WO2020040218A1 - グラフェンオキサイド吸着材及びその製造方法 - Google Patents
グラフェンオキサイド吸着材及びその製造方法 Download PDFInfo
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- WO2020040218A1 WO2020040218A1 PCT/JP2019/032695 JP2019032695W WO2020040218A1 WO 2020040218 A1 WO2020040218 A1 WO 2020040218A1 JP 2019032695 W JP2019032695 W JP 2019032695W WO 2020040218 A1 WO2020040218 A1 WO 2020040218A1
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- 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
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- 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
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Definitions
- the present disclosure relates to a graphene oxide adsorbent and a method for producing the same.
- the present disclosure relates to a light water adsorbent mainly used for separating light water and heavy water.
- a carbon-based material such as activated carbon having a different light water adsorption amount and heavy water adsorption amount is used as an adsorbent.
- the separation method used is known (Patent Document 1).
- adsorbent for example, when water vapor containing light water and heavy water is supplied, one of light water or heavy water is adsorbed by the adsorbent, and the other remains in water vapor in the air. Heavy water can be separated.
- activated carbon has a large surface area, the amount of water vapor adsorbed is as large as 30 to 50 mmol / g, and can adsorb a large amount of water.
- the maximum adsorption amount of water vapor of light water and heavy water to activated carbon is almost the same. Therefore, in the method of separating light water and heavy water using activated carbon, the separation efficiency is poor, and it is necessary to repeatedly adsorb water vapor to obtain light water or heavy water.
- the use of graphene oxide (hereinafter referred to as GO) as another adsorbent is being studied.
- the Hummers method is known as a method for producing GO.
- graphite is chemically oxidized to release the layered graphene oxide to obtain a dispersion aqueous solution.
- This method is a major method for preparing an aqueous dispersion of layered graphene oxide.
- the aqueous dispersion obtained in this manner is generally used for producing a GO thin film by casting or spin coating and drying.
- a method of ultracentrifuging the aqueous dispersion and powdering the precipitate by heating and drying is used.
- GO prepared by the Hummers method is usually obtained in the form of a dispersion.
- the adsorbent obtained by simply drying the dispersion has an amount of adsorbing water vapor of less than 10 mmol / g, and the amount of water vapor that can be separated at a time is small. Therefore, the adsorbent obtained by the above method is not sufficient as an adsorbent used for a method of separating light water or heavy water on an industrial scale.
- the number of moles of light water and the number of moles of heavy water adsorbed on the above-mentioned adsorbent are the same. Therefore, the difference between the amounts of light water and heavy water adsorbed is almost the same as the difference in the molecular weight, and there is room for improvement in the above adsorbent from the viewpoint of separation efficiency.
- the present disclosure aims to provide a graphene oxide adsorbent having a large maximum adsorption amount of a substance to be adsorbed.
- the present disclosure also aims to provide a method for producing a graphene oxide adsorbent as described above.
- One aspect of the present disclosure includes a plurality of layered graphene oxides overlapping each other, an interlayer material interposed between the plurality of layered graphene oxides, and pores formed by the plurality of layered graphene oxides and the interlayer material. To provide a graphene oxide adsorbent.
- the graphene oxide adsorbent can adsorb a gas on both exposed surfaces of the layered graphene oxide by partially having an interlayer material between the layers of the layered graphene oxide. That is, the effective surface area of the graphene oxide adsorbent can be increased, and the amount of the adsorption target substance can be increased.
- the interlayer material may include at least one selected from the group consisting of water, methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide, acetonitrile, dimethylsulfoxide, and hexane.
- the gap between the layered graphene oxides can be more easily controlled.
- the distance between the layered graphene oxides constituting the obtained graphene oxide adsorbent is an optimal interlayer distance for adsorbing a gas containing the compound. Can have. By such an action, the compound exhibits specific adsorption to the compound. In other words, by selecting a compound constituting the interlayer substance according to the compound to be adsorbed, the selectivity to the compound can be further improved.
- the interlayer distance of the layered graphene oxide may be 0.335 to 2.50 nm.
- the above-mentioned graphene oxide adsorbent may be used to adsorb the same substance as the above-mentioned interlayer substance.
- the inter-layer substance in the graphene oxide adsorbent is the same as the substance adsorbed using the graphene oxide adsorbent (the substance to be adsorbed)
- the distance between the layered graphene oxides in the graphene oxide adsorbent is more suitable for the substance to be adsorbed. Because of the presence of voids, the amount of adsorption and the selectivity can be compatible at a higher level.
- One aspect of the present disclosure provides a method for separating a substance, comprising a step of bringing a gas containing a substance to be adsorbed and another substance into contact with the above-mentioned graphene oxide adsorbent, and adsorbing the substance to be adsorbed. I do.
- One aspect of the present disclosure includes a step of freeze-drying a solvent containing a substance to be an interlayer substance and a graphene oxide dispersion containing layered graphene oxide to obtain a graphene oxide adsorbent by reducing the content of the solvent.
- a method for producing a graphene oxide adsorbent is provided.
- the method for producing a graphene oxide adsorbent includes preparing a graphene oxide adsorbent while maintaining the interlayer material between the layered graphene oxides by freeze-drying the layered graphene oxide while including a substance to be an interlayer material. Can be.
- the obtained graphene oxide adsorbent can adsorb a gas on the exposed surfaces on both surfaces of the layered graphene oxide by partially having an interlayer substance between the layers of the layered graphene oxide.
- the method for producing the graphene oxide adsorbent it is possible to produce a graphene oxide adsorbent having a large effective surface area, and the obtained graphene oxide adsorbent has an excellent maximum adsorption amount to the substance to be adsorbed. Have.
- the interlayer material may include at least one selected from the group consisting of water, methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide, acetonitrile, dimethylsulfoxide, and hexane.
- the content of the solvent may be reduced so that the interlayer distance of the layered graphene oxide is 0.335 to 2.50 nm.
- FIG. 1 is a schematic sectional view showing an example of the graphene oxide adsorbent.
- FIG. 2 is a schematic diagram for explaining an example of a method for producing a graphene oxide adsorbent.
- FIG. 3 is an adsorption isotherm showing the amount of light water and heavy water adsorbed on the graphene oxide adsorbent.
- FIG. 4 is an adsorption isotherm showing the adsorption amount of light water and heavy water after the graphene oxide adsorbent is heated at 80 ° C. to deactivate it.
- FIG. 5 is a graph showing a thermogravimetric analysis of the graphene oxide adsorbent.
- FIG. 6 is a schematic diagram for explaining a conventional method for producing a graphene oxide adsorbent by the modified Hummers method.
- graphene oxide in this specification is a material in which an oxygen-containing functional group is bonded to a monolayer of graphite.
- the above-mentioned graphene oxide may be referred to as a layered graphene oxide.
- the oxygen-containing functional group include a hydroxyl group, a carbonyl group, a carboxy group, and an epoxy group.
- One embodiment of the graphene oxide adsorbent includes a plurality of layered graphene oxides overlapping each other, an interlayer material interposed between the plurality of layered graphene oxides, and a pore formed of the plurality of layered graphene oxides and the interlayer material.
- FIG. 1 is a schematic cross-sectional view showing an example of a graphene oxide adsorbent.
- the graphene oxide adsorbent 10 has a plurality of layered graphene oxides 2 and an interlayer material 4 interposed between the layered graphene oxides.
- the graphene oxide adsorbent 10 has pores composed of the above-described layered graphene oxide 2 and the interlayer substance 4. By providing the pores, the graphene oxide adsorbent 10 can adsorb gas on the exposed surfaces on both surfaces of the layered graphene oxide 2.
- a compound of the same type as the interlayer material and a compound having the same molecular size as the interlayer material are likely to enter the pores formed by the interlayer material.
- a compound having the same molecular size as the interlayer material for example, a compound of the same diameter
- the graphene oxide adsorbent is a graphene oxide adsorbent which is formed by laminating graphene oxide and is used for adsorbing a substance. It can also be characterized as having an interlaminar adsorbing substance that forms pores into which the substance enters.
- the graphene oxide adsorbent has pores into which the substance to be adsorbed is formed by maintaining a predetermined distance between the graphene oxide layers by an interlayer substance. Since the pores serve as spaces into which the substance to be adsorbed enters, the adsorption performance of the graphene oxide adsorbent can be greatly improved.
- the interlayer material 4 may be composed of a single molecule or may include a cluster composed of a plurality of molecules.
- the selectivity of the substance to be adsorbed can be further improved.
- the interlayer substance 4 includes a cluster composed of a plurality of molecules, the interlayer distance of the layered graphene oxide 2 tends to increase, so that the maximum adsorption amount of the adsorption target substance can be further improved.
- the interlayer material 4 is, for example, at least one selected from the group consisting of water, methanol, ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF), acetonitrile (MeCN), dimethylsulfoxide (DMSO), and hexane. May be included.
- the interlayer material may be any of water, methanol, ethanol, acetone, THF, DMF, MeCN, DMSO, or hexane.
- the interlayer distance of the layered graphene oxide can be adjusted according to the molecular diameter of the interlayer material or the diameter of the cluster, it is possible to control the selectivity and the amount of the adsorbed material.
- the selected interlayer material can provide an optimum interlayer distance for itself to be adsorbed
- the graphene oxide adsorbent has a specific adsorption to the same material as the constituent interlayer material. You can indicate the quantity. As a result, the selectivity between the substance to be adsorbed and another substance can be improved.
- the content of the interlayer material 4 in the graphene oxide adsorbent 10 may be, for example, 1% by mass or more based on the graphene oxide adsorbent 10.
- the lower limit of the content of the interlayer material 4 is within the above range, the interlayer material 4 sufficiently remains between the layered graphene oxides, and the maximum amount of the substance to be adsorbed to the graphene oxide adsorbent 10 is further improved. be able to.
- the content of the interlayer substance 4 in the graphene oxide adsorbent 10 may be, for example, 45% by mass or less based on the graphene oxide adsorbent 10.
- the content of the interlayer material 4 in the graphene oxide adsorbent 10 may be adjusted within the above range, and may be, for example, 1 to 45% by mass based on the graphene oxide adsorbent 10.
- the water content in the graphene oxide adsorbent 10 may be, for example, 1% by mass or more and 20% by mass or less based on the graphene oxide adsorbent 10. Good.
- the water content in the graphene oxide adsorbent 10 may be adjusted within the above range, and may be, for example, 1 to 20% by mass based on the graphene oxide adsorbent 10.
- the content of ethanol in the graphene oxide adsorbent 10 may be, for example, 1.5% by mass or more, and 40% by mass based on the graphene oxide adsorbent 10. It may be: The content of ethanol in the graphene oxide adsorbent 10 may be adjusted within the above range, and may be, for example, 1.5 to 40% by mass based on the graphene oxide adsorbent 10.
- the content of acetone in the graphene oxide adsorbent 10 may be, for example, 3% by mass or more and 45% by mass or less based on the graphene oxide adsorbent 10. May be.
- the content of acetone in the graphene oxide adsorbent 10 may be adjusted within the above range, and may be, for example, 3 to 45% by mass based on the graphene oxide adsorbent 10.
- the selected interlayer material can provide an optimum interlayer distance for adsorbing the selected above-mentioned compound. Shows specific adsorption for the same substance as the substance. As a result, the selectivity between the substance to be adsorbed and another substance can be improved. That is, the graphene oxide adsorbent can be suitably used to adsorb the same substance as the above-mentioned interlayer substance.
- the interlayer distance of the layered graphene oxide may be, for example, 0.335 to 2.50 nm.
- the interlayer distance of graphene oxide due to the interposition of the above-mentioned interlayer material is 0.335 to 2.50 nm, which is the distance between carbon atom centers, a large pore volume can be provided, and the selectivity of the substance to be adsorbed can be improved. And a large amount of the substance to be adsorbed can be adsorbed while increasing the water content.
- the distance is not the distance between the surfaces of the layered graphene oxide but the distance between the atom centers of the carbon atoms constituting the layered graphene oxide facing each other, and is a value measured by X-ray analysis.
- the graphene oxide adsorbent 10 is suitable as an adsorbent for light water.
- the interlayer distance is 0.335 nm or more, the amount of light water adsorbed can be improved.
- the interlayer distance is equal to or less than 2.50 nm, an increase in the amount of adsorption of heavy water, which is not a substance to be adsorbed, can be suppressed.
- the above-mentioned graphene oxide adsorbent can be manufactured, for example, by the following manufacturing method.
- One embodiment of a method for manufacturing a graphene oxide adsorbent is a method for freeze-drying a graphene oxide dispersion containing a solvent containing a substance to be an interlayer substance and a layered graphene oxide, and reducing the content of the solvent to obtain a graphene oxide.
- a step of obtaining an adsorbent is a method for freeze-drying a graphene oxide dispersion containing a solvent containing a substance to be an interlayer substance and a layered graphene oxide, and reducing the content of the solvent to obtain a graphene oxide.
- a graphene oxide dispersion containing a solvent containing a substance to be an interlayer substance and layered graphene oxide may be a dispersion prepared in advance or may be separately prepared. That is, the method for producing a graphene oxide adsorbent may further include a step of dispersing the graphene oxide in a solvent containing the substance to be the interlayer substance.
- the solvent contained in the dispersion contains a substance that becomes an interlayer substance in the graphene oxide adsorbent.
- the substance serving as the interlayer substance include at least one selected from the group consisting of water, methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide, acetonitrile, dimethylsulfoxide, and hexane.
- the dispersion may further include other substances in addition to the solvent containing the substance to be an interlayer substance and the layered graphene oxide.
- the dispersion preferably contains only a solvent containing a substance to be an interlayer substance and layered graphene oxide.
- freeze-drying is a method of drying after freezing a solvent, and specifically means drying at a temperature lower than the freezing point of the substance to be an interlayer substance. Lyophilization is generally performed under reduced pressure. When freeze-drying is performed at a temperature below the freezing point, vacuum drying is preferably performed from the viewpoint of easy drying.
- freeze-drying can be performed at 0 ° C. or lower, which is the freezing point of water at normal pressure.
- the temperature may be, for example, ⁇ 5 ° C. or lower, ⁇ 10 ° C. or lower, ⁇ 30 ° C. or lower, or ⁇ 40 ° C. or lower, in order to freeze more reliably in a vacuum state.
- freeze-drying is performed at a temperature of ⁇ 40 ° C. or less, drying can be performed more quickly.
- the freeze-drying temperature and time can be adjusted according to the substance to be an interlayer substance.
- the solvent contains light water (water)
- the freeze-drying temperature when the solvent contains light water within the above range, light water as an interlayer substance is vaporized, the graphene oxide adsorbent is deactivated, and the performance is comparable to that of the conventional graphene oxide adsorbent. Can be avoided.
- the solvent contains light water (water), for example, even when drying at a temperature of 60 ° C.
- a method for producing a graphene oxide adsorbent having an interlayer adsorbent that maintains a predetermined distance between layers of graphene oxide comprising: a dispersing step of dispersing graphene oxide in a solvent that is the interlayer material. Drying the graphene oxide dispersed in the solvent as the interlayer material at a temperature equal to or lower than the freezing point of the solvent as the interlayer material.
- intercalation method in which a layered graphene oxide is laminated to form a solid and then a specific substance (intercalant) is introduced between the layers, the types of intercalants are limited.
- elements or substances such as metals, acids, halogens, and metal halides can be easily intercalated by a conventional intercalation method, but substances other than the above are intercalated between the layered graphene oxides. It was difficult to do.
- the layers are usually filled with an intercalant, and a gap such as a pore is not formed.
- the interlayer material separates the layers of the layered graphene oxide by the size of the molecular size or the size of the molecular cluster and connects them like a pillar, thereby forming pores and forming voids into which the substance to be adsorbed enters. Can be provided.
- the graphene oxide adsorbent obtained by the above production method can be suitably used for a method for separating substances.
- One embodiment of the method for separating a substance includes a step of bringing a gas containing a substance to be adsorbed and another substance into contact with the above-mentioned graphene oxide adsorbent, and adsorbing the substance to be adsorbed.
- the substance is desirably supplied to the graphene oxide adsorbent in a gaseous state.
- Example 1 A graphene oxide adsorbent was manufactured by the method shown in FIG. First, 0.5 g of graphite powder was measured and placed in a container, and 2.5 g of phosphoric acid aqueous solution (H 3 PO 4 aqueous solution, concentration: 85% by mass), 20 g of concentrated sulfuric acid (H 2 SO 4 , concentration: 97 mass) %) And 2.5 g of potassium permanganate (KMnO 4 ) powder to prepare a mixed solution, and the mixture was stirred at 35 ° C. for 2 hours. Next, 50 mL of water (H 2 O) was added to the above mixed solution, followed by thorough stirring.
- H 3 PO 4 aqueous solution concentration: 85% by mass
- concentrated sulfuric acid H 2 SO 4 , concentration: 97 mass
- KMnO 4 potassium permanganate
- the GO solution was freeze-dried. Specifically, first, a rectangular parallelepiped made of copper was placed in an insulated container, and liquid nitrogen was charged. The amount of liquid nitrogen was adjusted such that the upper surface of the rectangular parallelepiped of copper was approximately 1 cm above the liquid surface of liquid nitrogen. A straw-shaped plastic tube having a diameter (inner diameter) of 5 mm and a length of 10 cm was erected on the upper surface of a copper rectangular parallelepiped, and the GO solution was poured into the tube to freeze the GO solution in the tube. The frozen GO solution was extruded from the tube and placed in a freeze dryer and freeze-dried.
- the freeze-drying was performed using a vacuum freeze-dryer VFD-03 (manufactured by AS ONE Corporation) at -10 ° C. and a vacuum of 133 Pa for 12 hours. Thus, a solid graphene oxide adsorbent (GO adsorbent) was obtained.
- FIG. 3 is an adsorption isotherm showing the amount of light water and heavy water adsorbed on the graphene oxide adsorbent.
- the vertical axis of the adsorption isotherm indicates the amount of water adsorption (Water adsorption volume [mmol / g]), and the horizontal axis indicates the pressure of water vapor (P / P 0 [ ⁇ ]) during adsorption equilibrium.
- P / P 0 [ ⁇ ] the pressure of water vapor
- a black circle indicates the amount of light water adsorbed during adsorption
- a white circle indicates the amount of light water adsorbed during desorption
- a black triangle indicates heavy water during adsorption.
- the adsorption amount and the white triangle indicate the adsorption amount of heavy water at the time of desorption.
- the GO adsorbent of Example 1 can selectively adsorb the target substance to be adsorbed over the conventional GO adsorbent. That is, FIG. 3 shows that when water vapor is supplied and adsorbed to the GO adsorbent, light water adsorbs 23% more in molar ratio than heavy water in the amount of water vapor adsorbed during saturated adsorption.
- FIG. 3 shows that the GO adsorbent of Example 1 can adsorb more substances to be adsorbed per unit amount than in the past.
- the amount of water vapor adsorbed by a conventional adsorbent obtained by simply drying a graphene oxide dispersion prepared by the Hummers method is less than 10 mmol / g, whereas the amount shown in FIG.
- the GO adsorbent of Example 1 has an adsorbed amount of light water at a saturated vapor pressure of more than 30 mmol / g, and it can be confirmed that the adsorbed amount is significantly improved from the conventional GO adsorbent.
- the GO adsorbent is derived from having an interlayer substance between layers of the layered graphene oxide. That is, the interlayer material maintains a predetermined distance between the layers of the layered graphene oxide by maintaining a predetermined distance between the layers by separating the layers by the size of the molecule or the size of the molecular cluster and connecting them like columns, and the GO adsorbent has pores. It is considered that the above effect was obtained because the (gap) was formed. In the GO adsorbent of Example 1, light water slightly remaining after freeze-drying functions as an interlayer substance.
- the GO adsorbent of Example 1 ordinary water was used as a solvent for the GO dispersion, but light water functions as an interlayer substance because 99% or more of the water is light water. For this reason, as shown in FIG. 3, the adsorption amount of light water at the saturated vapor pressure is larger than the adsorption amount of heavy water.
- lighter water with higher purity may be used as the solvent. By doing so, it becomes easier for the same light water as the inter-layer adsorbent to enter between the GO layers, and both the adsorption amount and the selectivity of the light water can be improved.
- FIG. 5 is a graph showing a thermogravimetric analysis of the graphene oxide adsorbent.
- the mass decreased on average about 5% while heating the GO adsorbent to 0-100 ° C. This is because water as an interlayer substance was vaporized and released by heating. Since the water molecules adsorbed between the layers are in a more stable state than ordinary water due to the intermolecular interaction with the layered graphene oxide, the GO adsorbent is heated to 160 ° C. to completely desorb. Is maintained until It is shown that the mass of the GO adsorbent gradually decreases between 100 ° C. and 160 ° C.
- Example 1 The GO adsorbent of Example 1 was heated at 80 ° C. for 120 minutes to obtain a graphene oxide adsorbent. Such an operation corresponds to a normal drying operation performed in place of the freeze-drying of Example 1. The adsorption performance of the obtained graphene oxide adsorbent on light water and heavy water was evaluated. FIG. 4 shows the results.
- FIG. 4 is an adsorption isotherm showing the amount of adsorption of light water and heavy water after the GO adsorbent of Example 1 was deactivated by heating at 80 ° C. for 120 minutes.
- the black circle (solid line) indicates the amount of light water absorbed during adsorption
- the white circle (dashed line) indicates the amount of light water absorbed during desorption
- the black triangle (solid line) indicates the amount of heavy water absorbed during adsorption
- white The painted triangle (dashed line) indicates the amount of heavy water adsorbed during desorption.
- the GO adsorbent heated to 80 ° C. and having lost a part of light water as an interlayer substance has a light water adsorption amount at a saturated vapor pressure of more than 30 mmol / g in FIG. 3 to 8 mmol in FIG. / G was confirmed to have decreased.
- the heat-treated GO adsorbent also adsorbs more light water than heavy water, indicating that the GO adsorbent has selectivity for light water. However, it is considered that this is because a part of light water which is an interlayer substance remains in the GO adsorbent.
- the ultracentrifuged precipitate was dissolved in hydrochloric acid, and further ultracentrifuged.
- the obtained precipitate was dissolved in pure water and ultracentrifuged to obtain a precipitate.
- the liquid property was made neutral to obtain a layered graphene oxide dispersion aqueous solution.
- the dispersion aqueous solution was ultracentrifuged, and the precipitate was heated and dried to prepare a graphene oxide adsorbent.
- the same evaluation as in Example 1 was performed on the obtained graphene oxide adsorbent, and it was confirmed that the maximum amount of adsorption to water vapor was smaller than that of the adsorbent prepared in Comparative Example 1.
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Abstract
Description
図2に示す方法で、グラフェンオキサイド吸着材を製造した。まず、容器に、0.5gのグラファイト粉末を測り取り、2.5gのリン酸水溶液(H3PO4水溶液、濃度:85質量%)、20gの濃硫酸(H2SO4、濃度:97質量%)、2.5gの過マンガン酸カリウム(KMnO4)粉末を加え混合溶液を調製して、35℃で2時間撹拌した。次いで、上記混合溶液に、50mLの水(H2O)を加え、よく撹拌した。その後、上記混合溶液に、1mLの過酸化水素水(H2O2、濃度:10質量%)を加え、25℃で30分間撹拌した。この過程で、グラファイトのグラフェン層を酸化し、表面官能基を生じさせ、さらに酸化したグラフェン層をグラファイトからはく離させることによって層状グラフェンオキサイドを含む溶液を調製した。
得られたグラフェンオキサイド吸着材の軽水及び重水に対する吸着性能を評価した。結果を図3に示す。図3は、グラフェンオキサイド吸着材における、軽水と重水との吸着量を示す吸着等温線である。当該吸着等温線の縦軸は水の吸着量(Water adsorption volume[mmol/g])を示し、横軸は吸着平衡時の水蒸気の圧力(P/P0[-])を示す。図3中、黒塗りの円(実線)は吸着時の軽水の吸着量、白抜きの円(破線)は脱離時の軽水の吸着量、黒塗りの三角形(実線)は吸着時の重水の吸着量、白塗りの三角形(破線)は脱離時の重水の吸着量を示している。
実施例1のGO吸着材の安定性を確認するため、熱重量測定を行った。熱重量測定においては、GO吸着材を静置し、1分ごとにN2ガスを150mL供給するとともに、1分ごとに系の温度を室温から1Kずつ上昇させて行った。実験は3つのサンプルで行った。結果を図5に示す。
実施例1のGO吸着材を80℃で120分間加熱処理して、グラフェンオキサイド吸着材を得た。かかる操作は、実施例1の凍結乾燥に代えて、通常の乾燥操作を行ったものに相当する。得られたグラフェンオキサイド吸着材の軽水及び重水に対する吸着性能を評価した。結果を図4に示す。
以下に示すモディファイド・ハマーズメソッドを用いて、グラフェンオキサイド分散液を調製し、これを加熱乾燥することによってグラフェンオキサイド吸着材を得た。
Claims (8)
- 互いに重なり合う複数の層状グラフェンオキサイドと、
前記複数の層状グラフェンオキサイド間に介在する層間物質と、
前記複数の層状グラフェンオキサイドと前記層間物質とで構成される細孔と、を有する、グラフェンオキサイド吸着材。 - 前記層間物質が、水、メタノール、エタノール、アセトン、テトラヒドロフラン、ジメチルホルムアミド、アセトニトリル、ジメチルスルホキシド、及びヘキサンからなる群より選択される少なくとも1種を含む、請求項1に記載のグラフェンオキサイド吸着材。
- 前記層状グラフェンオキサイドの層間距離が0.335~2.50nmである、請求項1又は2に記載のグラフェンオキサイド吸着材。
- 前記層間物質と同じ物質を吸着させるために用いられる、請求項1~3のいずれか一項に記載のグラフェンオキサイド吸着材。
- 請求項1~3のいずれか一項に記載のグラフェンオキサイド吸着材に、吸着対象となる物質とその他の物質とを含む気体を接触させ、吸着対象となる物質を吸着させる工程を含む、物質の分離方法。
- 層間物質となる物質を含有する溶媒と、層状グラフェンオキサイドとを含むグラフェンオキサイド分散液を凍結乾燥し、前記溶媒の含有量を低減してグラフェンオキサイド吸着材を得る工程を有する、グラフェンオキサイド吸着材の製造方法。
- 前記層間物質が、水、メタノール、エタノール、アセトン、テトラヒドロフラン、ジメチルホルムアミド、アセトニトリル、ジメチルスルホキシド、及びヘキサンからなる群より選択される少なくとも1種を含む、請求項6に記載のグラフェンオキサイド吸着材の製造方法。
- 前記層状グラフェンオキサイドの層間距離が0.335~2.50nmとなるように前記溶媒の含有量を低減する、請求項6又は7に記載のグラフェンオキサイド吸着材の製造方法。
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CN201980054544.7A CN112584923A (zh) | 2018-08-23 | 2019-08-21 | 氧化石墨烯吸附材料及其制造方法 |
US17/268,354 US20210300761A1 (en) | 2018-08-23 | 2019-08-21 | Graphene oxide adsorbent and method for producing same |
EP19853010.7A EP3842137A4 (en) | 2018-08-23 | 2019-08-21 | GRAPHEMOXIDE ADsorbent AND PROCESS FOR ITS PRODUCTION |
AU2019324724A AU2019324724A1 (en) | 2018-08-23 | 2019-08-21 | Grapheme oxide adsorbent and method for producing same |
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