples 1-3
  • the graphite used was supplied by Sigma-Aldrich, and the graphite used was flake graphite with an average particle size of 50-500 ⁇ m.
  • the rest of the raw materials were supplied by Sinopharm Chemical Reagent Co., Ltd.
  • thermally expanded graphite oxide 5 g was mixed with 300 ml of sulfuric acid, 5 g of potassium persulfate (K 2 S 2 O 8 ), 7 g of phosphorus pentoxide in a 500 ml wide-mouthed conical flask, heated at 80 ° C for 4 hours, diluted with 2 L of water, filtered and washed. It was dried in air for 3 days to obtain pre-oxidized thermally expanded graphite.
  • the dried pre-oxidized hot-expanded graphite is mixed with 200 ml of sulfuric acid at a low temperature of 0-5 ° C, 20 g of potassium permanganate is added, slowly added, stirred at 35 ° C for 1 h, diluted with 2 L of water for 1 h, and then added with 10 ml of 30% hydrogen peroxide. After standing for 2 days, the supernatant was decanted, washed by centrifugation, and gently stirred to obtain a dispersed dispersion of graphene oxide;
  • step 2 mixing the graphene oxide dispersion prepared in step 1 with propylene glycol to prepare a mixed solution of 1 mg / ml of graphene oxide, wherein the mass of propylene glycol is 5% by mass of the graphene oxide mixed solution;
  • the irradiation dose is 300 kGy
  • Irradiation dose rate is 3kGy / hour, forming a graphene hydrogel in the reactor;
  • the graphene oxide dispersion prepared in the step (1) is mixed with ethanol to prepare a mixed solution of 4 mg/ml graphene oxide, wherein the ethanol The mass of the graphene oxide mixed solution is 20% by mass; in step (2), the unsealed (air atmosphere) irradiation reactor is irradiated with a cobalt 60 ⁇ ray source, the irradiation dose is 110 kGy, and the irradiation dose rate is 0.5. kGy / hour, a graphene hydrogel was formed in a thin tubular reactor, and dried by supercritical carbon dioxide to obtain an elongated rod-shaped graphene aerogel.
  • the graphene oxide dispersion prepared in the step (1) is mixed with methanol, isopropanol, butanol, polyvinyl alcohol (wherein The mass of methanol, isopropanol and butanol is 10% by mass of the graphene oxide mixed solution, and the mass of polyvinyl alcohol is 1% by mass of the graphene oxide mixture.
  • the 8 mg/ml graphene oxide mixture is prepared.
  • step (2) irradiating the argon gas deoxidized sealed irradiation reactor with a cobalt 60 ⁇ ray source, the irradiation dose is 600 kGy, the irradiation dose rate is 12 kGy / hour, and graphene is formed in the cylindrical reactor. Hydrogels. Freeze drying was carried out to obtain a dry graphene aerogel.
  • the graphene oxide dispersion prepared in the step (1) is mixed with propanol and butanediol (wherein propanol and butyl)
  • the mass of the diol is 20% by mass of the graphene oxide mixed solution) to prepare a mixed solution of 15 mg/ml graphene oxide
  • the step (2) is to irradiate the nitrogen-deoxygenated irradiated reactor with a cobalt 60 ⁇ -ray source
  • the irradiation dose was 400 kGy and the irradiation dose rate was 6 kGy/hour to form a graphene hydrogel in a cylindrical reactor. Freeze drying was carried out to obtain a dry graphene aerogel.
  • the graphene oxide dispersion prepared in the step (1) is mixed with glycerin and ethanol (wherein the mass of the glycerol accounts for the graphite oxide)
  • the mass percentage of the mixed solution of the olefin is 5%
  • the mass of the ethanol is 40% by mass of the mixed graphene oxide solution
  • the mixed solution of the graphene oxide of 30 mg/ml is prepared, and the step (2) is performed by removing the oxygen by oxygen removal.
  • the reactor was irradiated with a cobalt 60 gamma ray source at a dose of 500 kGy and an irradiation dose rate of 8 kGy/hour to form a graphene hydrogel in a cylindrical reactor. Freeze drying was carried out to obtain a dry graphene aerogel.
  • the graphene oxide dispersion prepared in the step (1) is mixed with methanol and isobutanol (wherein the mass of methanol accounts for graphene oxide)
  • the mass percentage of the mixed solution is 50%
  • the mass of isobutanol is 45% of the graphene oxide mixed solution
  • a mixed solution of 30 mg/ml of graphene oxide is prepared; and step (2) is performed by removing oxygen by oxygen.
  • the reactor was irradiated with a cobalt 60 gamma ray source at an irradiation dose of 500 kGy and an irradiation dose rate of 10 kGy/hour to form a graphene hydrogel in a cylindrical reactor. Freeze drying was carried out to obtain a dry graphene aerogel.
  • the graphene oxide dispersion prepared in the step (1) is mixed with ethanol to prepare a mixed solution of 10 mg/ml graphene oxide, wherein The mass of the alcohol accounts for 95% by mass of the graphene oxide mixed solution; the step (2) irradiates the nitrogen-deoxygenated irradiated reactor with a cobalt 60 ⁇ -ray source, and the irradiation dose is 300 kGy, and the irradiation dose rate is 6kGy / hour, forming a graphene hydrogel in a thin tubular reactor, The elongated rod-shaped graphene aerogel is obtained by supercritical carbon dioxide drying.
  • the graphene oxide dispersion prepared in the step (1) is mixed with propanol to prepare a mixed solution of 15 mg/ml graphene oxide, wherein The mass of the propanol is 2% by mass of the graphene oxide mixed solution; the step (2) irradiates the graphene oxide mixture in an unsealed flat irradiation reactor with an electron beam source, and the irradiation dose is At 600 kGy, the irradiation dose rate was 8 kGy/hour, and a flat graphene hydrogel was formed in a flat reactor, and freeze-dried to obtain a flat graphene aerogel.
  • Example 15 According to the preparation method of Example 15, except for the following differences, the other conditions are the same: a pure aqueous mixture of graphene oxide and propanol are mixed to prepare a mixture of 4 mg/ml graphene oxide, wherein the mass of propanol The mass percentage of the graphene oxide mixed solution is 1%; the step (2) irradiates the nitrogen-deoxygenated irradiated reactor with a cobalt 60 ⁇ -ray source, the irradiation dose is 300 kGy, and the irradiation dose rate is 1.5 kGy/ hour. As a result, graphene particles precipitated in the tube were obtained, and a continuous wet graphene hydrogel was not obtained, and a continuous dry graphene aerogel was also not obtained.
  • Example 15 According to the preparation method of Example 15, except for the following differences, the other conditions are the same: a pure 6 mg/ml graphene oxide aqueous dispersion is charged into a nitrogen-deaerating irradiation tube, and a cobalt 60 ⁇ -ray source is used.
  • the irradiation dose was 300 kGy and the irradiation dose rate was 10 kGy/hour.
  • a continuous graphene hydrogel is not obtained, and a continuous dry graphene aerogel is not obtained.
  • Example 15 According to the preparation method of Example 15, except for the following differences, the other conditions are the same: a mixture of pure graphene oxide and propanol is prepared to prepare a mixture of 4 mg/ml graphene oxide, wherein the mass of propanol accounts for graphite oxide.
  • the mass percentage of the mixed solution of the olefin was 99%; it was irradiated into the irradiation tube with a cobalt 60 ⁇ ray source, the irradiation dose was 300 kGy, and the irradiation dose rate was 6 kGy/hour.
  • a continuous graphene hydrogel is not obtained, and a continuous dry graphene aerogel is not obtained.
  • Example 15 According to the preparation method of Example 15, except for the following differences, the other conditions are the same: a mixture of pure graphene oxide and propanol is prepared to prepare a mixture of 4 mg/ml graphene oxide, wherein the mass of propanol accounts for graphite oxide.
  • the mass percentage of the mixed solution of the olefin was 30%; it was left in the irradiation tube for 12 hours without irradiation. As a result, a continuous graphene hydrogel is not obtained, and a continuous dry graphene aerogel is not obtained.
  • FIG. 4 is a photograph of the macroscopic graphene hydrogel obtained in the step (2) of Example 15, the macroscopic morphology of which is shown as a continuous cylindrical block structure.
  • Figure 5 is a photograph of the macroscopic graphene aerogel obtained in the step (3) of Example 15, the macroscopic morphology of which is also shown as a continuous cylindrical block structure, and the graphene aerogel is ultra-light, and its weight is conventional. Feathers can withstand.
  • the macroscopic topography of the graphene aerogels of Examples 17-20 and 22 was similar to that of Example 15.
  • Example 6 is a scanning electron microscope cross-sectional photograph of the graphene aerogel of Example 15, the microscopic morphology of which is shown as a porous structure, the pores of which are macroporous structures, and the pore size distribution is between 10 and 100 ⁇ m, which is relatively uniform.
  • the microstructure of the graphene aerogel of Examples 16-22 was similar to that of Example 15.
  • the carbon-oxygen ratio, aerogel density, and oil absorption performance data of the graphene aerogels obtained in Examples 15-22 and the products obtained in Comparative Examples 4-7 were measured.
  • element type, carbon content and oxygen content are obtained by X-ray photoelectron spectroscopy XPS, carbon-oxygen ratio is obtained according to the ratio of carbon content and oxygen content, impurity element is other elements except carbon and oxygen; aerogel
  • the density is tested according to conventional means in the art, and is obtained from the mass to volume ratio;
  • the oil absorption performance is tested according to conventional means in the art, and the values are obtained from the oil absorption mass and the aerogel mass ratio, and the test results are shown in Table 2.
  • the graphene aerogel of the present invention has a low density of at least 2.9 mg/cm 3 and has good oil absorption performance, and the adsorption capacity is between 20 and 250 g/g (the adsorption capacity is n-decane). example).
  • the products of Comparative Examples 4-7 did not have good oil absorption properties.
  • the graphite used was supplied by Sigma-Aldrich Co., Ltd., and the graphite used was flake graphite with an average particle diameter of 500 ⁇ m.
  • the remaining materials were supplied by Sinopharm Chemical Reagent Co., Ltd.
  • thermally expanded graphite oxide 5 g was mixed with 300 ml of sulfuric acid, 5 g of K 2 S 2 O 8 , 7 g of phosphorus pentoxide in a 500 ml wide-mouthed conical flask, heated at 80 ° C for 4 hours, diluted with 2 L of water, filtered and washed, and dried in air. The day is obtained by pre-oxidizing the thermally expanded graphite.
  • the dried pre-oxidized hot-expanded graphite is mixed with 200 ml of sulfuric acid at a low temperature of 0-5 ° C, 20 g of potassium permanganate is added, slowly added, stirred at 35 ° C for 1 h, diluted with 2 L of water for 1 h, and then added with 10 ml of 30% hydrogen peroxide. After standing for 2 days, the supernatant was decanted, washed by centrifugation, and gently stirred to obtain a dispersed dispersion of graphene oxide.
  • the graphene oxide mixed solution obtained in the step (2) is injected into a cylindrical irradiation reactor, and oxygen is removed by nitrogen.
  • the sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 100 kGy to form an amino-modified graphene hydrogel in the reactor.
  • the amino-modified graphene hydrogel obtained in the step (4) is freeze-dried to obtain a dry graphene aerogel.
  • the pores have a large pore structure, and the pore size is distributed between 10-100 ⁇ m, which is relatively uniform.
  • the nitrogen element content, carbon-oxygen ratio and density are shown in Table 3.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 141 g/g (for example, crude oil, the relative density is 0.86).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) was mixed with propylenediamine, isopropanol and butanediol to prepare 3 mg/ml of graphite oxide. a mixed solution of olefins, wherein the mass ratio of graphene oxide to propylenediamine is 1:100, (wherein the mass of isopropanol is 5% by mass of the mixed graphene oxide solution, and the mass of butanediol is mixed with graphene oxide) The percentage of the solution is 5%).
  • Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 50 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor.
  • the nitrogen element content, carbon-oxygen ratio and density are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 163 g/g (for example, edible oil soybean oil, the relative density is 0.92).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) was mixed with diethylenetriamine, methanol and ethylene glycol to prepare 5 mg/ml of graphene oxide. a mixed solution in which the mass ratio of graphene oxide to the amine water-soluble compound is 1:50 (wherein the mass of methanol accounts for 20% by mass of the graphene oxide mixed solution, and the mass of ethylene glycol accounts for the mixed graphene oxide solution) The percentage is 10%).
  • Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 50 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor.
  • the nitrogen element content, carbon-oxygen ratio and density are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 138 g/g (for example, diesel oil, the relative density is 0.84).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) was mixed with triethylenetetramine and glycerin, polyvinyl alcohol to prepare an oxidation of 10 mg/ml. a graphene mixed solution in which the mass ratio of graphene oxide to an amine water-soluble compound is 1:10 (wherein the mass of glycerol accounts for 2% by mass of the graphene oxide mixed solution, and the mass of polyvinyl alcohol accounts for graphite oxide) The percentage of the mixed solution of the ene is 2%).
  • Step (4) The sealed irradiation reactor was irradiated with a cobalt 60 ⁇ ray source at a dose of 50 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor.
  • the nitrogen element content, carbon-oxygen ratio and density are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 110 g/g (in the case of automobile engine oil, the relative density is 0.88).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion obtained in the step (1) and the amino water-soluble compound (propylenediamine and diethylenetriamine in a mass ratio of 1: Mixture of 1) and octanediol and ethanol to prepare a mixed solution of 3 mg/ml graphene oxide, wherein the mass ratio of graphene oxide to amine water-soluble compound is 1:100, (wherein the mass of octanediol accounts for graphite oxide The mass percentage of the mixed solution of the olefin is 2%, and the mass of the ethanol accounts for the graphene oxide. The percentage of the mixed solution was 50%) and the dose was 60 kGy.
  • the nitrogen element content, carbon-oxygen ratio and density of the obtained graphene aerogel are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 177 g/g (in the case of crude oil, the relative density is 0.96).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion obtained in the step (1) and the amino water-soluble compound (diethylamine and tetraethylenepentamine in a mass ratio of 1: a mixture of 1) and propanol, propylene glycol to prepare a 2mg / ml graphene oxide mixed solution, wherein the mass ratio of graphene oxide to the amine water-soluble compound is 1:50, (wherein the mass of propanol accounts for the mixture of graphene oxide The mass percentage of the solution was 85%, the mass of propylene glycol was 10% of the graphene oxide mixed solution, and the dose was 100 kGy.
  • the nitrogen element content, carbon-oxygen ratio and density of the obtained graphene aerogel are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 160 g/g (for example, a liquid alkane n-decane and a liquid ester methyl methacrylate mixture, the relative density is 0.83).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) and the amino water-soluble compound (polyallylamine and ethylenediamine in a mass ratio of 1) a mixture of: 2) and isobutanol were prepared to prepare a mixed solution of 5 mg/ml graphene oxide, wherein the mass ratio of graphene oxide to the amine water-soluble compound was 1:2, wherein the mass of isobutanol was mixed with graphene oxide. The mass percentage of the solution was 35% and the dose was 400 kGy.
  • the nitrogen element content, carbon-oxygen ratio and density of the obtained graphene aerogel are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 123 g/g (for example, a liquid alcohol n-butanol and a liquid carboxylic acid acrylic acid mixture, the relative density is 0.92).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) and the amino water-soluble compound (butanediamine and N,N'-bis(2-ammonium) were the same.
  • a mixture solution of graphene oxide and amine water-soluble compound prepared by mixing ethyl)-1,3-propanediamine in a mass ratio of 0.5:1 and butanediol to prepare a mixed solution of 3 mg/ml graphene oxide.
  • the 1:5 mass ratio of butanediol to the graphene oxide mixed solution was 30%, and the dose was 100 kGy.
  • the nitrogen element content, carbon-oxygen ratio and density of the obtained graphene aerogel are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the cylindrical graphene aerogel has good oil absorption performance and an adsorption capacity of 135 g/g (for example, a kerosene and diesel mixture, the relative density is 0.82).
  • Example 23 was repeated except that the following differences were made: the graphene oxide dispersion prepared in the step (1) and the amino water-soluble compound (polyallylamine and triethylenetetramine in terms of mass ratio) were a mixture of 1:2) and methanol to prepare a mixed solution of 4 mg/ml graphene oxide, wherein the mass ratio of graphene oxide to the amine water-soluble compound is 1:0.5, and the mass of methanol accounts for the mass percentage of the graphene oxide mixed solution. It is 30%.
  • Step (4) The sealed irradiation reactor was irradiated with an electron beam source at a dose of 500 kGy to form an amino-modified graphene hydrogel in a cylindrical reactor.
  • the nitrogen element content, carbon-oxygen ratio and density are shown in Table 3.
  • a photograph of the obtained graphene aerogel was similar to that of Example 23.
  • the graphene aerogel has good oil absorption performance, and the adsorption capacity can reach 120 g/g (for example, liquid aromatic hydrocarbon toluene, the relative density is 0.87).
  • Table 3 The nitrogen element content, carbon-oxygen ratio, aerogel density and oil absorption performance data of the graphene aerogel obtained in Examples 23-31 (for example, examples of organic solvents of different densities, see examples)
  • the graphite used was supplied by Sigma-Aldrich, and the graphite used was flake graphite with an average particle size of 50-500 ⁇ m.
  • the rest of the raw materials were supplied by Sinopharm Chemical Reagent Co., Ltd.
  • thermally expanded graphite oxide 5 g was mixed with 300 ml of sulfuric acid, 5 g of K 2 S 2 O 8 , 7 g of phosphorus pentoxide in a 500 ml wide-mouthed conical flask, heated at 80 ° C for 4 hours, diluted with 2 L of water, filtered and washed, and dried in air. The day is obtained by pre-oxidizing the thermally expanded graphite.
  • the dried pre-oxidized hot-expanded graphite is mixed with 200 ml of sulfuric acid at a low temperature of 0-5 ° C, 20 g of potassium permanganate is added, slowly added, stirred at 35 ° C for 1 h, diluted with 2 L of water for 1 h, and then added with 10 ml of 30% hydrogen peroxide. After standing for 2 days, the supernatant was decanted, washed by centrifugation, and gently stirred to obtain a dispersed dispersion of graphene oxide.
  • the micro-morphology of graphene-gold nanoparticle composite aerogels was tested and found to be porous.
  • the pore size distribution was between 10-100 ⁇ m and relatively uniform.
  • the graphene-gold nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • the graphene-platinum nanoparticle composite hydrogel obtained in the step (3) is subjected to supercritical carbon dioxide drying to obtain an elongated rod-like graphene-platinum nanoparticle composite aerogel.
  • the graphene-platinum nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • the graphene-ferric oxide nanoparticle composite hydrogel obtained in the step (3) is freeze-dried to obtain a dry cylindrical graphene-iron oxide nanoparticle aerogel.
  • the obtained graphene-ferric oxide nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • the graphene-tin dioxide nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • the total mass ratio of graphene oxide to inorganic nanoparticles is 1:10; glycerol accounts for 2% by mass of graphene oxide mixed solution, and ethanol accounts for 40% by mass of graphene oxide mixed solution, graphite oxide
  • the mass ratio of graphene oxide to propylenediamine is 1:100, and the mass ratio of graphene oxide to N,N'-bis(2-aminoethyl)-1,3-propanediamine is 1 :0.5.
  • the graphene-inorganic nanoparticle composite hydrogel obtained in the step (3) is freeze-dried to obtain a dry cylindrical graphene-inorganic nanoparticle aerogel.
  • the graphene-inorganic nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • isobutanol, diethylenetriamine, triethylenetetramine and tetraethylenepentamine are mixed to prepare a mixed solution of 10 mg/ml graphene oxide; wherein the total mass ratio of graphene oxide to nanoparticles is 1:20; graphite oxide In the mixture of olefins, the mass ratio of graphene oxide to diethylenetriamine is 1:0.3, the mass ratio of graphene oxide to triethylenetetramine is 1:0.1, and the mass ratio of graphene oxide to tetraethylenepentamine is 1. : 0.1; methanol accounts for 50% by mass of the graphene oxide mixed solution, and isobutanol accounts for 45% by mass of the graphene oxide mixed solution.
  • the graphene-inorganic nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • the graphene-titanium dioxide nanoparticle composite hydrogel obtained in the step (3) is subjected to supercritical carbon dioxide drying to obtain a dry cylindrical graphene-titanium dioxide nanoparticle aerogel.
  • the graphene-titanium dioxide nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • the graphene-titanium dioxide nanoparticle composite aerogel has good oil absorption performance, and its carbon-oxygen ratio, density and adsorption capacity are shown in Table 4.
  • the carbon-oxygen ratio, aerogel density, and oil absorption performance data of the graphene-inorganic nanoparticle composite aerogels obtained in Examples 32 to 39 and the products obtained in Comparative Examples 8-11 were measured.
  • the carbon content and the oxygen content are obtained by X-ray photoelectron spectroscopy XPS, and the carbon-to-oxygen ratio is obtained according to the ratio of the carbon element content to the oxygen element content;
  • the aerogel density is tested according to conventional means in the art, and the mass to volume ratio is obtained.
  • the oil absorption performance is tested according to conventional means in the art, and the value is obtained by the ratio of the oil absorption mass to the aerogel mass, and the adsorption capacity is exemplified by n-decane.
  • the test results are shown in Table 4.
  • the graphite used was supplied by Sigma-Aldrich, and the graphite used was flake graphite with an average particle size of 50-500 ⁇ m.
  • the rest of the raw materials were supplied by Sinopharm Chemical Reagent Co., Ltd.
  • Graphite 10g 98% concentrated sulfuric acid 150ml, 65% concentrated nitric acid 50ml, added to a 500ml Erlenmeyer flask and stirred at room temperature for 24h, slowly poured into 1L water to collect the solid, washed 3 times, dried at 80 ° C for 4 hours. The pre-oxidation process was repeated twice. The dried pre-oxidized graphite was placed in a box furnace and thermally expanded at 900 ° C for 10 s to obtain thermally expanded graphite oxide.
  • thermally expanded graphite oxide 5 g was mixed with 300 ml of 98% concentrated sulfuric acid, 4.2 g of K 2 S 2 O 8 , 6.2 g of phosphorus pentoxide in a 500 ml wide-mouthed conical flask, heated at 80 ° C for 4 hours, diluted with 2 L of water, filtered. Washing and drying in air for 3 days gave pre-oxidized thermally expanded graphite.
  • Fig. 7 is a scanning electron microscopy (low magnification) diagram of a porous structure in a graphene-silver inorganic nanoparticle composite aerogel prepared. It is found to be a porous, macroporous structure with a uniform structure and a pore size distribution of 10-100 ⁇ m.
  • Fig. 8 is a scanning electron microscopy (high magnification) diagram of silver nanoparticles in a graphene-silver inorganic nanoparticle composite aerogel prepared on a graphene sheet, and it is found that silver nanoparticles have a uniform size distribution and a diameter of 40-80 nm.
  • the graphene-silver inorganic nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Shown.
  • the graphene-precious metal nanoparticle composite hydrogel obtained in the step (3) is subjected to supercritical carbon dioxide drying to obtain an elongated rod-like graphene-platinum nanoparticle composite aerogel.
  • the graphene-precious metal nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the obtained graphene-gold nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the graphene-palladium nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the total mass ratio of graphene oxide to the noble metal compound is 1:5; the mass percentage of glycerol to the graphene oxide mixed solution is 1%, and the percentage of ethanol in the graphene oxide mixed solution is 40%, graphene oxide In the mixed solution, the mass ratio of graphene oxide to propylenediamine is 1:2.5, and the mass ratio of graphene oxide to N,N'-bis(2-aminoethyl)-1,3-propanediamine is 1: 2.5.
  • the graphene-precious metal inorganic nanoparticle composite hydrogel obtained in the step (3) is freeze-dried to obtain a dry cylindrical graphene-precious metal inorganic nanoparticle aerogel.
  • the graphene-precious metal inorganic nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the graphene-precious metal inorganic nanoparticle composite hydrogel obtained in the step (3) is freeze-dried to obtain a dry cylindrical graphene-precious metal inorganic nanoparticle aerogel.
  • the graphene-precious metal inorganic nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the graphene-bismuth nanoparticle composite hydrogel obtained in the step (3) is subjected to supercritical carbon dioxide drying to obtain a dry cylindrical graphene-tellurium nanoparticle aerogel.
  • the graphene-bismuth nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the graphene-bismuth nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the graphene-bismuth nanoparticle composite hydrogel obtained in the step (3) is subjected to supercritical carbon dioxide drying to obtain a dry cylindrical graphene-tellurium nanoparticle aerogel.
  • the graphene-bismuth nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its interior The microstructure is similar to that of Figures 7 and 8.
  • the graphene-bismuth nanoparticle composite hydrogel obtained in the step (3) is subjected to supercritical carbon dioxide drying to obtain a dry cylindrical graphene-tellurium nanoparticle aerogel.
  • the graphene-bismuth nanoparticle composite aerogel has good oil absorption performance, and has great potential application value in the field of organic reaction catalytic synthesis such as small molecule electroanalysis and electrocatalysis, and in the synthesis field of petroleum organic intermediates. Its carbon-oxygen ratio, density and adsorption capacity are shown in Table 5. Its internal microstructure is similar to that of Figures 7 and 8.
  • the content of the water-soluble reducing agent is relatively small, the graphene-gold nanocomposite particles suspended in the tube are obtained, and a continuous wet graphene-gold nanoparticle composite hydrogel having a certain self-supporting mechanical strength cannot be obtained, and the same Continuous dry graphene-gold nanoparticle composite aerogels were also not obtained.
  • the product did not have good oil absorption properties, and the carbon oxygen was as shown in Table 5.
  • the graphene oxide dispersion prepared in the step (1) is mixed with potassium chlorate to prepare a 2 mg/ml graphene oxide mixture; wherein the mass ratio of graphene oxide to potassium chlorate is 1:0.5.
  • a mixed metal chloride solution is prepared by mixing an aqueous solution of chloroauric acid with propanol; wherein, the propanol accounts for 30% by mass of the mixed solution, and the mass concentration of the chloroauric acid in the noble metal ion mixture is 4 mg/ml.
  • the noble metal ion mixture is charged into the irradiation tube, and the oxygen is removed by nitrogen; the sealed irradiation reactor is irradiated with a cobalt 60 ⁇ ray source; wherein the dose is 600 kGy, and the dose rate of the irradiation reaction is 10 kGy/ hour.
  • the carbon content and the oxygen content are obtained by X-ray photoelectron spectroscopy XPS, and the carbon-to-oxygen ratio is obtained according to the ratio of the carbon element content to the oxygen element content;
  • the aerogel density is tested according to conventional means in the art, and the mass to volume ratio is obtained.
  • the oil absorption performance is tested according to conventional means in the art, and the value is obtained by the ratio of the oil absorption mass to the aerogel mass, and the adsorption capacity is exemplified by n-decane. The test results are shown in Table 5.
  • Example 40 sample Carbon to oxygen ratio Density / mg / cm 3 Oil absorption performance / g / g Example 40 8.00 3.0 250 Example 41 7.72 6.2 140 Example 42 8.93 9.0 70 Example 43 8.11 23.2 35 Example 44 8.23 128 6 Example 45 8.31 5.7 120 Example 46 8.28 15.6 44 Example 47 9.17 twenty one 36 Example 48 9.31 43 18 Example 49 7.28 33 twenty three Comparative example 12 4.10 - - Comparative example 13 3.20 - - Comparative example 14 3.92 - - Comparative example 15 2.30 - - Comparative example 16 - - - -
  • Example 1 was repeated, and the prepared dry graphene aerogel was used to adsorb n-pentane having a relative density of 0.63, and the adsorption capacity was up to 90 g/g.
  • Example 15 was repeated, and the prepared dry graphene aerogel was used to adsorb diesel oil having a relative density of 0.84, and the adsorption capacity was up to 270 g/g.
  • Example 32 was repeated, and the prepared dry cylindrical graphene-gold nanoparticle aerogel was used for adsorbing carbon tetrachloride having an organic solvent having a relative density of 1.59, and the adsorption capacity was up to 500 g/g.
  • Example 40 was repeated, and the prepared dry cylindrical graphene-silver nanoparticle aerogel was used to adsorb a mixture of ethanol and acrylic acid having a relative density of 0.92, and the adsorption capacity was up to 300 g/g.

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Abstract

本发明公开了一种石墨烯水凝胶、气凝胶、其制备方法及应用。本发明的石墨烯水凝胶的制备方法包括：(1)将氧化石墨烯分散液与水溶性还原剂均匀混合得到氧化石墨烯混合液；(2)将所述氧化石墨烯混合液用高能射线照射进行辐照反应，得到石墨烯水凝胶。本发明的石墨烯气凝胶制备方法包括：将所述石墨烯水凝胶进行冷冻干燥或超临界二氧化碳干燥。本发明还提供了所述石墨烯气凝胶在吸附有机溶剂中的应用。本发明采用辐照法制备石墨烯气凝胶，操作简单，绿色环保，反应条件宽松；且制得的石墨烯气凝胶为多孔且大孔结构，结构较均匀，具有重大的应用价值。

Description

石墨烯水凝胶、气凝胶、其制备方法及应用
本申请要求申请日为2014年9月11日的中国专利申请CN201410461586.1、申请日为2015年3月19日的中国专利申请CN201510121541.4、申请日为2015年3月19日的中国专利申请CN201510122453.6、申请日为2015年6月4日的中国专利申请CN201510305992.3的优先权。本申请引用上述中国专利申请的全文。
技术领域
本发明涉及一种石墨烯水凝胶、气凝胶、其制备方法及应用。
背景技术
石墨烯(Graphene)是具有真正的单原子层厚度和严格的二维结构，具有很高的机械强度，弹性，导热性，导电性，以及量子霍尔效应等，近年来引起了学术界和工业界的广泛关注。自从2010年英国科学家安德列杰姆和克斯特亚诺沃塞诺发现石墨烯而获得诺贝尔奖以来，石墨烯研究达到前所未有的研究高潮，越来越多的研究发现，其在能量储存，电学器件，催化及环境科学的特殊领域具有巨大的应用前景。
从实际应用角度考虑，将纳米石墨烯材料转变为宏观结构材料中无疑是非常有价值的研究方向。已经有大量的研究针对宏观石墨烯结构材料的研究和制备，尤其是宏观三维石墨烯基块体凝胶材料的制备研究。目前高碳和全碳的气凝胶主要有以下几种：纯碳纳米管气凝胶(Cao AY,et al.Science,2005,310,1307-1310)、填充高分子的碳纳米管气凝胶(Mateusz,B.B.,et al.Adv.Mater.,2007,19,661-664)、填充高分子的石墨烯气凝胶(Chen,ZP,et al.Nature materials,2011,310,1307-1310)，填充碳纳米管的石墨烯复合气凝胶(Sun HY,et al.Adv.Mater.,2013,25,2554-2560)。纯碳纳米管气凝胶成本 高，难以规模化生产；以纯石墨烯或氧化石墨烯为原料，通常需填充高分子或通过高温化学还原来实现宏观气凝胶的制备，其制备过程比较复杂，反应条件为高温高压，对反应容器要求苛刻。
高能射线辐照，是一种高效率、低成本、低能耗、无污染的方法，所述高能射线包括伽马射线或电子束等，目前广泛应用于高分子合成与改性，环境污染物辐射降解，医药卫生、食品加工等领域，在石墨烯气凝胶制备方面尚未报道。因此，将高能射线辐照应用于制备石墨烯气凝胶的方法有待开发，其对石墨烯的应用研究及市场化生产具有十分重要的意义。
发明内容
本发明所要解决的技术问题在于为了克服现有技术中石墨烯气凝胶的制备方法温度高、工艺复杂的缺陷，提供了一种石墨烯水凝胶、气凝胶、其制备方法及应用。本发明采用辐照法制备石墨烯水凝胶和气凝胶，目前尚无报道，该制备方法操作简单，绿色环保，反应条件宽松；且利用本发明的制备方法制得的石墨烯气凝胶为多孔且大孔结构，结构较均匀，可用于有机溶剂的吸附，具有重大的应用价值。
本发明提供了一种石墨烯水凝胶的制备方法，其包括下述步骤：
(1)将氧化石墨烯分散液与水溶性还原剂均匀混合得到氧化石墨烯混合液；
(2)将所述氧化石墨烯混合液用高能射线照射进行辐照反应，得到石墨烯水凝胶。
步骤(1)中，所述的氧化石墨烯分散液可为本领域常规方法制得的氧化石墨烯分散液，较佳地通过下述步骤制得：①预氧化：将石墨、浓硫酸和硝酸倒入水中，过滤，烘干；重复上述预氧化过程2-3次，得到预氧化石墨；②热膨胀：将步骤①的预氧化石墨在400-900℃条件下热膨胀10-30s，得到热膨胀氧化石墨；③将步骤②的热膨胀氧化石墨与浓硫酸、过硫酸钾(K2S2O8) 和五氧化二磷的混合物在80-90℃条件下加热，加入水过滤洗涤，干燥，得到预氧化热膨胀石墨；④将步骤③的预氧化热膨胀石墨与浓硫酸在0-5℃条件下混合，加入高锰酸钾，反应，再加入双氧水，静置，离心洗涤，加入水搅拌即得氧化石墨烯分散液。
步骤(1)中，所述的氧化石墨烯分散液中氧化石墨烯的含量为本领域常规含量，较佳地为1-30mg/mL。
步骤(1)中，所述的水溶性还原剂可为水溶性醇和/或胺类水溶性还原剂。
步骤(1)中，当水溶性还原剂为水溶性醇时，所述水溶性还原剂较佳地占所述氧化石墨烯混合液的质量百分比为2-95％，更佳地5-90％，最佳地10-80％。
步骤(1)中，当水溶性还原剂为胺类水溶性还原剂时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的水溶性还原剂的质量比优选为(1:0.5)-(1:400)，较佳地(1：0.5)-(1：200)，更佳地(1：1)-(1：150)，最佳地(1：5)-(1：100)。
步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，所述水溶性醇占所述氧化石墨烯混合液的质量百分比较佳地为2-95％，优选4-95％，更佳地10-95％，更优选30-95％，最佳地52-95％；在所述的氧化石墨烯混合液中，氧化石墨烯与所述的胺类水溶性还原剂的质量比较佳地为(1：0.5)-(1：200)，优选(1：0.5)-(1：100)，更佳地(1：0.5)-(1：50)，更优选(1：0.5)-(1：10)，最佳地(1：0.5)-(1：5)，最优选(1：0.5)-(1：2)。
步骤(1)中，所述的水溶性醇为本领域常规使用的水溶性醇，较佳地为甲醇、乙醇、丙醇、异丙醇、丁醇、丁二醇、异丁醇、乙二醇、丙二醇、丙三醇、辛二醇和聚乙烯醇中的一种或多种。
步骤(1)中，所述的胺类水溶性还原剂为本领域内常规，较佳地为甲 胺、乙二胺、二乙胺、丙二胺、丁二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、聚烯丙基胺、N,N'-二(2-氨乙基)-1,3-丙二胺和氨中的一种或多种。
步骤(1)中，所述氧化石墨烯混合液中，氧化石墨烯的含量较佳地为1-20mg/mL，更佳地为2-10mg/mL。
步骤(1)中，所述的氧化石墨烯混合液中还可以添加无机纳米颗粒或水溶性贵金属化合物。
所述的无机纳米颗粒可为本领域内常规的无机纳米颗粒，较佳地为金属纳米颗粒和/或非金属纳米颗粒。所述金属纳米颗粒较佳地为银、金、铂、铁、钴、锡和铅中的一种或多种。所述非金属纳米颗粒较佳地为金属氧化物纳米颗粒、非金属氧化物纳米颗粒和硅纳米颗粒中的一种或多种，更佳地为金属氧化物纳米颗粒。所述金属氧化物纳米颗粒较佳地为二氧化钛、三氧化二铁、四氧化三铁、二氧化锰、二氧化锡和四氧化三钴中的一种或多种；所述的非金属氧化物纳米颗粒较佳地包括二氧化硅纳米颗粒。
所述的无机纳米颗粒的粒径可为本领域内常用的粒径，较佳地为1-500纳米，更佳地为1-20纳米、20-50纳米、50-100纳米、100-500纳米、100-200纳米或10-50纳米。所述无机纳米颗粒的粒径在本发明的限定范围内，制得的复合气凝胶容易成形得到块体结构。
所述的氧化石墨烯混合液中，氧化石墨烯与所述的无机纳米颗粒的质量比较佳地为(1：0.01)-(1：5)。
所述的水溶性贵金属化合物可为本领域内常规的水溶性贵金属化合物，较佳地为水溶性贵金属酸和/或水溶性贵金属盐。所述的水溶性贵金属酸为本领域内常规，较佳地为氯金酸、氯铂酸、氯钯酸和氯铑酸中的一种或多种。所述水溶性贵金属盐为本领域内常规，较佳地为硝酸银、氯钌酸钾、氯铑酸钾、三氯化钌、三氯化铑和三氯化铱中的一种或多种。所述水溶性是指能够在不同温度的水中溶解即可。
所述的水溶性贵金属化合物中的贵金属较佳地为金、铂、钯、铑、银、 钌和铱中的一种或多种。
步骤(1)中，若还含有水溶性贵金属化合物，水溶性贵金属化合物添加量过低，制备的复合气凝胶体现不出贵金属优异的性能；添加量过高，则宏观复合气凝胶材料较难成型。故在所述的氧化石墨烯混合液中，氧化石墨烯与所述的水溶性贵金属化合物的质量比较佳地为(1：0.05)-(1：3)。
其中，步骤(1)中，若水溶性还原剂的含量太少，得到的是悬浮在管内的石墨烯-贵金属无机纳米复合颗粒，得不到具有一定自支撑力学强度的连续湿态石墨烯-贵金属无机纳米复合水凝胶；若水溶性还原剂的含量较多，不仅增加成本还致使氧化石墨烯以及贵金属离子在溶液中的分散性较差，不容易得到连续的石墨烯-贵金属无机纳米颗粒复合水凝胶。
步骤(2)中，当采用胺类水溶性化合物作为水溶性还原剂且在制备过程中不添加无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应优选在无氧条件下进行。当采用水溶性醇作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应可在无氧气氛或有氧气氛条件下进行。所述的无氧气氛条件为本领域常规使用的无氧气氛条件，较佳地为氮气和/或氩气气氛条件。所述的有氧气氛条件为本领域常规使用的有氧气氛条件，一般为空气。
步骤(2)中，所述的高能射线较佳地为钴60γ射线或电子束射线。
步骤(2)中，当采用胺类水溶性化合物作为水溶性还原剂且在制备过程中不添加无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应可为本领域辐照工艺的常规操作，所述的辐照反应的剂量较佳地为5-500kGy，更佳地为20-200kGy；所述的辐照反应的剂量率较佳地为0.1-10kGy/小时。当采用水溶性醇，或水溶性醇和胺类水溶性化合物的混合物作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量较佳地为20-800kGy，更佳地为50-800kGy，最佳地为110-600kGy；所述的辐照反应的剂量率较佳地为0.1-15kGy/小时，更佳地为0.5-12kGy/小 时，最佳地为1-12kGy/小时。
本发明还提供由上述石墨烯水凝胶的制备方法制备得到的石墨烯水凝胶。
本发明还提供了一种石墨烯气凝胶的制备方法，其包括以下步骤：将上述石墨烯水凝胶进行冷冻干燥或超临界二氧化碳干燥，即可。
其中，所述的冷冻干燥可为本领域常规操作。
其中，所述的超临界二氧化碳干燥可为本领域常规操作。
若氧化石墨烯混合液中含有水溶性贵金属化合物且当水溶性还原剂为水溶性醇时，为了实现石墨烯-贵金属无机纳米颗粒复合气凝胶的成型效果，所述水溶性醇占所述氧化石墨烯混合液的质量百分比较佳地为5-90％，更佳地为10-80％。
若氧化石墨烯混合液中含有水溶性贵金属化合物且当所述水溶性还原剂含有所述胺类水溶性还原剂时，为了更好地实现石墨烯-贵金属无机纳米颗粒复合气凝胶的成型效果，在所述的氧化石墨烯混合液中，氧化石墨烯与所述胺类水溶性还原剂的质量比较佳地为(1：1)-(1：150)，更佳地为(1：5)-(1：100)。
若将贵金属纳米颗粒与石墨烯直接共混成型制备复合气凝胶，贵金属无机纳米颗粒仅填充在石墨烯气凝胶多孔结构的内部，在石墨烯表面是无法负载的，而且其团聚严重，分散性差，致使其自身良好的催化、电学性能等优异特性，因团聚致使其利用效率受限。而本发明采用水溶性贵金属化合物，制得的石墨烯-贵金属无机纳米颗粒复合气凝胶，与其截然不同。本发明的纳米颗粒是由离子原位形成在石墨烯的表面，其均匀负载在石墨烯复合气凝胶的框架结构上，包括外表面和内部多孔结构上，所以本发明的贵金属纳米粒子不仅仅分散性较好，而且其粘合在石墨烯片层上慢慢成型，两者紧密结合而无团聚现象，使制备的复合气凝胶在吸收有机溶剂的过程中，有利于充分发挥贵金属无机纳米粒子自身良好的催化、电学性能等有益特性，具有极 大的潜在应用价值。
本发明还提供了一种由上述石墨烯气凝胶的制备方法制备得到的石墨烯气凝胶。
当所述水溶性还原剂为胺类水溶性化合物且在制备过程中不添加有无机纳米颗粒或水溶性贵金属化合物时，所述石墨烯气凝胶的密度优选为4-9mg/cm3，属于超轻气凝胶的范围(低于10mg/cm3)，孔径分布在10-100μm之间。
当所述水溶性还原剂为水溶性醇且在制备过程中不添加有无机纳米颗粒或水溶性贵金属化合物时，所述石墨烯气凝胶孔径分布在10-100μm之间，密度可调控，密度较佳地为2.9-41mg/cm3。
若制备过程中还含有无机纳米颗粒时，其制备得到的气凝胶为多孔结构，孔径分布在1-100μm之间。
若在制备过程中还含有水溶性贵金属化合物，其制备得到的气凝胶为多孔、大孔结构，结构较均匀，孔径分布在10-100μm之间，其中贵金属无机纳米颗粒的直径较佳地为40-80nm。
本发明还提供了上述石墨烯气凝胶在吸附有机溶剂中的应用。
所述的有机溶剂可为本领域常规的有机溶剂，优选相对密度在0.63-1.59g/cm3(25℃)的有机液体溶剂，该相对密度相对于25℃下水的密度1g/cm3。
所述的有机溶剂可为本领域常规的有机溶剂，优选液态烷烃(正十烷)，液态芳香烃(甲苯)，液态醇(正丁醇，乙醇)，液态羧酸(丙烯酸)，液态酯(甲基丙烯酸甲酯)，原油，食用油(大豆油)，柴油和煤油中的一种或几种。
当所述水溶性还原剂为水溶性醇且在制备过程中不添加有无机纳米颗粒或水溶性贵金属化合物时，制备得到的石墨烯气凝胶用于吸附正十烷时，在气凝胶密度为2.9mg/cm3下，吸油性能可高达250g/g。密度为3.1mg/cm3的圆柱状石墨烯-金纳米颗粒气凝胶用于吸附相对密度为1.59的有机溶剂四 氯化碳，其吸附容量可达500g/g。
在不违背本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：
1、本发明的石墨烯水凝胶和气凝胶，以氧化石墨烯分散液为原料通过一步法辐照还原组装并借助冷冻干燥方法直接得到，辐照还原反应在环境温度下进行，操作简洁，反应条件宽松，有望实现技术产业化。
2、本发明利用的原材料为氧化石墨烯，来源非常广泛，成本低，且利用率较高，所用氧化石墨烯原料反应后完全凝胶成型，凝胶周围水溶液为透明，原料几乎无损失。
3、本发明选用水溶性醇作为辐照反应体系的技术方案，配制过程简单，不涉及苛刻的化学反应条件，避免了复杂而困难的化学反应和纯化过程，所制备的石墨烯气凝胶较为纯净，除碳、氧元素外无其他元素掺杂。
4、本发明的石墨烯水凝胶和气凝胶的形状和大小可调，通过采用不同形状和大小的辐照反应器即可得到不同形状和大小的石墨烯水凝胶和气凝胶。在添加水溶性贵金属化合物的技术方案中，贵金属纳米颗粒分布非常均匀，基本无团聚现象；其比表面积大、导电性好、热传导性能优异。
5、本发明的石墨烯气凝胶的密度可调控，通过改变反应物浓度即可得到不同密度的石墨烯气凝胶。
6、本发明的石墨烯气凝胶为多孔且大孔结构，较为均匀，可用于有机溶剂的吸附，具有重大的应用价值。
7、在添加水溶性贵金属化合物的技术方案中，本发明的制备方法可以得到不同贵金属种类的单一金属纳米颗粒-石墨烯复合气凝胶，也可以得到两种或两种以上贵金属复合的石墨烯-贵金属纳米颗粒复合气凝胶材料。
石墨烯气凝胶的石墨烯片层提供了贵金属纳米颗粒的负载位点，为贵金 属纳米颗粒的原位形成、均匀分散性和应用性提供了载体；石墨烯-贵金属纳米颗粒复合气凝胶结合了石墨烯气凝胶与贵金属纳米颗粒的功能，负载有贵金属纳米颗粒的石墨烯复合凝胶在吸附有机溶剂的过程中，具有良好的电导性，可以为相应的电催化反应提供可行性，使其在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。
附图说明
图1为本发明实施例1中得到的宏观石墨烯气凝胶照片。
图2为本发明实施例1中得到的石墨烯气凝胶扫描电镜照片。
图3为本发明实施例2中得到的宏观石墨烯气凝胶照片。
图4为本发明实施例23中得到的宏观石墨烯水凝胶照片。
图5为本发明实施例23中得到的宏观石墨烯气凝胶照片。
图6为本发明实施例23中得到的石墨烯气凝胶的扫描电镜照片。
图7为实施例40制备的石墨烯-银无机纳米颗粒复合气凝胶中多孔结构扫描电镜(低倍)图。
图8为实施例40制备的石墨烯-银无机纳米颗粒复合气凝胶中银纳米颗粒在石墨烯片层上的负载扫描电镜(高倍)图。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
本发明中，吸附容量的评价标准是：每克本发明的石墨烯气凝胶吸附多少克有机溶剂。
下述实施例中，所用石墨由西格玛奥德里奇(Sigma-Aldrich)公司提供， 所用石墨为鳞片石墨，平均粒径为500μm，其余原料均由国药集团化学试剂有限公司提供。
实施例1
(1)利用改进的氧化剥离石墨法制备氧化石墨烯分散液：
石墨10g，98％硫酸150ml，硝酸30ml，加入到500ml锥形瓶中室温搅拌24h，慢慢倒入1L水中过滤收集固体，洗涤3次，80℃烘干4小时。重复预氧化过程两次。将干燥后的预氧化石墨放入箱式炉中900℃热膨胀10s得到热膨胀氧化石墨。在500ml广口锥形瓶中将5g热膨胀氧化石墨与300ml硫酸，5g K2S2O8，7g五氧化二磷混合后80℃加热4小时，用2L水稀释，过滤洗涤，空气中干燥3天得到预氧化热膨胀石墨。将干燥的预氧化热膨胀石墨与200ml硫酸在低温0-5℃下混合，加入20g高锰酸钾，慢慢加入，35℃搅拌1h，加2L水稀释静置1h后加入10ml 30％的双氧水，静置2天，倒掉上清液，离心洗涤，温和搅拌得到分散较好的氧化石墨烯分散液。
(2)将步骤(1)制得的氧化石墨烯分散液与乙二胺混合制备得4mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:50。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧。
(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为100kGy，在反应器中形成氨基修饰石墨烯水凝胶。
(5)将步骤(4)所得氨基修饰石墨烯水凝胶进行冷冻干燥，得到干态的石墨烯气凝胶。其宏观形貌照片如图1所示为连续的圆柱状块体结构，其微观多孔形貌如图2所示为石墨烯气凝胶的扫描电子显微镜断面照片，从图中可以看出，其孔为大孔结构，孔径分布在10-100μm之间，较为均匀。其氮元素含量、碳氧比和密度如表1中所示。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达120g/g(以正十烷为例)。
实施例2
重复实施例1，除有以下不同点外，其他条件均相同：
步骤(1)预氧化石墨在400℃条件热膨胀30s得到热膨胀氧化石墨；
步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为50kGy，在细管状反应器中形成氨基修饰石墨烯水凝胶，经过超临界二氧化碳干燥得到细长棒状石墨烯气凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的细长棒状石墨烯气凝胶摆成了一个“王”字的照片如图3所示。该棒状石墨烯气凝胶具有良好的吸油性能，吸附容量达110g/g(以正十烷为例)。
实施例3
重复实施例1，除有以下不同点外，其他条件均相同：步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为5kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达112g/g(以正十烷为例)。
实施例4
重复实施例1，除有以下不同点外，其他条件均相同：步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为100kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达115g/g(以正十烷为例)。
实施例5
重复实施例1，除有以下不同点外，其他条件均相同：步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为200kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达120g/g(以正十烷为例)。
实施例6
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与乙二胺混合制备得1mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:400。步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为500kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达150g/g(以正十烷为例)。
实施例7
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与乙二胺混合制备得3mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:50。步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为50kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达130g/g(以正十烷为例)。
实施例8
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与乙二胺混合制备得5mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:1。步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为50kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达100g/g(以正十烷为例)。
实施例9
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与乙二胺混合制备得10mg/ml氧化石墨烯混合溶液，其 中氧化石墨烯与胺类水溶性化合物的质量比为1:0.5。步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为50kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达90g/g(以正十烷为例)。
实施例10
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(丙二胺和二乙烯三胺按照质量比为1:1的混合物)混合制备得3mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:100，其剂量为60kGy。得到的石墨烯气凝胶的氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达135g/g(以正十烷为例)。
实施例11
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(二乙胺和四乙烯五胺按照质量比为1:1的混合物)混合制备得2mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:250，其剂量为100kGy。得到的石墨烯气凝胶的氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达140g/g(以正十烷为例)。
实施例12
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(聚烯丙基胺和乙二胺按照质量比为1:2的混合物)混合制备得5mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:300，其剂量为400kGy。得到的石墨烯 气凝胶的氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达98g/g(以正十烷为例)。
实施例13
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(丁二胺和N,N'-二(2-氨乙基)-1,3-丙二胺按照质量比为0.5:1的混合物)混合制备得3mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:50，其剂量为100kGy。得到的石墨烯气凝胶的氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达120g/g(以正十烷为例)。
实施例14
重复实施例1，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(聚烯丙基胺和三乙烯四胺按照质量比为1:2的混合物)混合制备得4mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:50。步骤(4)将封好的辐照反应器用电子束射线源辐照，剂量为500kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表1中所示。得到的石墨烯气凝胶的照片与实施例1类似。该石墨烯气凝胶具有良好的吸油性能，吸附容量可达100g/g(以正十烷为例)。
对比例1
重复实施例1，除有以下不同点外，其他条件均相同：将纯净的氧化石墨烯分散液与胺类水溶性化合物水合肼(NH2-NH2(H2O))混合制备的氧化石墨烯混合液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:100。其结果得到的是沉淀在管内的石墨烯颗粒，得不到连续的湿态石墨烯水凝胶，同样也得不到连续的干态石墨烯气凝胶，不具有良好吸油性能。其产物的氮元 素含量和碳氧比如表1中所示。
对比例2
重复实施例1，除有以下不同点外，其他条件均相同：将纯净的6mg/ml氧化石墨烯分散液装入辐照管中进行辐照。其结果是得不到连续的石墨烯水凝胶，也得不到连续的干态石墨烯气凝胶，不具有良好吸油性能。其产物的氮元素含量和碳氧比如表1中所示。
对比例3
重复实施例1，除有以下不同点外，其他条件均相同：将纯净的2mg/ml氧化石墨烯分散液与胺类水溶性化合物丙二胺混合制备的氧化石墨烯混合液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:100。装入辐照管中静置12小时不进行辐照。其结果是得不到连续的石墨烯水凝胶，不具有良好吸油性能，也得不到连续的干态石墨烯气凝胶。其产物的氮元素含量和碳氧比如表1中所示。
效果实施例1
测定实施例1-13所得石墨烯气凝胶和对比例1-3所得产物的氮元素含量、碳氧比、气凝胶密度和吸油性能数据。其中，氮元素含量、碳元素含量和氧元素含量通过X射线光电子能谱XPS得到，碳氧比是根据碳元素含量和氧元素含量比值得到；气凝胶密度根据本领域常规手段测试，由质量与体积比得到；吸油性能根据本领域常规手段测试，其数值由吸油质量与气凝胶质量比得到，测试结果见表1。
表1实施例1-13所得石墨烯气凝胶和对比例1-3所得产物的氮元素含量、碳氧比、气凝胶密度和吸油性能数据
Figure PCTCN2015089216-appb-000001
Figure PCTCN2015089216-appb-000002
下述实施例中，所用石墨由西格玛奥德里奇(Sigma-Aldrich)公司提供，所用石墨为鳞片石墨，平均粒径为50-500μm，其余原料均由国药集团化学试剂有限公司提供。
实施例15
(1)①利用改进的氧化剥离石墨法制备氧化石墨烯分散液：
石墨10g，98％硫酸150ml，硝酸30ml，加入到500ml锥形瓶中室温搅拌24h，慢慢倒入1L水中过滤收集固体，洗涤3次，80℃烘干4小时。重复预氧化过程两次。将干燥后的预氧化石墨放入箱式炉中900℃热膨胀10s得到热膨胀氧化石墨。在500ml广口锥形瓶中将5g热膨胀氧化石墨与300ml硫酸，5g过硫酸钾(K2S2O8)，7g五氧化二磷混合后80℃加热4小时，用2L水稀释，过滤洗涤，空气中干燥3天得到预氧化热膨胀石墨。将干燥的预氧化热膨胀石墨与200ml硫酸在低温0-5℃下混合，加入20g高锰酸钾，慢慢加入，35℃搅拌1h，加2L水稀释静置1h后加入10ml 30％的双氧水，静置2天，倒掉上清液，离心洗涤，温和搅拌得到分散较好的氧化石墨烯分散液；
②将步骤①制得的氧化石墨烯分散液与丙二醇混合，制备得到1mg/ml的氧化石墨烯混合溶液，其中丙二醇的质量占氧化石墨烯混合溶液的质量百分比为5％；
(2)将步骤(1)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照，辐照剂量为300kGy，辐照剂量率为3kGy/小时，在反应器中形成石墨烯水凝胶；
(3)将步骤(2)所得石墨烯水凝胶进行冷冻干燥，得到干态的石墨烯气凝胶。
实施例16
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与乙醇混合制备得4mg/ml氧化石墨烯混合溶液，其中乙醇的质量占氧化石墨烯混合溶液的质量百分比为20％；步骤(2)将不封口(空气气氛)的辐照反应器用钴60γ射线源辐照，辐照剂量为110kGy，辐照剂量率为0.5kGy/小时，在细管状反应器中形成石墨烯水凝胶，经过超临界二氧化碳干燥得到细长棒状石墨烯气凝胶。
实施例17
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与甲醇、异丙醇、丁醇、聚乙烯醇混合(其中甲醇、异丙醇和丁醇的质量占氧化石墨烯混合溶液的质量百分比均为10％，聚乙烯醇的质量占氧化石墨烯混合液的质量百分数为1％)制备得8mg/ml氧化石墨烯混合溶液；步骤(2)将通氩气除氧封好的辐照反应器用钴60γ射线源辐照，辐照剂量为600kGy，辐照剂量率为12kGy/小时，在圆柱状反应器中形成石墨烯水凝胶。进行冷冻干燥，得到干态的石墨烯气凝胶。
实施例18
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与丙醇和丁二醇混合(其中丙醇和丁 二醇的质量占氧化石墨烯混合溶液的质量百分比均为20％)制备得15mg/ml氧化石墨烯混合溶液；步骤(2)将通氮气除氧封好的辐照反应器用钴60γ射线源辐照，辐照剂量为400kGy，辐照剂量率为6kGy/小时，在圆柱状反应器中形成石墨烯水凝胶。进行冷冻干燥，得到干态的石墨烯气凝胶。
实施例19
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与丙三醇和乙醇混合(其中丙三醇的质量占氧化石墨烯混合溶液的质量百分比为5％，乙醇的质量占氧化石墨烯混合溶液的质量百分比为40％)制备得30mg/ml氧化石墨烯混合溶液；步骤(2)将通氮气除氧封好的辐照反应器用钴60γ射线源辐照，剂量为500kGy，辐照剂量率为8kGy/小时，在圆柱状反应器中形成石墨烯水凝胶。进行冷冻干燥，得到干态的石墨烯气凝胶。
实施例20
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与甲醇和异丁醇混合(其中甲醇的质量占氧化石墨烯混合溶液的质量百分比为50％，异丁醇的质量占氧化石墨烯混合溶液的百分比为45％)制备得30mg/ml氧化石墨烯混合溶液；步骤(2)将通氮气除氧封好的辐照反应器用钴60γ射线源辐照，辐照剂量为500kGy，辐照剂量率为10kGy/小时，在圆柱状反应器中形成石墨烯水凝胶。进行冷冻干燥，得到干态的石墨烯气凝胶。
实施例21
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与乙醇混合制备得10mg/ml氧化石墨烯混合溶液，其中丙醇的质量占氧化石墨烯混合溶液的质量百分比为95％；步骤(2)将通氮气除氧封好的辐照反应器用钴60γ射线源辐照，辐照剂量为300kGy，辐照剂量率为6kGy/小时，在细管状反应器中形成石墨烯水凝胶， 经过超临界二氧化碳干燥得到细长棒状石墨烯气凝胶。
实施例22
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与丙醇混合制备得15mg/ml氧化石墨烯混合溶液，其中丙醇的质量占氧化石墨烯混合溶液的质量百分比为2％；步骤(2)将氧化石墨烯混合液在未封口的扁平状辐照反应器中用电子束射线源辐照，辐照剂量为600kGy，辐照剂量率为8kGy/小时，在扁平状反应器中形成扁平状石墨烯水凝胶，经过冷冻干燥得到扁平状石墨烯气凝胶。
对比例4
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将纯净的氧化石墨烯水分散液与丙醇混合制备得4mg/ml氧化石墨烯混合液，其中丙醇的质量占氧化石墨烯混合溶液的质量百分比为1％；步骤(2)将通氮气除氧封好的辐照反应器用钴60γ射线源辐照，辐照剂量为300kGy，辐照剂量率为1.5kGy/小时。其结果得到的是沉淀在管内的石墨烯颗粒，得不到连续的湿态石墨烯水凝胶，同样也得不到连续的干态石墨烯气凝胶。
对比例5
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将纯净的6mg/ml氧化石墨烯水分散液装入通氮气除氧的辐照管中用钴60γ射线源辐照，辐照剂量为300kGy，辐照剂量率为10kGy/小时。其结果是得不到连续的石墨烯水凝胶，也得不到连续的干态石墨烯气凝胶。
对比例6
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将纯净的氧化石墨烯与丙醇混合制备得4mg/ml氧化石墨烯混合液，其中丙醇的质量占氧化石墨烯混合溶液的质量百分比为99％；装入辐照管中用钴60γ射线源辐照，辐照剂量为300kGy，辐照剂量率为6kGy/小时。其结果是得不到连续的石墨烯水凝胶，也得不到连续的干态石墨烯气凝胶。
对比例7
按照实施例15的制备方法进行，除有以下不同点外，其他条件均相同：将纯净的氧化石墨烯与丙醇混合制备得4mg/ml氧化石墨烯混合液，其中丙醇的质量占氧化石墨烯混合溶液的质量百分比为30％；装入辐照管中静置12小时不进行辐照。其结果是得不到连续的石墨烯水凝胶，也得不到连续的干态石墨烯气凝胶。
效果实施例2
评价实施例制得的石墨烯气凝胶的宏观形貌和微观形貌。图4为实施例15步骤(2)中得到的宏观石墨烯水凝胶照片，其宏观形貌显示为连续的圆柱状块体结构。图5为实施例15步骤(3)中得到的宏观石墨烯气凝胶照片，其宏观形貌也显示为连续的圆柱状块体结构，而且该石墨烯气凝胶超轻，其重量连常规羽毛都可承受。实施例17-20和22的石墨烯气凝胶的宏观形貌与实施例15类似。图6为实施例15石墨烯气凝胶的扫描电子显微镜断面照片，其微观形貌显示为多孔结构，其孔为大孔结构，孔径分布在10-100μm之间，较为均匀。实施例16-22的石墨烯气凝胶的微观形貌结构与实施例15类似。
效果实施例3
测定实施例15-22所得石墨烯气凝胶和对比例4-7所得产物的碳氧比、气凝胶密度和吸油性能数据。其中，元素种类、碳元素含量和氧元素含量通过X射线光电子能谱XPS得到，碳氧比是根据碳元素含量和氧元素含量比值得到，杂质元素是除碳氧外的其它元素；气凝胶密度根据本领域常规手段测试，由质量与体积比得到；吸油性能根据本领域常规手段测试，其数值由吸油质量与气凝胶质量比得到，测试结果见表2。
表2实施例15-22所得石墨烯气凝胶和对比例4-7所得产物的碳氧比、气凝胶密度和吸油性能数据
样品 碳氧比 杂质元素 气凝胶密度 吸油性能(吸附容量以
     (mg/cm3) 正十烷为例)(g/g)
实施例15 8.20 无 2.9 250
实施例16 7.92 无 6.3 130
实施例17 9.13 无 11.3 64
实施例18 8.41 无 22.2 30
实施例19 8.53 无 41 20
实施例20 8.61 无 40.0 22
实施例21 8.38 无 13.6 60
实施例22 9.37 无 6.8 125
对比例4 4.10 无 — —
对比例5 3.2 无 — —
对比例6 3.92 无 — —
对比例7 2.3 无 — —
如表2所示，本发明石墨烯气凝胶密度低，最低仅为2.9mg/cm3，且具有良好的吸油性能，吸附容量在20-250g/g之间(吸附容量以正十烷为例)。而对比例4-7的产物不具有良好的吸油性能。
下述实施例中，所用石墨由西格玛奥德里奇(Sigma-Aldrich)公司提供，所用石墨为鳞片石墨，平均粒径为500μm，其余原料均由国药集团化学试剂有限公司提供。
实施例23
(1)利用改进的氧化剥离石墨法制备氧化石墨烯分散液：
石墨10g，98％硫酸150ml，硝酸30ml，加入到500ml锥形瓶中室温搅拌24h，慢慢倒入1L水中过滤收集固体，洗涤3次，80℃烘干4小时。重复预氧化过程两次。将干燥后的预氧化石墨放入箱式炉中900℃热膨胀10s得到热膨胀氧化石墨。在500ml广口锥形瓶中将5g热膨胀氧化石墨与300ml 硫酸，5g K2S2O8，7g五氧化二磷混合后80℃加热4小时，用2L水稀释，过滤洗涤，空气中干燥3天得到预氧化热膨胀石墨。将干燥的预氧化热膨胀石墨与200ml硫酸在低温0-5℃下混合，加入20g高锰酸钾，慢慢加入，35℃搅拌1h，加2L水稀释静置1h后加入10ml 30％的双氧水，静置2天，倒掉上清液，离心洗涤，温和搅拌得到分散较好的氧化石墨烯分散液。
(2)将步骤(1)制得的氧化石墨烯分散液与乙二胺和乙醇混合制备得4mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:200，乙醇的质量占氧化石墨烯混合溶液的质量百分比为2％。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧。
(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为100kGy，在反应器中形成氨基修饰石墨烯水凝胶。
(5)将步骤(4)所得氨基修饰石墨烯水凝胶进行冷冻干燥，得到干态的石墨烯气凝胶。其孔为大孔结构，孔径分布在10-100μm之间，较为均匀。其氮元素含量、碳氧比和密度如表3中所示。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达141g/g(以原油为例，相对密度为0.86)。
实施例24
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与丙二胺和异丙醇、丁二醇混合制备得3mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与丙二胺的质量比为1:100，(其中异丙醇的质量占氧化石墨烯混合溶液的质量百分比为5％，丁二醇的质量占氧化石墨烯混合溶液的百分比为5％)。步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为50kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达163g/g(以食用油大豆油为例，相对密度为0.92)。
实施例25
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与二乙烯三胺和甲醇、乙二醇混合制备得5mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:50(其中甲醇的质量占氧化石墨烯混合溶液的质量百分比为20％，乙二醇的质量占氧化石墨烯混合溶液的百分比为10％)。步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为50kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达138g/g(以柴油为例，相对密度为0.84)。
实施例26
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与三乙烯四胺和丙三醇、聚乙烯醇混合制备得10mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:10(其中丙三醇的质量占氧化石墨烯混合溶液的质量百分比为2％，聚乙烯醇的质量占氧化石墨烯混合溶液的百分比为2％)。步骤(4)将封好的辐照反应器用钴60γ射线源辐照，剂量为50kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达110g/g(以汽车机油为例，相对密度为0.88)。
实施例27
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(丙二胺和二乙烯三胺按照质量比为1:1的混合物)和辛二醇、乙醇混合制备得3mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:100，(其中辛二醇的质量占氧化石墨烯混合溶液的质量百分比为2％，乙醇的质量占氧化石墨烯 混合溶液的百分比为50％)其剂量为60kGy。得到的石墨烯气凝胶的氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达177g/g(以原油为例，相对密度为0.96)。
实施例28
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(二乙胺和四乙烯五胺按照质量比为1:1的混合物)和丙醇、丙二醇混合制备得2mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:50，(其中丙醇的质量占氧化石墨烯混合溶液的质量百分比为85％，丙二醇的质量占氧化石墨烯混合溶液的百分比为10％)其剂量为100kGy。得到的石墨烯气凝胶的氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达160g/g(以液态烷烃正十烷和液态酯类甲基丙烯酸甲酯混合液为例，相对密度为0.83)。
实施例29
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(聚烯丙基胺和乙二胺按照质量比为1:2的混合物)和异丁醇混合制备得5mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:2，其中异丁醇的质量占氧化石墨烯混合溶液的质量百分比为35％，其剂量为400kGy。得到的石墨烯气凝胶的氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达123g/g(以液态醇类正丁醇和液态羧酸类丙烯酸混合液为例，相对密度为0.92)。
实施例30
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(丁二胺和N,N'-二(2-氨乙基)-1,3-丙二胺按照质量比为0.5:1的混合物)和丁二醇混合制备得3mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:5，丁二醇的质量占氧化石墨烯混合溶液的质量百分比为30％，其剂量为100kGy。得到的石墨烯气凝胶的氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该圆柱状石墨烯气凝胶具有良好的吸油性能，吸附容量达135g/g(以煤油和柴油混合液为例，相对密度为0.82)。
实施例31
重复实施例23，除有以下不同点外，其他条件均相同：将步骤(1)制得的氧化石墨烯分散液与氨基水溶性化合物(聚烯丙基胺和三乙烯四胺按照质量比为1:2的混合物)和甲醇混合制备得4mg/ml氧化石墨烯混合溶液，其中氧化石墨烯与胺类水溶性化合物的质量比为1:0.5，甲醇的质量占氧化石墨烯混合溶液的质量百分比为30％。步骤(4)将封好的辐照反应器用电子束射线源辐照，剂量为500kGy，在圆柱状反应器中形成氨基修饰石墨烯水凝胶。其氮元素含量、碳氧比和密度如表3中所示。得到的石墨烯气凝胶的照片与实施例23类似。该石墨烯气凝胶具有良好的吸油性能，吸附容量可达120g/g(以液态芳香烃甲苯为例，相对密度为0.87)。
表3实施例23-31所得石墨烯气凝胶的氮元素含量、碳氧比、气凝胶密度和吸油性能数据(以不同密度有机溶剂为例，见实施例)
Figure PCTCN2015089216-appb-000003
Figure PCTCN2015089216-appb-000004
下述实施例中，所用石墨由西格玛奥德里奇(Sigma-Aldrich)公司提供，所用石墨为鳞片石墨，平均粒径为50-500μm，其余原料均由国药集团化学试剂有限公司提供。
实施例32
(1)氧化石墨烯分散液的制备方法：
石墨10g，98％硫酸150ml，硝酸30ml，加入到500ml锥形瓶中室温搅拌24h，慢慢倒入1L水中过滤收集固体，洗涤3次，80℃烘干4小时。重复预氧化过程两次。将干燥后的预氧化石墨放入箱式炉中900℃热膨胀10s得到热膨胀氧化石墨。在500ml广口锥形瓶中将5g热膨胀氧化石墨与300ml硫酸，5g K2S2O8，7g五氧化二磷混合后80℃加热4小时，用2L水稀释，过滤洗涤，空气中干燥3天得到预氧化热膨胀石墨。将干燥的预氧化热膨胀石墨与200ml硫酸在低温0-5℃下混合，加入20g高锰酸钾，慢慢加入，35℃搅拌1h，加2L水稀释静置1h后加入10ml 30％的双氧水，静置2天，倒掉上清液，离心洗涤，温和搅拌得到分散较好的氧化石墨烯分散液。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为1-20nm的金纳米颗粒和丙二醇混合制备得1mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与金纳米颗粒的质量比为1：0.1，丙二醇占氧化石墨烯混合溶液的质量百分比为2％。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-金纳米颗粒复合水凝胶；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
(4)将步骤(3)所得石墨烯-金纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-金纳米颗粒气凝胶。
通过对石墨烯-金纳米颗粒复合气凝胶微观形貌测试分析发现其为多孔结构，孔径分布在10-100μm之间，较为均匀。该石墨烯-金纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
实施例33
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为20-50nm的铂纳米颗粒、乙醇、聚乙烯醇、氨水混合制备得4mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与铂纳米颗粒的质量比为1：0.01；乙醇占氧化石墨烯混合溶液的质量百分比为20％，聚乙烯醇占氧化石墨烯混合液的质量百分比为1％；氧化石墨烯混合液中，氧化石墨烯与氨的质量比为1：50。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入细管状反应器中，将不封口(空气气氛)的辐照反应器用钴60γ射线源辐照得石墨烯-铂纳米颗粒复合水凝胶；其中，剂量为110kGy，辐照反应的剂量率为0.1kGy/小时。
(4)将步骤(3)所得石墨烯-铂纳米颗粒复合水凝胶进行超临界二氧化碳干燥，得细长棒状石墨烯-铂纳米颗粒复合气凝胶。
该石墨烯-铂纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
实施例34
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为50-100nm的三氧化二铁颗粒和甲醇、异丙醇、丁醇和甲胺混合制备得8mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与纳米三氧化二铁颗粒的质量比为1：1；甲醇、异丙醇和丁醇占氧化石墨烯混合溶液的质量百分比均为10％，氧化石墨烯混合液中，氧化石墨烯与甲胺的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氩气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-三氧化二铁 纳米颗粒复合水凝胶；其中，剂量为600kGy，辐照反应的剂量率为10kGy/小时。
(4)将步骤(3)所得石墨烯-三氧化二铁纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-三氧化二铁纳米颗粒气凝胶。
所得石墨烯-三氧化二铁纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
实施例35
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为100-500nm的二氧化锡颗粒、丙醇、丁二醇、乙二胺混合制备得15mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与纳米二氧化锡颗粒的质量比为1：0.5；丙醇和丁二醇占氧化石墨烯混合溶液的质量百分比均为20％；氧化石墨烯混合液中，氧化石墨烯与乙二胺的质量比为1：200。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-二氧化锡纳米颗粒复合水凝胶；其中，剂量为400kGy，辐照反应的剂量率为15kGy/小时。
(4)将步骤(3)所得石墨烯-二氧化锡纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-二氧化锡纳米颗粒气凝胶。
该石墨烯-二氧化锡纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
实施例36
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为20-50nm的四氧化三钴颗粒和二氧化锰颗粒的混合物(四氧化三钴颗粒和二氧化锰颗粒的质量比为1：1)、丙三醇、乙醇、丙二胺和N,N'-二(2-氨乙基)-1,3-丙二胺混 合制备得20mg/ml氧化石墨烯混合溶液。其中，氧化石墨烯与无机纳米颗粒的总质量比为1：10；丙三醇占氧化石墨烯混合溶液的质量百分比为2％，乙醇占氧化石墨烯混合溶液的质量百分比为40％，氧化石墨烯混合液中，氧化石墨烯与丙二胺的质量比为1：100，氧化石墨烯与N,N'-二(2-氨乙基)-1,3-丙二胺的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-无机纳米颗粒复合水凝胶；其中，剂量为500kGy，辐照反应的剂量率为6kGy/小时。
(4)将步骤(3)所得石墨烯-无机纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-无机纳米颗粒气凝胶。
该石墨烯-无机纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
实施例37
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为100-200nm的银纳米颗粒和铅纳米颗粒的混合物(银纳米颗粒和铅纳米颗粒的质量比为1：1)甲醇、异丁醇、二乙烯三胺、三乙烯四胺和四乙烯五胺混合制备得10mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与纳米颗粒的总质量比为1：20；氧化石墨烯混合液中，氧化石墨烯与二乙烯三胺的质量比为1：0.3，氧化石墨烯与三乙烯四胺的质量比为1：0.1，氧化石墨烯与四乙烯五胺的质量比为1：0.1；甲醇占氧化石墨烯混合溶液的质量百分比为50％，异丁醇占氧化石墨烯混合溶液的质量百分比为45％。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-无机纳米颗粒复合水凝胶；其中，剂量为500kGy，辐照反应的剂量率为12kGy/小时。
(4)将步骤(3)所得石墨烯-无机纳米颗粒复合水凝胶进行冷冻干燥， 得干态的圆柱状石墨烯-无机纳米颗粒气凝胶。
该石墨烯-无机纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
实施例38
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为20-50nm的二氧化钛颗粒和乙醇、聚烯丙基胺混合制备得10mg/ml氧化石墨烯混合溶液；其中，乙醇占氧化石墨烯混合溶液的质量百分比为95％；氧化石墨烯混合液中，氧化石墨烯与聚烯丙基胺的质量比为1:0.5；氧化石墨烯与纳米二氧化钛颗粒的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-二氧化钛纳米颗粒复合水凝胶；其中，剂量为300kGy，辐照反应的剂量率为15kGy/小时。
(4)将步骤(3)所得石墨烯-二氧化钛纳米颗粒复合水凝胶进行超临界二氧化碳干燥，得干态的圆柱状石墨烯-二氧化钛纳米颗粒气凝胶。
该石墨烯-二氧化钛纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
实施例39
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液与粒径为20-50nm的二氧化硅颗粒和丙醇混合制备得15mg/ml氧化石墨烯混合溶液；其中，丙醇占氧化石墨烯混合溶液的质量百分比为5％，氧化石墨烯与二氧化硅纳米颗粒的质量比为1：0.5。
(3)将氧化石墨烯混合液在未封口的扁平状辐照反应器中用电子束射线源辐照，得扁平状石墨烯-二氧化硅纳米颗粒复合水凝胶；其中，剂量为 600kGy，辐照反应的剂量率为8kGy/小时。
(4)将步骤(3)所得石墨烯-二氧化硅纳米颗粒复合水凝胶进行冷冻干燥，得扁平状石墨烯-二氧化硅纳米颗粒复合气凝胶。
该石墨烯-二氧化钛纳米颗粒复合气凝胶具有良好的吸油性能，其碳氧比、密度和吸附容量如表4所示。
对比例8
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制得的氧化石墨烯分散液、粒径为1-20nm的金纳米颗粒、丙醇混合制备得4mg/ml氧化石墨烯混合液；其中，丙醇占氧化石墨烯混合溶液的质量百分比为1％，氧化石墨烯与金纳米颗粒的质量比为1：0.5。
(3)将氧化石墨烯混合液装入通氮气除氧封好的辐照反应器中，用钴60γ射线源辐照，剂量为300kGy。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
由于水溶性还原剂的含量比较少，得到的是悬浮在管内的石墨烯-金纳米复合颗粒，得不到具有一定自支撑力学强度的连续湿态石墨烯-金纳米颗粒复合水凝胶，同样也得不到连续的干态石墨烯-金纳米颗粒复合气凝胶。其产物不具有良好吸油性能，碳氧比如表4中所示。
对比例9
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制备的氧化石墨烯分散液与粒径为1-20nm的二氧化硅纳米颗粒混合制备得氧化石墨烯混合液；其中，氧化石墨烯与二氧化硅纳米颗粒的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中， 通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
由于无水溶性还原剂存在，其结果得到的是氧化石墨烯与二氧化硅纳米颗粒的混合液，得不到连续的块体石墨烯-二氧化硅纳米颗粒复合水凝胶，也得不到干态的石墨烯-二氧化硅纳米颗粒复合气凝胶。其产物不具有良好吸油性能，碳氧比如表4中所示。
对比例10
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制备的氧化石墨烯分散液、粒径为1-20nm的铅纳米颗粒与丙醇混合制备得4mg/ml氧化石墨烯混合液；其中，丙醇占氧化石墨烯混合溶液的质量百分比为99％，氧化石墨烯与铅纳米颗粒的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
由于水溶性还原剂的含量较多，其结果是得不到连续的石墨烯-铅纳米颗粒复合水凝胶，也得不到连续的干态石墨烯-铅纳米颗粒气凝胶。其产品不具有良好吸油性能，碳氧比如表4中所示。
对比例11
(1)氧化石墨烯分散液的制备方法与实施例32相同。
(2)将步骤(1)制备的氧化石墨烯分散液、粒径为1-20nm的铅纳米颗粒与丙醇混合制备得4mg/ml氧化石墨烯混合液；其中，丙醇占氧化石墨烯混合溶液的质量百分比为30％，氧化石墨烯与铅纳米颗粒的质量比为1：0.5。
(3)将氧化石墨烯混合液装入辐照管中静置24小时不进行辐照。
由于没有进行辐照反应，其结果是得不到连续的石墨烯-铅纳米颗粒复 合水凝胶，也得不到连续的干态石墨烯-铅纳米颗粒复合气凝胶。其产物不具有良好吸油性能，碳氧比如表4中所示。
效果实施例4
测定实施例32-39所得石墨烯-无机纳米颗粒复合气凝胶和对比例8-11所得产物的碳氧比、气凝胶密度和吸油性能数据。其中，碳元素含量和氧元素含量通过X射线光电子能谱XPS得到，碳氧比是根据碳元素含量和氧元素含量比值得到；气凝胶密度根据本领域常规手段测试，由质量与体积比得到；吸油性能根据本领域常规手段测试，其数值由吸油质量与气凝胶质量比得到，吸附容量以正十烷为例。测试结果见表4。
表4实施例及对比例终产品的碳氧比、密度和吸油性能数据
样品 碳氧比 密度/mg/cm3 吸油性能/g/g
实施例32 8.10 3.1 240
实施例33 7.82 6.4 140
实施例34 9.03 21.3 32
实施例35 8.31 32.2 25
实施例36 8.43 410 2
实施例37 8.51 800.0 1
实施例38 8.28 19.6 30
实施例39 9.27 10.8 68
对比例8 4.00 — —
对比例9 3.10 — —
对比例10 3.82 — —
对比例11 2.20 — —
下述实施例中，所用石墨由西格玛奥德里奇(Sigma-Aldrich)公司提供，所用石墨为鳞片石墨，平均粒径为50-500μm，其余原料均由国药集团化学试剂有限公司提供。
实施例40
(1)氧化石墨烯分散液的制备方法：
石墨10g，98％浓硫酸150ml，65％的浓硝酸50ml，加入到500ml锥形瓶中室温搅拌24h，慢慢倒入1L水中过滤收集固体，洗涤3次，80℃烘干4小时。重复预氧化过程两次。将干燥后的预氧化石墨放入箱式炉中900℃热膨胀10s得到热膨胀氧化石墨。在500ml广口锥形瓶中将5g热膨胀氧化石墨与300ml 98％的浓硫酸，4.2g K2S2O8，6.2g五氧化二磷混合后80℃加热4小时，用2L水稀释，过滤洗涤，空气中干燥3天得到预氧化热膨胀石墨。将干燥的预氧化热膨胀石墨5g与200ml 98％的浓硫酸在低温0-5℃下混合，加入15g高锰酸钾，慢慢加入，35℃搅拌2h，加2L水稀释静置1h后加入20ml 30％的双氧水，静置2天，离心洗涤，加入水搅拌，即可，得到分散较好的氧化石墨烯分散液。
(2)将步骤(1)制得的氧化石墨烯分散液、硝酸银和丙二醇混合制备得1mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与硝酸银的质量比为1：0.1，丙二醇占氧化石墨烯混合溶液的质量百分比为2％。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-银纳米颗粒复合水凝胶；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
(4)将步骤(3)所得石墨烯-银纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-银纳米颗粒气凝胶。
图7为制备的石墨烯-银无机纳米颗粒复合气凝胶中多孔结构扫描电镜(低倍)图，发现其为多孔、大孔结构，结构较均匀，孔径分布在10-100μm之间。图8为制备的石墨烯-银无机纳米颗粒复合气凝胶中银纳米颗粒在石墨烯片层上的负载扫描电镜(高倍)图，发现银纳米颗粒大小分布均匀，直径在40-80nm。该石墨烯-银无机纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5 所示。
实施例41
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯金酸、三氯化钌、乙醇、聚乙烯醇、氨水混合制备得4mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与贵金属化合物总量的质量比为1：0.05(氯金酸和三氯化钌的质量比为1：1)；乙醇占氧化石墨烯混合溶液的质量百分比为20％，聚乙烯醇占氧化石墨烯混合溶液的质量百分比为1％；氧化石墨烯混合液中，氧化石墨烯与氨的质量比为1：50。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入细管状反应器中，将不封口(空气气氛)的辐照反应器用钴60γ射线源辐照得石墨烯-贵金属纳米颗粒复合水凝胶；其中，剂量为110kGy，辐照反应的剂量率为1kGy/小时。
(4)将步骤(3)所得石墨烯-贵金属纳米颗粒复合水凝胶进行超临界二氧化碳干燥，得细长棒状石墨烯-铂纳米颗粒复合气凝胶。
该石墨烯-贵金属纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
实施例42
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯金酸和甲醇、丙二醇、丁醇和甲胺混合制备得8mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与氯金酸的质量比为1：0.01；甲醇、丙二醇和丁醇占氧化石墨烯混合溶液的质量百分比均为5％，氧化石墨烯混合液中，氧化石墨烯与甲胺的质量比为1：1。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中， 通氩气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-金纳米颗粒复合水凝胶；其中，剂量为600kGy，辐照反应的剂量率为10kGy/小时。
(4)将步骤(3)所得石墨烯-金纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-金纳米颗粒气凝胶。
所得石墨烯-金纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
实施例43
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯钯酸、丙醇、丁二醇和乙二胺混合制备得15mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与氯钯酸的质量比为1：0.5；丙醇、丁二醇占氧化石墨烯混合溶液的质量百分比均为2.5％；氧化石墨烯混合液中，氧化石墨烯与乙二胺的质量比为1：100。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-钯纳米颗粒复合水凝胶；其中，剂量为400kGy，辐照反应的剂量率为15kGy/小时。
(4)将步骤(3)所得石墨烯-钯纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-钯纳米颗粒气凝胶。
该石墨烯-钯纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
实施例44
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯钯酸和氯铂酸的混合物 (氯金酸和氯铂酸的质量比为1：1)、丙三醇、乙醇和丙二胺、N,N'-二(2-氨乙基)-1,3-丙二胺混合制备得20mg/ml氧化石墨烯混合溶液。其中，氧化石墨烯与贵金属化合物的总质量比为1：5；丙三醇占氧化石墨烯混合溶液的质量百分比为1％，乙醇占氧化石墨烯混合溶液的质量百分比为40％，氧化石墨烯混合液中，氧化石墨烯与丙二胺的质量比为1：2.5，氧化石墨烯与N,N'-二(2-氨乙基)-1,3-丙二胺的质量比为1：2.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-贵金属无机纳米颗粒复合水凝胶；其中，剂量为500kGy，辐照反应的剂量率为6kGy/小时。
(4)将步骤(3)所得石墨烯-贵金属无机纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-贵金属无机纳米颗粒气凝胶。
该石墨烯-贵金属无机纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
实施例45
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、三氯化铑和三氯化铱的混合物(三氯化铑和三氯化铱的质量比为1：1)、甲醇、异丁醇和二乙烯三胺、三乙烯四胺、四乙烯五胺混合制备得2mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与贵金属化合物的总质量比为1：1；氧化石墨烯混合液中，氧化石墨烯与二乙烯三胺的质量比为1：0.5，氧化石墨烯与三乙烯四胺的质量比为1：0.1，氧化石墨烯与四乙烯五胺的质量比为1：0.1；甲醇占氧化石墨烯混合溶液的质量百分比为40％，异丁醇占氧化石墨烯混合溶液的质量百分比为40％。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-贵金属无机纳米颗粒复合水凝胶；其中，剂量为500kGy，辐照反应的剂量率为12kGy/小时。
(4)将步骤(3)所得石墨烯-贵金属无机纳米颗粒复合水凝胶进行冷冻干燥，得干态的圆柱状石墨烯-贵金属无机纳米颗粒气凝胶。
该石墨烯-贵金属无机纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
实施例46
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯钌酸钾和乙醇、聚烯丙基胺混合制备得10mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与氯钌酸钾的质量比为1：0.5；乙醇占氧化石墨烯混合溶液的质量百分比为90％；氧化石墨烯混合液中，氧化石墨烯与聚烯丙基胺的质量比为1:0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氩气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-钌纳米颗粒复合水凝胶；其中，剂量为300kGy，辐照反应的剂量率为15kGy/小时。
(4)将步骤(3)所得石墨烯-钌纳米颗粒复合水凝胶进行超临界二氧化碳干燥，得干态的圆柱状石墨烯-钌纳米颗粒气凝胶。
该石墨烯-钌纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
实施例47
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、三氯化钌和丙醇混合制备得15mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与三氯化钌的质量比为1：0.5，丙醇占氧化石墨烯混合溶液的质量百分比为10％。
(3)将氧化石墨烯混合液的扁平状辐照反应器中，在通氮气除氧，用电子束射线源辐照，得扁平状石墨烯-钌纳米颗粒复合水凝胶；其中，剂量为600kGy，辐照反应的剂量率为8kGy/小时。
(4)将步骤(3)所得石墨烯-钌纳米颗粒复合水凝胶进行冷冻干燥，得扁平状石墨烯-钌纳米颗粒复合气凝胶。
该石墨烯-钌纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
实施例48
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯铑酸和乙二胺混合制备得10mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与氯铑酸的质量比为1：3；氧化石墨烯混合液中，氧化石墨烯与乙二胺的质量比为1:200。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-铑纳米颗粒复合水凝胶；其中，剂量为800kGy，辐照反应的剂量率为15kGy/小时。
(4)将步骤(3)所得石墨烯-铑纳米颗粒复合水凝胶进行超临界二氧化碳干燥，得干态的圆柱状石墨烯-铑纳米颗粒气凝胶。
该石墨烯-铑纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部 微观结构与图7和图8类似。
实施例49
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯铑酸钾和乙二胺混合制备得10mg/ml氧化石墨烯混合溶液；其中，氧化石墨烯与氯铑酸钾的质量比为1：3；氧化石墨烯混合液中，氧化石墨烯与乙二胺的质量比为1:150。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照得石墨烯-铑纳米颗粒复合水凝胶；其中，剂量为50kGy，辐照反应的剂量率为0.1kGy/小时。
(4)将步骤(3)所得石墨烯-铑纳米颗粒复合水凝胶进行超临界二氧化碳干燥，得干态的圆柱状石墨烯-铑纳米颗粒气凝胶。
该石墨烯-铑纳米颗粒复合气凝胶具有良好的吸油性能，在小分子电分析和电催化等有机反应催化合成领域、石油有机中间体的合成领域等方面均具有巨大的潜在应用价值。其碳氧比、密度和吸附容量如表5所示。其内部微观结构与图7和图8类似。
对比例12
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制得的氧化石墨烯分散液、氯金酸、丙醇混合制备得4mg/ml氧化石墨烯混合液；其中，丙醇占氧化石墨烯混合溶液的质量百分比为0.5％，氧化石墨烯与氯金酸的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
由于水溶性还原剂的含量比较少，得到的是悬浮在管内的石墨烯-金纳米复合颗粒，得不到具有一定自支撑力学强度的连续湿态石墨烯-金纳米颗粒复合水凝胶，同样也得不到连续的干态石墨烯-金纳米颗粒复合气凝胶。 其产物不具有良好吸油性能，碳氧比如表5中所示。
对比例13
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制备的氧化石墨烯分散液与氯钌酸钾混合制备得2mg/ml氧化石墨烯混合液；其中，氧化石墨烯与氯钌酸钾的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
由于无水溶性还原剂存在，其结果得到的是氧化石墨烯与氯钌酸钾的混合液，得不到连续的块体石墨烯-钌纳米颗粒复合水凝胶，也得不到干态的石墨烯-钌纳米颗粒复合气凝胶。其产物不具有良好吸油性能，碳氧比如表5中所示。
对比例14
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制备的氧化石墨烯分散液、三氯化铑与丙醇混合制备得4mg/ml氧化石墨烯混合液；其中，丙醇占氧化石墨烯混合溶液的质量百分比为99％，氧化石墨烯与三氯化铑的质量比为1：0.5。
(3)将步骤(2)得到的氧化石墨烯混合溶液注入圆柱状辐照反应器中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照；其中，剂量为300kGy，辐照反应的剂量率为3kGy/小时。
由于水溶性还原剂的含量较多，致使氧化石墨烯以及贵金属离子在溶液中的分散性较差，其结果是得不到连续的石墨烯-铑纳米颗粒复合水凝胶，也得不到连续的干态石墨烯-铑纳米颗粒气凝胶。其产品不具有良好吸油性能，碳氧比如表5中所示。
对比例15
(1)氧化石墨烯分散液的制备方法与实施例40相同。
(2)将步骤(1)制备的氧化石墨烯分散液、氯钯酸与丙醇混合制备得4mg/ml氧化石墨烯混合液；其中，丙醇占氧化石墨烯混合溶液的质量百分比为30％，氧化石墨烯与氯钯酸的质量比为1：0.5。
(3)将氧化石墨烯混合液装入辐照管中，通氮气除氧；静置24小时不进行辐照。
由于没有进行辐照反应，其结果是得不到连续的石墨烯-钯纳米颗粒复合水凝胶，也得不到连续的干态石墨烯-钯纳米颗粒复合气凝胶。其产物不具有良好吸油性能，碳氧比如表5中所示。
对比例16
(1)将氯金酸水溶液与丙醇混合制备得贵金属离子混合液；其中，丙醇占混合溶液的质量百分比为30％，氯金酸在贵金属离子混合液的质量浓度为4mg/ml。
(2)将贵金属离子混合液装入辐照管中，通氮气除氧；将封好的辐照反应器用钴60γ射线源辐照；其中，剂量为600kGy，辐照反应的剂量率为10kGy/小时。
由于没有氧化石墨烯的引入，其结果得到的是团聚的肉眼可见(毫米级)金颗粒。
效果实施例5
测定实施例40-49所得石墨烯-贵金属无机纳米颗粒复合气凝胶和对比例12-16所得产物的碳氧比、气凝胶密度和吸油性能数据。
其中，碳元素含量和氧元素含量通过X射线光电子能谱XPS得到，碳氧比是根据碳元素含量和氧元素含量比值得到；气凝胶密度根据本领域常规手段测试，由质量与体积比得到；吸油性能根据本领域常规手段测试，其数值由吸油质量与气凝胶质量比得到，吸附容量以正十烷为例。测试结果见表5。
表5实施例及对比例终产品的碳氧比、密度和吸油性能数据
样品 碳氧比 密度/mg/cm3 吸油性能/g/g
实施例40 8.00 3.0 250
实施例41 7.72 6.2 140
实施例42 8.93 9.0 70
实施例43 8.11 23.2 35
实施例44 8.23 128 6
实施例45 8.31 5.7 120
实施例46 8.28 15.6 44
实施例47 9.17 21 36
实施例48 9.31 43 18
实施例49 7.28 33 23
对比例12 4.10 — —
对比例13 3.20 — —
对比例14 3.92 — —
对比例15 2.30 — —
对比例16 — — —
实施例50
重复实施例1，将制备得到的干态的石墨烯气凝胶用于吸附相对密度为0.63的正戊烷，其吸附容量可达90g/g。
实施例51
重复实施例15，将制备得到的干态的石墨烯气凝胶用于吸附相对密度为0.84的柴油，其吸附容量可达270g/g。
实施例52
重复实施例32，将制备得到的干态的圆柱状石墨烯-金纳米颗粒气凝胶其用于吸附相对密度为1.59的有机溶剂四氯化碳，其吸附容量可达500g/g。
实施例53
重复实施例40，将制备得到的干态的圆柱状石墨烯-银纳米颗粒气凝胶用于吸附相对密度为0.92的乙醇与丙烯酸的混合液，其吸附容量可达300g/g。

Claims (17)

  1. 一种石墨烯水凝胶的制备方法，其包括下述步骤：
    (1)将氧化石墨烯分散液与水溶性还原剂均匀混合得到氧化石墨烯混合液；
    (2)将所述氧化石墨烯混合液用高能射线照射进行辐照反应，得到石墨烯水凝胶。
  2. 如权利要求1所述的石墨烯水凝胶的制备方法，其特征在于：步骤(1)中，所述的氧化石墨烯分散液的制备方法包括如下步骤：①预氧化：将石墨、浓硫酸和硝酸倒入水中，过滤，烘干；重复上述预氧化过程2-3次，得到预氧化石墨；②热膨胀：将步骤①的预氧化石墨在400-900℃条件下热膨胀10-30s，得到热膨胀氧化石墨；③将步骤②的热膨胀氧化石墨与浓硫酸、过硫酸钾(K2S2O8)和五氧化二磷的混合物在80-90℃条件下加热，加入水过滤洗涤，干燥，得到预氧化热膨胀石墨；④将步骤③的预氧化热膨胀石墨与浓硫酸在0-5℃条件下混合，加入高锰酸钾，反应，再加入双氧水，静置，离心洗涤，加入水搅拌即得氧化石墨烯分散液；
    和/或，步骤(1)中，所述的氧化石墨烯混合液中还添加无机纳米颗粒或水溶性贵金属化合物；
    和/或，步骤(1)中，所述的水溶性还原剂为水溶性醇和/或胺类水溶性还原剂；
    和/或，步骤(1)中，所述的氧化石墨烯分散液中氧化石墨烯的含量为1-30mg/mL；
    和/或，步骤(2)中，所述的高能射线为钴60γ射线或电子束射线。
  3. 如权利要求2所述的石墨烯水凝胶的制备方法，其特征在于：
    步骤(2)中，当采用胺类水溶性化合物作为水溶性还原剂且在制备过程中不添加无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应在无氧条件下进行；
    步骤(2)中，当采用水溶性醇作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应在无氧气氛或有氧气氛条件下进行；
    和/或，步骤(2)中，当采用胺类水溶性化合物作为水溶性还原剂且在制备过程中不添加无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量为5-500kGy；
    和/或，步骤(2)中，当采用胺类水溶性化合物作为水溶性还原剂且在制备过程中不添加无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量率为0.1-10kGy/小时；
    和/或，步骤(2)中，当采用水溶性醇，或水溶性醇和胺类水溶性化合物的混合物作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量为20-800kGy；
    和/或，步骤(2)中，当采用水溶性醇，或水溶性醇和胺类水溶性化合物的混合物作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量率为0.1-15kGy/小时。
  4. 如权利要求3所述的石墨烯水凝胶的制备方法，其特征在于：
    步骤(1)中，当水溶性还原剂为水溶性醇时，所述水溶性还原剂占所述氧化石墨烯混合液的质量百分比为2-95％；
    步骤(1)中，当水溶性还原剂为胺类水溶性还原剂时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的水溶性还原剂的质量比为(1:0.5)-(1:400)；
    步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，所述水溶性醇占所述氧化石墨烯混合液的质量百分比为2-95％；在所述的氧化石墨烯混合液中，氧化石墨烯与所述的胺类水溶性还原剂的质量比为(1：0.5)-(1：200)；
    和/或，步骤(1)中，所述的水溶性醇为甲醇、乙醇、丙醇、异丙醇、 丁醇、丁二醇、异丁醇、乙二醇、丙二醇、丙三醇、辛二醇和聚乙烯醇中的一种或多种；
    和/或，步骤(1)中，所述的胺类水溶性还原剂为甲胺、乙二胺、二乙胺、丙二胺、丁二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、聚烯丙基胺、N,N'-二(2-氨乙基)-1,3-丙二胺和氨中的一种或多种；
    和/或，步骤(1)中，所述氧化石墨烯混合液中，氧化石墨烯的含量为1-20mg/mL；
    和/或，所述的无氧气氛条件为氮气和/或氩气气氛条件；所述的有氧气氛条件为空气气氛条件；
    和/或，步骤(2)中，当采用胺类水溶性化合物作为水溶性还原剂且在制备过程中不添加无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量为20-200kGy；
    和/或，步骤(2)中，当采用水溶性醇，或水溶性醇和胺类水溶性化合物的混合物作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量为50-800kGy；
    和/或，步骤(2)中，当采用水溶性醇，或水溶性醇和胺类水溶性化合物的混合物作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量率为0.5-12kGy/小时。
  5. 如权利要求4所述的石墨烯水凝胶的制备方法，其特征在于：
    步骤(1)中，当水溶性还原剂为水溶性醇时，所述水溶性还原剂占所述氧化石墨烯混合液的质量百分比为5-90％；
    步骤(1)中，当水溶性还原剂为胺类水溶性还原剂时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的水溶性还原剂的质量比为(1：0.5)-(1：200)；
    步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，所述水溶性醇占所述氧化石墨烯混合液的质量百分比为4-95％；
    和/或，步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的胺类水溶性还原剂的质量比为(1：0.5)-(1：100)；
    和/或，步骤(1)中，所述氧化石墨烯混合液中，氧化石墨烯的含量为2-10mg/mL；
    和/或，步骤(2)中，当采用水溶性醇，或水溶性醇和胺类水溶性化合物的混合物作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量为110-600kGy；
    和/或，步骤(2)中，当采用水溶性醇，或水溶性醇和胺类水溶性化合物的混合物作为水溶性还原剂，或制备过程中添加了无机纳米颗粒或水溶性贵金属化合物时，所述的辐照反应的剂量率为1-12kGy/小时。
  6. 如权利要求5所述的石墨烯水凝胶的制备方法，其特征在于：步骤(1)中，当水溶性还原剂为水溶性醇时，所述水溶性还原剂占所述氧化石墨烯混合液的质量百分比为10-80％；
    步骤(1)中，当水溶性还原剂为胺类水溶性还原剂时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的水溶性还原剂的质量比为(1：1)-(1：150)；
    步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，所述水溶性醇占所述氧化石墨烯混合液的质量百分比为10-95％；
    和/或，步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的胺类水溶性还原剂的质量比为(1：0.5)-(1：50)。
  7. 如权利要求6所述的石墨烯水凝胶的制备方法，其特征在于：步骤(1)中，当水溶性还原剂为胺类水溶性还原剂时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的水溶性还原剂的质量比为(1：5)-(1：100)；
    步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合 物时，所述水溶性醇占所述氧化石墨烯混合液的质量百分比为30-95％；
    和/或，步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的胺类水溶性还原剂的质量比为(1：0.5)-(1：10)。
  8. 如权利要求7所述的石墨烯水凝胶的制备方法，其特征在于：步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，所述水溶性醇占所述氧化石墨烯混合液的质量百分比为52-95％；
    和/或，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的胺类水溶性还原剂的质量比为(1：0.5)-(1：5)。
  9. 如权利要求7所述的石墨烯水凝胶的制备方法，其特征在于：步骤(1)中，当水溶性还原剂为水溶性醇和胺类水溶性还原剂的混合物时，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的胺类水溶性还原剂的质量比为(1：0.5)-(1：2)。
  10. 如权利要求2-9中至少一项所述的石墨烯水凝胶的制备方法，其特征在于：所述的无机纳米颗粒为金属纳米颗粒和/或非金属纳米颗粒；所述金属纳米颗粒为银、金、铂、铁、钴、锡和铅中的一种或多种；所述非金属纳米颗粒为金属氧化物纳米颗粒、非金属氧化物纳米颗粒和硅纳米颗粒中的一种或多种；所述金属氧化物纳米颗粒为二氧化钛、三氧化二铁、四氧化三铁、二氧化锰、二氧化锡和四氧化三钴中的一种或多种；所述的非金属氧化物纳米颗粒包括二氧化硅纳米颗粒；
    和/或，所述的无机纳米颗粒的粒径为1-500纳米；
    和/或，所述的氧化石墨烯混合液中，氧化石墨烯与所述的无机纳米颗粒的质量比为(1：0.01)-(1：5)；
    和/或，所述的水溶性贵金属化合物为水溶性贵金属酸和/或水溶性贵金属盐；
    和/或，所述的水溶性贵金属化合物中的贵金属为金、铂、钯、铑、银、 钌和铱中的一种或多种；
    和/或，在所述的氧化石墨烯混合液中，氧化石墨烯与所述的水溶性贵金属化合物的质量比为(1：0.05)-(1：3)。
  11. 如权利要求10所述的石墨烯水凝胶的制备方法，其特征在于：
    所述的无机纳米颗粒的粒径为1-20纳米、20-50纳米、50-100纳米、100-500纳米、100-200纳米或10-50纳米；
    和/或，所述的水溶性贵金属酸为氯金酸、氯铂酸、氯钯酸和氯铑酸中的一种或多种；所述水溶性贵金属盐为硝酸银、氯钌酸钾、氯铑酸钾、三氯化钌、三氯化铑和三氯化铱中的一种或多种。
  12. 如权利要求1-11中至少一项所述的石墨烯水凝胶的制备方法制备得到的石墨烯水凝胶。
  13. 一种石墨烯气凝胶的制备方法，其包括以下步骤：将如权利要求12所述的石墨烯水凝胶进行冷冻干燥或超临界二氧化碳干燥，即可。
  14. 一种如权利要求13所述的石墨烯气凝胶的制备方法制备得到的石墨烯气凝胶。
  15. 如权利要求14所述的石墨烯气凝胶在吸附有机溶剂中的应用。
  16. 如权利要求15所述的应用，其特征在于：所述的有机溶剂为液态烷烃，液态芳香烃，液态醇，液态羧酸，液态酯，原油，食用油，柴油，煤油中的一种或几种；
    和/或，所述的有机溶剂在25℃下，相对密度为0.63-1.59g/cm3，该相对密度相对于25℃下水的密度1g/cm3。
  17. 如权利要求16所述的应用，其特征在于：所述液态烷烃为正十烷；所述的液态芳香烃为甲苯；所述的液态醇为正丁醇和/或乙醇；所述的液态羧酸为丙烯酸；所述的液态酯为甲基丙烯酸甲酯；所述的食用油为大豆油。
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