CN116059978B - Graphene aerogel with directional ordered pore structure, and preparation method and application thereof - Google Patents
Graphene aerogel with directional ordered pore structure, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000004964 aerogel Substances 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- 239000011148 porous material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920001661 Chitosan Polymers 0.000 claims abstract description 65
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000007710 freezing Methods 0.000 claims abstract description 24
- 230000008014 freezing Effects 0.000 claims abstract description 24
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 238000006722 reduction reaction Methods 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 5
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000001116 FEMA 4028 Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- 239000004317 sodium nitrate Substances 0.000 description 2
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- 238000001132 ultrasonic dispersion Methods 0.000 description 2
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- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
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Classifications
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- 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
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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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- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B01J20/28047—Gels
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
The invention belongs to the technical field of porous material preparation, and particularly relates to graphene aerogel with a directional ordered pore structure, and a preparation method and application thereof. According to the invention, the graphene oxide is modified by adopting the polyethyleneimine and the chitosan, and the addition amount of the two solvents is controlled, so that the graphene oxide has a weak crosslinking effect, can not generate hydrogel after hydrothermal reaction, and is still a suspension product. Then selecting a specific mould for freezing and vacuum drying treatment, wherein the heat conductivity coefficient of the bottom of the mould is larger than that of the side wall, the bottom of the mould is contacted with a cold source, the bottom of the slurry is supercooled, and the top of the slurry is exposed to the air to form a temperature gradient, in the freezing process, ice crystals firstly form ice cores at the bottom of the slurry, then grow upwards along the direction (vertical direction) of the temperature gradient, and finally highly ordered straight holes are obtained after sublimation, so that the obtained product has high specific surface area and high porosity and can provide rich CO 2 Adsorption sites which are more beneficial to CO adsorption 2 。
Description
Technical Field
The invention belongs to the technical field of porous material preparation, and particularly relates to graphene aerogel with a directional ordered pore structure, and a preparation method and application thereof.
Background
With the rapid development of economy and society, CO caused by fossil energy combustion and human activities 2 The discharge amount rises year by year and is changed from CO 2 Climate change by isothermal chamber gases has become one of the most serious challenges facing humans in the 21 st century, and active management of climate change has become a global consensus and trend.
Carbon dioxide capture, utilization and sequestration (CCUS) technology has become the primary area of concern in various countries. CCUS refers to the treatment of CO 2 Separation from, or direct use of, the source of emissions, or sequestration, to effect CO 2 The technical process of emission reduction is the only technical choice for realizing low carbonization utilization of fossil energy. Taking into account CO 2 The CO in the greenhouse gas is taken as a cheap and easily available carbon source 2 Changing waste into valuables has important strategic significance for alleviating greenhouse effect and reducing dependence on fossil energy.
Currently, CO 2 The trapping method of (a) mainly comprises a solvent absorption method, a cryogenic separation method, an adsorption separation method and the like. Among them, the solvent absorption method and the cryogenic separation method have the problems of high energy consumption, high separation cost and the like, and the adsorption separation method has attracted a great deal of attention by the advantages of simple and flexible equipment, low cost and wide application temperature range, and has become a relatively popular research topic in the world at present. However, solid adsorbent materials such as zeolite molecular sieves, metal Organic Frameworks (MOFs), porous polymers, and the like, which have been developed so farThe adsorbent generally has good adsorption effect under high pressure environment, and the adsorption amount and adsorption capacity are reduced under low pressure condition. To expand CO 2 The application range of the trapping technology is significant in researching and developing a novel high-efficiency solid adsorption material suitable for a low-pressure environment.
The graphene aerogel is high-strength oxidized aerogel, has the characteristics of high elasticity and strong adsorption, and has a wide application prospect. However, the graphene aerogel prepared by the existing method is formed by self-assembling graphene oxide under the action of a cross-linking agent, the pore structure is irregular, closed pores are easy to appear, and the specific surface area and the porosity are required to be further improved.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the pore structure of the graphene oxide aerogel in the prior art is irregular, closed pores are easy to occur, the specific surface area and the porosity are required to be further improved, and the like, so that the graphene aerogel with the directional ordered pore structure, and the preparation method and the application thereof are provided.
Therefore, the invention provides the following technical scheme:
the invention provides a preparation method of graphene aerogel with a directional ordered pore structure, which comprises the following steps:
dispersing graphene oxide into water to obtain a GO solution;
dissolving polyethylenimine in a phosphate buffer solution or an ethanol solution to obtain a PEI solution;
dissolving chitosan in acetic acid to obtain CS solution;
adding the PEI solution and the CS solution into the GO solution, uniformly mixing, and performing hydrothermal reduction reaction to obtain Gr-PEI-CS composite slurry;
adding the Gr-PEI-CS composite slurry into a mold, freezing, and vacuum drying to obtain graphene aerogel with an oriented ordered pore structure;
wherein, the coefficient of heat conductivity of mould bottom is greater than the coefficient of heat conductivity of lateral wall.
Optionally, the heat conductivity coefficient of the side wall of the die is 0.2-10W/(m.K); for example, the material of the side wall may be plastic;
the heat conductivity coefficient of the bottom of the die is 200-600W/(m.K); for example, the material of the bottom of the mold may be metallic copper.
Alternatively, the method is characterized in that the temperature of the hydrothermal reduction reaction is 100-250 ℃ and the reaction time is 10-20 h. For example, the hydrothermal reduction reaction may be at a temperature of 100 ℃,120 ℃,140 ℃,150 ℃,170 ℃,180 ℃,200 ℃,210 ℃,230 ℃,240 ℃,250 ℃; the reaction time may be 10h,11h,12h,13h,14h,15h,16h,17h,18h,19h,20h.
Optionally, the freezing temperature is-10 to-90 ℃ and the time is 0.5 to 2 hours; for example, the freezing temperature may be-10 ℃, -20 ℃, -30 ℃, -40 ℃, -50 ℃, -60 ℃, -70 ℃, -80 ℃, -90 ℃.
The vacuum drying time is 12-24 h, the pressure is 3-10 Pa, and the drying temperature is-40-15 ℃.
Optionally, the concentration of the GO solution is 1-10 g/L, and the pH is 5-7; optionally, the concentration of the GO solution is 1g/L,2g/L,3g/L,4g/L,5g/L,6g/L,7g/L,8g/L,9g/L and 10g/L.
Optionally, dispersing for 30-120 min under ultrasonic condition.
Optionally, the concentration of the PEI solution is 0.1-1 mg/mL. For example, the concentration of the PEI solution is 0.1mg/mL,0.2mg/mL,0.3mg/mL,0.4mg/mL,0.5mg/mL,0.6mg/mL,0.7mg/mL,0.8mg/mL,0.9mg/mL,1mg/mL.
The concentration of the CS solution is 0.1-1 mg/mL, and the mass concentration of the acetic acid is 1-10%; for example, the CS solution may have a concentration of 0.1mg/mL,0.2mg/mL,0.3mg/mL,0.4mg/mL,0.5mg/mL,0.6mg/mL,0.7mg/mL,0.8mg/mL,0.9mg/mL,1mg/mL.
Optionally, the mass ratio of the PEI solution to the CS solution to the GO solution is (0.1-0.6) based on the mass of the PEI, the CS and the GO: (0.1-0.6): (1-6).
Optionally, the hydrothermal reduction reaction further comprises a step of water washing;
optionally, the GO-PEI-CS composite slurry with the concentration of 5-10 mg/mL is prepared by water after washing.
The invention also provides the graphene aerogel with the directional ordered pore structure, which is prepared by the preparation method.
Alternatively, the specific surface area is 300-800 m 2 And/g, the porosity is 50-90%.
The invention also provides application of the graphene aerogel with the oriented ordered pore structure in carbon dioxide adsorption.
Specifically, the preparation method of the graphene aerogel with the directional ordered pore structure can comprise the following steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method. The modified Hummers method involves a two-step oxidation process of pre-oxidation and re-oxidation, with potassium permanganate and concentrated sulfuric acid being used primarily to modify the oxidation process of graphite. Adding the graphite oxide product into deionized water, fully stirring, performing ultrasonic dispersion, centrifuging to remove sediment, obtaining a GO solution with a certain concentration, and adjusting the pH value to be 7.0.
(2) A solution of Polyethylenimine (PEI) and Chitosan (CS) was formulated. A PEI solution was prepared by dissolving an amount of polyethylenimine in PBS (phosphate buffered saline, ph=7.0); adding a certain amount of Chitosan (CS) into a certain amount of acetic acid, stirring and dispersing to prepare CS solution.
(3) The Gr-PEI-CS compound is prepared by adopting a hydrothermal reduction method. Adding a certain amount of Polyethyleneimine (PEI) solution and Chitosan (CS) solution into a certain volume of GO solution, fully stirring, then placing into a stainless steel autoclave with a lining of polytetrafluoroethylene, carrying out hydrothermal reduction at a certain temperature, taking out the product, naturally cooling, washing with deionized water, and then adding deionized water to prepare Gr-PEI-CS composite slurry with a certain concentration.
In the preparation of Graphene Oxide (GO) by adopting the improved Hummers method, the reaction temperature in the pre-oxidation process for preparing GO by adopting the improved Hummers method can be 80 ℃ for 3-10 hours; the reaction temperature can be 35 ℃ and the duration is 1-10 h in the reoxidation process in the preparation of GO by the improved Hummers method.
The specific operation is as follows: adding 40-60 mL of concentrated sulfuric acid (98 wt%), 5.0-10.0 g of potassium persulfate and 5.0-10.0 g of phosphorus pentoxide into a round-bottomed flask in sequence, and vigorously stirring to obtain a clear solution; heating in water bath to 80+/-2 ℃, adding 4.0-8.0 g of natural graphite powder for reaction for 3-8 h, cooling to room temperature after the reaction is finished, and adding 100-300 mL of deionized water for slow dilution; and (3) carrying out suction filtration on the reactant, washing to neutrality, and drying at 40-60 ℃ for 12-24 h to obtain the graphite pre-oxide. Weighing 100-180 mL of concentrated sulfuric acid, adding the concentrated sulfuric acid into a round-bottom flask, adding 3.0-8.0 g of the graphite pre-oxide under the stirring condition, then adding 13.0-20.0 g of potassium permanganate for a small amount for multiple times, stirring for reaction, and strictly controlling the temperature within 20 ℃; then adding 3.0g of sodium nitrate, and carrying out water bath reaction for 1-4 h at the temperature of 35+/-2 ℃; adding 200-500 mL deionized water for dilution, and continuously reacting in a water bath at 35+/-2 ℃ for 1-4 h; adding 3-20 mL of hydrogen peroxide with mass fraction of 35wt%, and obtaining the graphite oxide after the brown reaction liquid changes into bright yellow. 50-200 mL of 10vol% diluted hydrochloric acid is added into the graphite oxide, the mixture is fully stirred, and then deionized water is used for washing to neutrality, so that the GO product is obtained.
The technical scheme of the invention has the following advantages:
according to the preparation method of the graphene aerogel with the directional ordered pore structure, graphene oxide, polyethyleneimine (PEI) and Chitosan (CS) are used as raw materials, and a hydrothermal reduction method and a freeze drying method are adopted to prepare the composite graphene aerogel (Gr-PEI-CS) with high specific surface area and high porosity. The invention adopts Polyethyleneimine (PEI) and Chitosan (CS) to modify graphene oxide, and the main purpose of PEI and CS is to introduce amino groups into graphene oxide sheets so as to improve CO 2 Is used for the adsorption capacity of the catalyst; however, the invention controls the addition amount of the two solvents, so that the two solvents have weak crosslinking effect, and can not generate hydrogel after hydrothermal reaction, and the hydrogel is still a suspension product. Then selecting a specific mould for freezing and vacuum drying treatment, wherein the heat conductivity coefficient of the bottom of the mould is larger than that of the side wall, the bottom of the mould is contacted with a cold source, the bottom of the slurry is supercooled, the top of the slurry is exposed to the air, a temperature gradient is formed, and during the freezing process, ice crystals are firstly frozen inIce cores are formed at the bottom of the slurry, then the slurry grows upwards along the direction of the temperature gradient (vertical direction), highly ordered straight holes are finally obtained after sublimation, and the obtained product has the advantages of ordered straight holes, high specific surface area and high porosity (50-90 percent), and can provide rich CO 2 Adsorption sites more beneficial to CO 2 At the same time, the mechanical strength of the aerogel is improved; in addition, the preparation method provided by the invention is simple and can be used for large-scale production.
According to the preparation method of the graphene aerogel with the directional ordered pore structure, provided by the invention, through limiting parameters of each step, the graphene oxide aerogel with high directional degree, high porosity and large specific surface can be obtained.
The application of the graphene aerogel with the directional ordered pore structure in carbon dioxide adsorption is applicable to adsorption in a low-pressure environment, and the adsorption quantity of carbon dioxide is 10-105 mg/g.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a longitudinal section scanning electron microscope image of graphene aerogel obtained in example 1 of the present invention;
FIG. 2 is a cross-sectional scanning electron microscope image of graphene aerogel obtained in example 1 of the present invention;
FIG. 3 is a photograph of Gr-PEI-CS composite slurry obtained in example 1 and comparative examples 2 and 3 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method. 50mL of concentrated sulfuric acid, 8.0g of potassium persulfate and 8.0g of phosphorus pentoxide are sequentially added into a round-bottomed flask, and the mixture is vigorously stirred to obtain a clear solution; heating in water bath to 80 ℃, adding 4.0g of natural graphite powder for reaction for 5 hours, cooling to room temperature after the reaction is finished, and adding 200mL of deionized water for slow dilution; and (3) carrying out suction filtration on the reactant, washing to neutrality, and drying at 60 ℃ for 12 hours to obtain the graphite pre-oxide. 140mL of concentrated sulfuric acid is weighed and added into a round-bottom flask, 3.0g of the graphite pre-oxide is added under the stirring condition, then 18.0g of potassium permanganate is added for a plurality of times, stirring is carried out for reaction, and the temperature is strictly controlled within 20 ℃; then adding 3.0g of sodium nitrate, and carrying out water bath reaction for 2 hours at 35 ℃; adding 300mL of deionized water for dilution, and continuously reacting for 2h in a water bath at 35 ℃; adding 10mL of hydrogen peroxide with mass fraction of 35wt%, and obtaining the graphite oxide after the brown reaction liquid is suddenly changed into bright yellow. 100mL of 10vol% diluted hydrochloric acid is added into the graphite oxide, the mixture is fully stirred, and then deionized water is used for washing to neutrality, so that the GO product is obtained.
(2) Adding the GO product into 100mL of deionized water, stirring for 30min, performing ultrasonic dispersion for 2h, centrifuging at 4000rpm for 10min to remove precipitate, obtaining 2g/L of stable dispersed GO solution, and adjusting the pH of the GO solution to 7.0 by adopting 0.5mol/L of NaOH.
(3) A solution of Polyethylenimine (PEI) and Chitosan (CS) was formulated. 200mg of polyethylenimine was dissolved in 1000mL of PBS (phosphate buffered saline, ph=7.0) to prepare a PEI solution; 100mg of Chitosan (CS) was added to 100mL of 1% acetic acid, and the mixture was dissolved and stirred to prepare a CS solution.
(4) The Gr-PEI-CS compound is prepared by adopting a hydrothermal reduction method. PEI solution and CS solution were added to GO solution, PEI: CS: the mass ratio of the GO solute to the nano-powder is 0.3:0.1:1, the mixture is fully stirred for 30min, then the mixture is put into a stainless steel autoclave with a polytetrafluoroethylene lining, the mixture is subjected to hydrothermal reduction for 12h at 200 ℃, the product is taken out and naturally cooled, the product is washed with deionized water for 3 times, and 80mL of deionized water is used for preparing Gr-PEI-CS composite slurry with the concentration of 5 mg/mL.
(5) And integrally preparing Gr-PEI-CS aerogel by adopting a freeze drying method. 8mL of Gr-PEI-CS composite slurry is injected into a self-made hollow cylindrical polytetrafluoroethylene mould, the diameter of the mould is 2cm, the height of the mould is 5cm, and the bottom material is a copper plate. Freezing at-70 ℃ for 1h, and drying at-40-15 ℃ for 12h under the pressure of 5Pa after freezing molding to obtain the Gr-PEI-CS-1 aerogel with highly oriented pore channels.
CO is carried out on Gr-PEI-CS-1 aerogel by adopting a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 101.4mg/g.
Fig. 1 and fig. 2 are longitudinal and cross-sectional Scanning Electron Microscope (SEM) images of the graphene aerogel structure obtained in example 1, and from the images, it can be seen that the graphene aerogel structure has a bottom-up directional communication duct structure. Longitudinal and cross-section Scanning Electron Microscope (SEM) images of products obtained in other embodiments of the present invention are similar and will not be described again.
FIG. 3 is a photograph of Gr-PEI-CS composite slurry obtained in example 1 and comparative examples 2 and 3 (from left to right) of the present invention, from which it can be seen that when beta cyclodextrin and phytic acid are used as cross-linking agents, a shaped graphene aerogel can be obtained after hydrothermal process; however, the self-assembly of the hydrogel by using polyethyleneimine is impossible, and the self-assembly can be performed by a subsequent freeze-drying step.
Example 2
The embodiment provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method. In order to secure comparability between data, the preparation methods of graphene oxide in the following examples and comparative examples are the same as example 1.
(2) A solution of Polyethylenimine (PEI) and Chitosan (CS) was formulated. 200mg of polyethylenimine was dissolved in 1000mL of PBS (phosphate buffered saline, ph=7.0) to prepare a PEI solution; 100mg of Chitosan (CS) was added to 100mL of 1% acetic acid, and the mixture was dissolved and stirred to prepare a CS solution.
(3) The Gr-PEI-CS compound is prepared by adopting a hydrothermal reduction method. PEI solution and CS solution were added to GO solution, PEI: CS: the mass ratio of the GO solute to the nano-powder is 0.2:0.1:1, the mixture is fully stirred for 30min, then the mixture is put into a stainless steel autoclave with a polytetrafluoroethylene lining, the mixture is subjected to hydrothermal reduction for 12h at 200 ℃, the product is taken out and naturally cooled, the product is washed with deionized water for 3 times, and 80mL of deionized water is used for preparing Gr-PEI-CS composite slurry with the concentration of 5 mg/mL.
(4) And integrally preparing Gr-PEI-CS aerogel by adopting a freeze drying method. 8mL of Gr-PEI-CS composite slurry was injected into a self-made round polytetrafluoroethylene mold with a diameter of 2cm and a height of 5cm. Freezing at-70 ℃ for 1h, and drying at-40-15 ℃ for 12h under the pressure of 5Pa after freezing molding to obtain the Gr-PEI-CS-2 aerogel with highly oriented pore channels.
CO is carried out on Gr-PEI-CS-2 aerogel by adopting a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 83.7mg/g.
Example 3
The embodiment provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method, for specific procedures with reference to example 1.
(2) A solution of Polyethylenimine (PEI) and Chitosan (CS) was formulated. 200mg of polyethylenimine was dissolved in 1000mL of PBS (phosphate buffered saline, ph=7.0) to prepare a PEI solution; 100mg of Chitosan (CS) was added to 100mL of 1% acetic acid, and the mixture was dissolved and stirred to prepare a CS solution.
(3) The Gr-PEI-CS compound is prepared by adopting a hydrothermal reduction method. PEI solution and CS solution were added to GO solution, PEI: CS: the mass ratio of the GO solute to the nano-powder is 0.2:0.1:2, the mixture is fully stirred for 30min, then the mixture is put into a stainless steel autoclave with a polytetrafluoroethylene lining, the mixture is subjected to hydrothermal reduction for 12h at 200 ℃, the product is taken out and naturally cooled, the product is washed with deionized water for 3 times, and 80mL of deionized water is used for preparing Gr-PEI-CS composite slurry with the concentration of 5 mg/mL.
(4) And integrally preparing Gr-PEI-CS aerogel by adopting a freeze drying method. 8mL of Gr-PEI-CS composite slurry was injected into a self-made round polytetrafluoroethylene mold with a diameter of 2cm and a height of 5cm. Freezing at-50 ℃ for 1h, and drying at-40-15 ℃ for 12h under the pressure of 5Pa after freezing molding to obtain the Gr-PEI-CS-3 aerogel with highly oriented pore channels.
CO is carried out on Gr-PEI-CS-3 aerogel by adopting a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 58.0mg/g.
Example 4
The embodiment provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method, for specific procedures with reference to example 1.
(2) A solution of Polyethylenimine (PEI) and Chitosan (CS) was formulated. 200mg of polyethylenimine was dissolved in 1000mL of PBS (phosphate buffered saline, ph=7.0) to prepare a PEI solution; 100mg of Chitosan (CS) was added to 100mL of 1% acetic acid, and the mixture was dissolved and stirred to prepare a CS solution.
(3) The Gr-PEI-CS compound is prepared by adopting a hydrothermal reduction method. PEI solution and CS solution were added to GO solution, PEI: CS: the GO solute mass ratio is 0.1:0.1:4, fully stirring for 30min, then putting into a stainless steel autoclave with polytetrafluoroethylene lining, carrying out hydrothermal reduction for 12h at 200 ℃, taking out the product, naturally cooling, washing 3 times with deionized water, and preparing Gr-PEI-CS composite slurry with the concentration of 5mg/mL with 80mL of deionized water.
(4) And integrally preparing Gr-PEI-CS aerogel by adopting a freeze drying method. 8mL of Gr-PEI-CS composite slurry was injected into a self-made round polytetrafluoroethylene mold with a diameter of 2cm and a height of 5cm. And then freezing for 1h at the temperature of minus 50 ℃, and drying for 12h at the temperature of minus 40-15 ℃ under the pressure of 5Pa after freezing molding to obtain the Gr-PEI-CS-4 aerogel with highly oriented pore channels.
CO is carried out on Gr-PEI-CS-4 aerogel by adopting a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 33.9mg/g.
Example 5
The embodiment provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method, for specific procedures with reference to example 1.
(2) A solution of Polyethylenimine (PEI) and Chitosan (CS) was formulated. 200mg of polyethylenimine was dissolved in 1000mL of PBS (phosphate buffered saline, ph=7.0) to prepare a PEI solution; 100mg of Chitosan (CS) was added to 100mL of 1% acetic acid, and the mixture was dissolved and stirred to prepare a CS solution.
(3) The Gr-PEI-CS compound is prepared by adopting a hydrothermal reduction method. PEI solution and CS solution were added to GO solution, PEI: CS: the mass ratio of the GO solute to the nano-powder is 0.2:0.1:1, the mixture is fully stirred for 30min, then the mixture is put into a stainless steel autoclave with a polytetrafluoroethylene lining, the mixture is subjected to hydrothermal reduction for 12h at 160 ℃, the product is taken out and naturally cooled, the product is washed with deionized water for 3 times, and 80mL of deionized water is used for preparing Gr-PEI-CS composite slurry with the concentration of 5 mg/mL.
(4) And integrally preparing Gr-PEI-CS aerogel by adopting a freeze drying method. 8mL of Gr-PEI-CS composite slurry was injected into a self-made round polytetrafluoroethylene mold with a diameter of 2cm and a height of 5cm. Then freezing for 1h at the temperature of minus 60 ℃, drying for 12h at the temperature of minus 40-15 ℃ under 5Pa after freezing molding, and obtaining the Gr-PEI-CS-4 aerogel with highly directional pore channels.
CO is carried out on Gr-PEI-CS-4 aerogel by adopting a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 80.5mg/g.
Comparative example 1
The embodiment provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method, for specific procedures with reference to example 1.
(2) A solution of Polyethylenimine (PEI) and Chitosan (CS) was formulated. 200mg of polyethylenimine was dissolved in 1000mL of PBS (phosphate buffered saline, ph=7.0) to prepare a PEI solution; 100mg of Chitosan (CS) was added to 100mL of 1% acetic acid, and the mixture was dissolved and stirred to prepare a CS solution.
(3) The Gr-PEI-CS compound is prepared by adopting a hydrothermal reduction method. PEI solution and CS solution were added to GO solution, PEI: CS: the GO solute mass ratio is 0.1:0.1:8, fully stirring for 30min, then putting into a stainless steel autoclave with polytetrafluoroethylene lining, carrying out hydrothermal reduction for 12h at 200 ℃, taking out the product, naturally cooling, washing 3 times with deionized water, and preparing Gr-PEI-CS composite slurry with the concentration of 5mg/mL with 80mL of deionized water.
(4) And integrally preparing Gr-PEI-CS aerogel by adopting a freeze drying method. 8mL of Gr-PEI-CS composite slurry was injected into a self-made round polytetrafluoroethylene mold with a diameter of 2cm and a height of 5cm. Then freezing for 1h at the temperature of minus 60 ℃, drying for 12h at the temperature of minus 40-15 ℃ under 5Pa after freezing molding, and obtaining the Gr-PEI-CS-5 aerogel with highly directional pore channels.
CO is carried out on Gr-PEI-CS-5 by a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 16.1mg/g.
Comparative example 2
The comparative example provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method, for specific procedures with reference to example 1.
(2) Beta Cyclodextrin (CD) solutions were formulated. 500mg of beta cyclodextrin was dissolved in 1000mL of deionized water, and dispersed by ultrasound for 1 hour to prepare a CD solution at a concentration of 0.5g/L.
(3) The CD-CS complex is prepared by adopting a hydrothermal reduction method. Slowly add CD solution to GO solution, CD: the mass ratio of GO solute is 1:6, fully stirring for 30min, then placing the mixture into a stainless steel autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reduction for 12h at 200 ℃, taking out the product, naturally cooling, washing with deionized water for 3 times, and drying at room temperature.
CO is carried out on the CD-GO aerogel by adopting a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 21.2mg/g.
Comparative example 3
The comparative example provides a graphene aerogel with a directional ordered pore structure, and the preparation method comprises the following specific steps:
(1) Graphene Oxide (GO) was prepared using a modified Hummers method, for specific procedures with reference to example 1.
(2) Preparing Phytic Acid (PA) solution. 0.7mL of 50% phytic acid solution was diluted 1000-fold with deionized water to prepare a phytic acid solution at a concentration of about 0.5g/L.
(3) The PA-CS compound is prepared by adopting a hydrothermal reduction method. Slowly adding the PA solution into the GO solution, wherein the mass ratio of the PA to the GO solute is 1:6, fully stirring for 30min, then placing the mixture into a stainless steel autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reduction for 12h at 200 ℃, taking out the product, naturally cooling, washing with deionized water for 3 times, and drying at room temperature.
CO is carried out on the PA-GO aerogel by adopting a specific surface analyzer under the conditions of low pressure (0-101.3 kPa) and 298K 2 The adsorption amount is tested, and the result shows that: the graphene aerogel is used for CO 2 The adsorption amount of (C) was 15.8mg/g.
Performance testing
The graphene aerogel obtained in the embodiment and the comparative example is tested, wherein the graphene aerogel comprises specific surface area and porosity, and a specific surface analyzer and a mercury porosimeter are adopted for testing; the specific test results are shown in the following table:
TABLE 1
As can be seen from the data in the table, the specific surface area and the porosity of the aerogel obtained by the freeze-drying method are better than those of the aerogel directly prepared by the hydrothermal reduction method. CO 2 The adsorption amount is related to the specific surface area and amino content of the aerogel. (1) The lower the freezing temperature is, the more the number of the prepared aerogel pore channels is, even the dendrite structure is generated, the larger the specific surface is, the CO is 2 The better the adsorption effect; (2) the higher the addition amount of PEI and CS, the more amino groups are introduced, and CO 2 The more the adsorption sites are, the better the adsorption effect is. The lower the freezing temperature of example 1, the optimum PEI/CS content, the tighter the structure of the aerogel produced, the greater the specific surface area, so the CO 2 The adsorption quantity is the highest.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the graphene aerogel with the directional ordered pore structure for carbon dioxide adsorption is characterized by comprising the following steps of:
dispersing graphene oxide into water to obtain a GO solution;
dissolving polyethylenimine in a phosphate buffer solution or an ethanol solution to obtain a PEI solution;
dissolving chitosan in acetic acid to obtain CS solution;
adding the PEI solution and the CS solution into the GO solution, uniformly mixing, and performing hydrothermal reduction reaction to obtain Gr-PEI-CS composite slurry;
adding the Gr-PEI-CS composite slurry into a mold, freezing, and vacuum drying to obtain graphene aerogel with an oriented ordered pore structure;
wherein the heat conductivity coefficient of the bottom of the die is larger than that of the side wall;
the mass ratio of PEI, CS and GO in the PEI solution, CS solution and GO solution is (0.1-0.6): (0.1 to 0.6): (1-6);
the freezing temperature is-10 to-90 ℃;
the temperature of the hydrothermal reduction reaction is 100-250 ℃, and the reaction time is 10-20 h.
2. The method for preparing graphene aerogel with a directional ordered pore structure for carbon dioxide adsorption according to claim 1, wherein the thermal conductivity coefficient of the side wall of the mold is 0.2-10W/(m.k);
the heat conductivity coefficient of the bottom of the die is 200-600W/(m.K).
3. The method for preparing graphene aerogel with directional ordered pore structure for carbon dioxide adsorption according to claim 1 or 2, wherein the freezing time is 0.5-2 h;
the vacuum drying time is 12-24 hours, the pressure is 3-10 Pa, and the drying temperature is-40-15 ℃.
4. The method for preparing graphene aerogel with directional ordered pore structure for carbon dioxide adsorption according to claim 1 or 2, wherein the concentration of the GO solution is 1-10 g/L and the pH is 5-7.
5. The method for preparing graphene aerogel with directional ordered pore structure for carbon dioxide adsorption according to claim 1 or 2, wherein the concentration of the PEI solution is 0.1-1 mg/mL;
the concentration of the CS solution is 0.1-1 mg/mL, and the mass concentration of the acetic acid is 1-10%.
6. The method for preparing graphene aerogel having a directional ordered pore structure for carbon dioxide adsorption according to claim 1 or 2, wherein the hydrothermal reduction reaction is followed by a water washing step.
7. The method for preparing the graphene aerogel with the directional ordered pore structure for carbon dioxide adsorption, which is disclosed in claim 6, is characterized in that the graphene aerogel is prepared into GO-PEI-CS composite slurry with the concentration of 5-10 mg/mL by water after water washing.
8. A graphene aerogel having a directional ordered pore structure for carbon dioxide adsorption prepared by the preparation method of any one of claims 1 to 7.
9. The graphene aerogel with a directional ordered pore structure for carbon dioxide adsorption according to claim 8, wherein the specific surface area is 300-800 m 2 And/g, wherein the porosity is 50-90%.
10. Use of the graphene aerogel for carbon dioxide adsorption having a directional ordered pore structure according to claim 8 or 9 in carbon dioxide adsorption.
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