CN111974396A - Preparation method and application of graphene aerogel loaded with cobalt-based catalyst - Google Patents
Preparation method and application of graphene aerogel loaded with cobalt-based catalyst Download PDFInfo
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- CN111974396A CN111974396A CN202010721451.XA CN202010721451A CN111974396A CN 111974396 A CN111974396 A CN 111974396A CN 202010721451 A CN202010721451 A CN 202010721451A CN 111974396 A CN111974396 A CN 111974396A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- 239000004964 aerogel Substances 0.000 title claims abstract description 68
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 50
- 239000010941 cobalt Substances 0.000 title claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 50
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- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
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- 229910052742 iron Inorganic materials 0.000 abstract description 5
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- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000003426 co-catalyst Substances 0.000 abstract description 2
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- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 9
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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Abstract
A preparation method and application of a graphene aerogel loaded with a cobalt-based catalyst belong to the technical field of chemical synthesis, and can solve the problems that the cobalt-based, iron-based and nickel-based catalysts cannot be directly applied to CO removal in air, the catalytic performance of granular cobalt-based catalysts is reduced, and the like. Cobalt-based metal oxide serving as a CO catalyst is uniformly dispersed in the gaps of the graphene aerogel material to form negative ionsA catalyst-loaded graphene aerogel composite. Can be at room temperature and has O2Catalytic conversion of CO to CO in the presence of2The filter can bear the low-concentration moisture in the filtered gas, and is applied to CO gas filtering materials of gas masks or other air filtering fields. The used catalyst composite material can be regenerated and reused after being treated at the high temperature of 300 ℃.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method and application of a graphene aerogel loaded with a cobalt-based catalyst.
Background
Carbon monoxide (CO) is one of the common pollutants in the atmosphere, is commonly called coal gas, is colorless, odorless, tasteless, free of irritant gases, and is not easy to liquefy and solidify. The main source of CO is the products of incomplete combustion of carbonaceous materials, e.g., high concentrations of CO in the smoke of a fire; in the production of chemical industry, coal mine and other industrial industries, high-concentration CO may be leaked to the production environment due to gas leakage. The human body is exposed in CO to face serious health and life risks, and CO with lower concentration is easily combined with hemoglobin in blood after being inhaled by the human body to form carboxyhemoglobin, so that the hemoglobin loses the oxygen carrying capacity and effect, tissues are suffocated in a short time and die seriously, and therefore the CO is extremely toxic gas. Effective protection and elimination of CO are realized, and the device is especially important for emergency rescue under emergency conditions such as fire and the like under the normal temperature condition.
The currently widely used ambient temperature CO elimination technology is a catalytic oxidation method, and the adopted catalyst is mainly a proportional (about 2: 1) mixture of oxides of Mn-Cu two metals, and the catalyst is invented by John Hopkins university and California university in the United states earlier than 1919Also known as "hopcalite catalyst". The catalyst is usually made into 1-3mm particles, and is filled into a poison filtering box of a gas mask or other gas filtering devices, CO contained in air reacts on the surface of the catalyst when passing through the poison filtering box, and is converted into less harmful CO2. The defects of the hopcalite catalyst are obvious that (1) the hopcalite catalyst is easy to absorb moisture and lose efficacy, (2) the used catalyst is difficult to regenerate and reuse, (3) a filter device filled with the catalyst is heavy and large in size, is uncomfortable to wear for a long time, and the weight of poison filter boxes of the hopcalite catalyst of multiple brands at home and abroad reaches 480 grams of 450-grade poison materials, and (4) alkali liquor and waste water containing heavy metals are discharged in the production process of the catalyst, so that environmental pollution is caused. In addition, researches have been made on adding precious metals such as Pt and Pd into the hopcalite catalyst, so that the catalytic performance is improved to a certain extent, but the defects of overhigh use cost, high precious metal recovery difficulty and the like are caused.
In recent years, some research and new technologies have catalyzed CO using cobalt-based, iron-based, nickel-based catalysts, in which high-valence cobalt-based metal oxides (CO)3O4) The catalyst has excellent conversion performance on CO, and the catalytic conversion reaction temperature can be even as low as minus 90 ℃. At the same time, an oxide of an element such as cerium (Ce) (e.g., Ce)2O3) The cobalt-based catalyst is added, so that the water resistance and the recycling property of the catalyst are improved, and the catalyst is obviously superior to iron-based, nickel-based and other catalysts. This is because expensive Co is used3O4Oxidative conversion of CO to CO2After that, the O element is lost and becomes unstable Co2O3(ii) a The addition of Ce can strengthen the oxygen in the intake air2To transfer it to Co2O3Make it turn into Co again3O4Thereby realizing continuous CO catalytic conversion.
However, in practical applications, these catalysts still have a series of problems: (1) common cobalt-based and iron-based catalysts are powdery, micron or nano-particle materials, fine powder materials cannot be packaged and cannot be directly applied to CO removal in air, (2) after the cobalt-based catalysts are made into particles, the specific surface area is reduced, so that the catalytic performance is reduced, (3) the price of the cobalt-based catalysts with the same usage is obviously higher than that of the hopcalite catalysts, the cobalt catalysts are higher in price and cannot be massively used like the hopcalite catalysts, (4) the existing research is limited to laboratory research on the CO removal performance of the cobalt-based catalysts, the catalysts are in powder accumulation shapes, the gas flow rate is slow (less than 2L/min), and the catalytic conversion test and application under the conditions of high CO concentration and large gas flow under the real application condition are lacked. Research shows that the respiratory rate of normal people under moderate labor intensity is more than 20L/min. Thus, existing cobalt-based catalysts cannot be successfully applied to filter device products such as gas masks for fire rescue or CO leakage events.
Disclosure of Invention
The invention provides a preparation method of a graphene aerogel loaded with a cobalt-based catalyst, aiming at the problems that the cobalt-based, iron-based and nickel-based catalysts cannot be directly applied to CO removal in air, the catalytic performance of granular cobalt-based catalysts is reduced and the like. The cobalt-based metal oxide serving as a CO catalyst is uniformly dispersed in the gaps of the graphene aerogel material to form the catalyst-loaded graphene aerogel composite material. Can be at room temperature and has O2Catalytic conversion of CO to CO in the presence of2The filter can bear the low-concentration moisture in the filtered gas, and is applied to CO gas filtering materials of gas masks or other air filtering fields. The used catalyst composite material can be regenerated and reused after being treated at the high temperature of 300 ℃. The catalyst can be applied to low-temperature catalytic oxidation of carbon monoxide, and is suitable for the field of emergency rescue and rescue in occasions such as fire or carbon monoxide leakage. Can also be applied to the field of catalytic oxidation of small molecule VOC.
The invention adopts the following technical scheme:
a preparation method of graphene aerogel loaded with a cobalt-based catalyst comprises the following steps:
dissolving water-soluble cobalt salt or water-soluble cobalt salt and an oxygenation auxiliary agent thereof in deionized water to prepare a solution I with the concentration of 1-5 mol/L, preparing a precipitator into a solution II with the concentration of less than 0.2mol/L by using the deionized water, heating the solution II to 60-80 ℃, keeping the temperature, adding the solution I into the solution II at a constant speed under the condition of high-speed mechanical stirring to obtain a mixed solution, and gradually changing the mixed solution into purple or brown to generate purple or brown nanoparticle precipitates;
secondly, adding NaOH into the mixed solution to adjust the mixed solution to be alkalescent, continuing to react for 1-3h, adding sodium hydroxide or hydrogen peroxide solution, and continuing to react for 1 h;
thirdly, after the reaction is finished, cooling the reaction liquid to room temperature, centrifuging and cleaning the precipitate for more than 3 times, drying the precipitate at 110 ℃ for 2 hours to obtain powder, directly mixing the powder with the graphene oxide, the cross-linking agent and the organic solvent, or roasting the precipitate at 300-400 ℃ for 3-4 hours to obtain a cobalt-based catalyst of black powder, and then mixing the cobalt-based catalyst with the graphene oxide, the cross-linking agent and the organic solvent to obtain a mixture;
fourthly, stirring and ultrasonically treating the mixture for more than 30 minutes to obtain uniform mixed dispersion liquid, pouring the mixed dispersion liquid into a high-pressure reaction kettle with a tetrafluoroethylene inner container, and reacting for 3 hours at 120-140 ℃ to obtain the elastic frozen graphene hydrogel;
and fifthly, freezing the graphene hydrogel at the temperature of-20 ℃ for 6-8h, then carrying out freeze drying for 8h to obtain the graphene aerogel loaded with the cobalt-based catalyst, and then carrying out microwave annealing treatment on the graphene aerogel loaded with the cobalt-based catalyst for 60-180 seconds at the power of 300-600W to further reduce polar groups in the aerogel, thereby obtaining the final product of the graphene aerogel loaded with the cobalt-based catalyst with enhanced structural strength.
In the first step the cobalt salt comprises a water soluble cobalt salt.
In the first step, the cobalt salt comprises any one of cobalt nitrate, cobalt chloride and cobalt acetate.
In the first step, the oxygen increasing agent comprises water-soluble cerium salt or water-soluble bismuth salt.
In the first step, the oxygenation agent comprises any one of cerium nitrate, cerium chloride, bismuth nitrate and bismuth chloride.
In the first step the precipitating agent comprises sodium hydroxide or sodium carbonate.
The crosslinking agent in the third step comprises a polyol containing no nitrogen atom or amino group.
The cross-linking agent in the third step includes any one of oligomeric starch, water-soluble starch, lactose and ascorbic acid.
And in the third step, the organic solvent comprises ethanol or tetrahydrofuran with the purity of more than 95%.
In the third step, the concentration of the graphene oxide is higher than 6mg/mL calculated by the mass of graphite, the addition amount of the cross-linking agent is 0.2-0.5g/100mL of the mixture, and the addition amount of the organic solvent is 10-20mL/100mL of the mixture.
The graphene aerogel loaded with the cobalt-based catalyst is applied to removal of CO.
The invention has the following beneficial effects:
in the method, water-soluble starch or lactose is used as a cross-linking agent of the graphene oxide, and other cross-linking agents or reducing agents are not needed, so that the method has multiple advantages:
(1) the number of oxygen-containing functional groups in the polysaccharide molecule is higher than that of any other reported reducing agent and crosslinking agent, and the reactivity is high;
(2) the polysaccharide has larger molecular size and is a flexible long-chain molecule, and the graphite oxide sheets with different sizes can be efficiently polymerized and crosslinked;
(3) the polymerization reaction sites are many, the steric effect of catalyst particles is small, and the load of the catalyst particles with different particle sizes is more stable;
(4) avoids the complexation of other crosslinking agents or reducing agents (such as ethylenediamine and the like) containing nitrogen atoms and the catalyst, which leads to the instability of the aerogel structure and the loss of the catalyst to the outside of the aerogel.
(5) The synthesis time of the aerogel composite material is obviously shortened, due to the efficient crosslinking reaction characteristic of polysaccharide, the hydrogel with complete structure and smooth appearance can be obtained by hydrothermal reaction for 2-3 hours at the temperature of 120-140 ℃, and the reaction time is obviously shorter than that of 11-50 hours reported by other methods. The hydrogel had good strength and could be placed upright without being soaked in solution (fig. 6).
In the method reported by the invention, the addition of a certain amount of organic solvent has 2 important advantages:
(1) the freeze-drying time of the composite material is shortened because the organic solvent molecules have lower melting point and easy volatility, the organic solvent and water are added to form a uniform binary solvent, after freezing, the organic solvent molecules are quickly volatilized to leave the pores of the aerogel in the freeze-drying process, and the residual ice obtains huge specific surface area due to losing the space occupation of the organic solvent molecules and leaves the aerogel at a higher sublimation speed. Thereby greatly shortening the drying time from the traditional time more than 48 hours to within 8 hours;
(2) adding organic solvent molecules makes the hydrone after freezing, and the ice crystal volume that generates reduces to reduce the structural damage degree of freezing to the aerogel, obtain more complete aerogel material, can distinguish the difference (fig. 7) of the aerogel that adds organic solvent and pure water reaction system on the surface of outward appearance through people's eye, surface crack, the structure shrink phenomenon take place easily for the synthetic aerogel of pure water solvent, and the synthetic aerogel form of binary solvent system is plump, and the outward appearance is comparatively smooth.
In conclusion, the invention reports a rapid and stable synthesis method of a cobalt-based catalyst-loaded graphene aerogel composite monolithic material, and the obtained graphene aerogel composite material can be used for eliminating CO in the air.
Drawings
FIG. 1 shows graphene aerogel @ Co prepared according to the present invention3O4/Ce2O3A physical diagram of the composite catalyst monolithic material.
FIG. 2 shows the Co prepared by the present invention3O4/Ce2O3Scanning electron microscopy of the nano-catalyst particles.
FIG. 3 shows graphene aerogel @ Co prepared according to the present invention3O4/Ce2O3Scanning electron microscopy of composite catalyst monoliths。
Fig. 4 is a scanning electron microscope image of pure graphene aerogel without supported catalyst.
FIG. 5 shows the Co-supported catalyst prepared by the present invention3O4-Ce2O3An X-ray diffraction pattern of the graphene aerogel.
FIG. 6 shows the Co prepared by the present invention3O4-Ce2O3-graphene hydrogel vertical placement object diagram.
Fig. 7 is a comparison graph of graphene aerogel prepared by the pure water solvent reaction system and graphene aerogel prepared by the invention, wherein a is graphene aerogel prepared by the pure water solvent reaction system, and B is graphene aerogel prepared by adding an organic solvent according to the invention.
Fig. 8 is a diagram illustrating the catalytic conversion of carbon monoxide CO by the graphene aerogel loaded with the cobalt-based catalyst prepared by the present invention.
Detailed Description
The specific synthetic route for the composite material of the present invention includes two methods. The first is a stepwise synthesis, first, a cobalt-based catalyst is prepared: dissolving cobalt salt (water-soluble salt such as cobalt chloride, cobalt nitrate, cobalt acetate, etc.) in deionized water to prepare solution; then, dissolving sodium carbonate in deionized water to prepare a low-concentration (less than 0.2 mol/L) solution; heating a sodium carbonate solution to 60 ℃, keeping the temperature constant, and adding a cobalt salt solution into the sodium carbonate solution dropwise at a constant speed under the condition of high-speed mechanical stirring to gradually generate purple and uniform precipitates; adding NaOH to adjust to alkalescence (pH is about 9), continuously reacting for 1-3 hours, dropwise adding hydrogen peroxide solution with the same amount as cobalt salt to obtain dark brown precipitate, continuously reacting for 1 hour, cooling to room temperature, centrifuging the precipitate, cleaning for more than 3 times to remove Na+And anions (NO)3 -、Cl-And the like), drying the obtained brown or purple precipitate at 60-100 ℃, and directly carrying out a composite reaction with graphene oxide in the next step; or calcining the precipitate at 300 deg.C for 3-4 hr to obtain black cobaltosic oxide (Co)3O4) Catalyst powder for the next step and the oxidized stoneAnd (4) carrying out a composite reaction of graphene.
In the above process, cerium salt (such as water soluble salt of cerium nitrate, cerium chloride, etc.) or bismuth salt (such as water soluble salt of bismuth nitrate, etc.) and cobalt salt can be added into low concentration (less than 0.2 mol/L) 60 deg.C sodium carbonate solution with quick mechanical stirring according to the proportion (Co: Ce or Bi =10: 1-6: 1) to produce precipitate, NaOH is added to adjust to alkalescence (pH is about 9), hydrogen peroxide with 1.5 times of amount of metal salt substance is added dropwise after continuous reaction for 1-3 hours, the precipitate is turned into dark brown, the precipitate is cooled to room temperature after continuous reaction for 1 hour, centrifuged and washed for more than 3 times to remove Na+And anions (NO)3 -、Cl-Etc.), drying the precipitate, and calcining at 300 deg.C for 3-4 hr to obtain black Co powder3O4/Ce2O3Or Co3O4/Bi2O3The enhanced binary catalyst is stored in a sealed manner for later use. Wherein Co3O4/Ce2O3The material can be characterized by scanning electron microscopy, as shown in FIG. 2, Co3O4/Ce2O3The morphology of (A) is in the form of particles with the size of 20-80 nm.
And secondly, rapidly synthesizing the catalyst-loaded graphene aerogel composite material. A certain mass of Co obtained in the last step3O4Or Co3O4/Ce2O3Or Co3O4/Bi2O3Mixing with Graphene Oxide (GO), water-soluble polysaccharide (water-soluble starch or lactose), and organic solvent (ethanol or tetrahydrofuran), wherein the GO concentration is higher than 6mg/mL (calculated by graphite mass), the addition amount of polysaccharide is 0.2-0.5g/100mL of the mixture, and the addition amount of organic solvent is 10-20mL/100mL of the mixture. Fully stirring the mixture, carrying out ultrasonic treatment for 30min, transferring the mixture into a stainless steel reaction kettle with a tetrafluoroethylene inner container, carrying out hydrothermal reaction for 2-3 h at the temperature of 120-140 ℃ to obtain cylindrical high-strength catalyst-loaded graphene hydrogel, freezing the hydrogel at the temperature of ̵ 10 ℃ for 6 h, transferring the hydrogel into a freeze drier, and carrying out drying treatment for 8h to obtain catalyst-loaded graphene aerogelAnd (3) placing the composite material in a microwave reactor, and heating for 60-180 seconds under the power of 300-600W for annealing treatment to obtain the final graphene aerogel composite material loaded with the cobalt-based catalyst. As shown in fig. 3, after the obtained aerogel composite material is magnified by a scanning electron microscope, Co loaded on the surface of the graphene sheet layer is visible3O4/Ce2O3The morphology of the particles, in contrast to the pure graphene aerogel (fig. 4).
Example 1
(1) 29.1g of cobalt nitrate hexahydrate was dissolved in deionized water to prepare a solution. Then, 15.9g of sodium carbonate is dissolved in deionized water to prepare a low-concentration (less than 0.2 mol/L) solution, and the quantity ratio n of the two substances isCobalt nitrate:nSodium carbonateEqual to 1: 1.5. Heating the sodium carbonate solution to 60 ℃ and keeping the temperature constant, and adding the cobalt salt solution into the sodium carbonate solution dropwise at a constant speed under the condition of high-speed mechanical stirring to gradually generate purple and uniform precipitates. Adding NaOH to adjust to alkalescence (pH is about 9), continuously reacting for 1-3 hours, dropwise adding hydrogen peroxide solution with the same amount as cobalt salt to obtain dark brown precipitate, continuously reacting for 1 hour, cooling to room temperature, centrifuging the precipitate, cleaning for more than 3 times to remove Na+And anions (NO)3 -、Cl-Etc.), drying the precipitate, and calcining at 300 deg.C for 3-4 hr to obtain black Co3O4A catalyst. (2) Mixing 8g of Co3O4Mixing with 90mL of 8mg/mL GO, 0.5g of lactose and 20mL of ethanol, stirring the mixture fully, carrying out ultrasonic treatment for 30min, transferring the mixture into a stainless steel reaction kettle with a tetrafluoroethylene inner container, and carrying out hydrothermal reaction for 3 hours at 130 ℃ to obtain cylindrical high-strength Co-loaded material3O4Placing the hydrogel below ̵ ℃ below zero and 20 ℃ for freezing for 6 hours, performing freeze-drying and drying treatment for 8 hours to obtain a catalyst-loaded graphene aerogel composite material, placing the composite material in a microwave reactor, heating for 120 seconds under 400W power for annealing treatment to obtain the final Co-loaded graphene aerogel composite material (figure 6)3O4Graphene aerogel of catalystA composite material.
Example 2
(1) 23.8g of cobalt chloride hexahydrate and 4.4g of cerous nitrate hexahydrate are respectively dissolved in deionized water to prepare solutions with the concentration of 2 mol/L. Then, a solution was prepared by dissolving 17.5g of sodium carbonate in 800mL of deionized water, heating to 60 ℃ and maintaining the temperature. Under the condition of high-speed mechanical stirring, cobalt nitrate and cerium nitrate solutions are respectively added into a sodium carbonate solution drop by drop at a constant speed to gradually generate purple and uniform precipitates. Adding NaOH to adjust to alkalescence (pH is about 9), continuously reacting for 3 hr, adding 30mL hydrogen peroxide (content is 33%) to turn brown, continuously reacting for 1 hr, cooling to room temperature, centrifuging the precipitate, cleaning to remove Na+And adding deionized water again to obtain brown high-valence Co-Ce hydroxide nano material dispersion liquid. (2) Mixing the dispersion liquid obtained in the last step with 180mL of GO with the concentration of 12mg/mL, 1.5g of lactose and 30mL of tetrahydrofuran to obtain a mixed dispersion liquid with the total volume of 270mL, stirring the mixture for 15min, carrying out ultrasonic treatment for 30min, transferring the mixture into a stainless steel reaction kettle with a tetrafluoroethylene inner container, carrying out hydrothermal reaction for 3 hours at 130 ℃ to obtain cylindrical high-strength Co-Ce hydroxide-loaded graphene hydrogel, freezing the hydrogel below-20 ℃ for 8 hours, carrying out freeze drying treatment for 8 hours to obtain Co-Ce hydroxide-loaded graphene aerogel, heating the Co-Ce hydroxide-loaded graphene aerogel at 300 ℃ for 240 minutes for annealing treatment to obtain the final Co-Ce hydroxide-loaded graphene aerogel3O4-Ce2O3Graphene aerogel composites of catalysts.
Example 3
(1) 24.9g of cobalt acetate tetrahydrate and 4.85g of bismuth nitrate pentahydrate are respectively dissolved in deionized water to prepare a solution with the concentration of 2 mol/L. Then, a solution was prepared by dissolving 17.5g of sodium carbonate in 800mL of deionized water, heating to 60 ℃ and maintaining the temperature. Under the condition of high-speed mechanical stirring, Co is mixed2+And Bi3+The solution was added dropwise to the sodium carbonate solution at a constant rate, gradually producing a purple and uniform precipitate. Further reacting for 3 hr, cooling to room temperature, centrifuging the precipitate, washing for more than 3 times to remove Na+And an anion, drying the precipitate at 60 ℃ overnight,obtaining the purple cobalt carbonate-cerium carbonate nano-particle material. (2) Mixing 9g of cobalt carbonate-cerium carbonate with 90mL of GO with the concentration of 8mg/mL, 0.5g of water-soluble starch and 10mL of ethanol, stirring the mixture for 15min, carrying out ultrasonic treatment for 30min, transferring the mixture into a stainless steel reaction kettle with a tetrafluoroethylene inner container, carrying out hydrothermal reaction for 3 hours at 130 ℃ to obtain cylindrical and high-strength graphene hydrogel loaded with the cobalt carbonate-cerium carbonate catalyst, placing the hydrogel below ̵ ℃ below zero and 20 ℃ for freezing for 8 hours, carrying out freeze-drying treatment for 8 hours to obtain graphene aerogel loaded with the cobalt carbonate-cerium carbonate, heating the graphene aerogel at 300 ℃ for 240 minutes for annealing treatment to obtain the final Co-cerium-loaded graphene aerogel3O4-Ce2O3Graphene aerogel composites of catalysts.
Application of the invention
The graphene aerogel composite material loaded with the cobalt-based catalyst is filled into a cylindrical toxicity filtering box with an inner cavity diameter of 76mm and a height of 60mm, and the carbon monoxide toxicity filtering box is prepared. The toxin filtering box shell is formed by 3D printing of a polylactic acid material, the total mass is 95.2g, the mass of the contained composite material is only 38.4g, and 32.0g of cobalt-based catalyst is contained in the toxin filtering box shell.
The specific test conditions are as follows: the toxin filtering box is arranged in a fixed bed tester, the air tightness is checked, the testing temperature is set to be 25 ℃, air is used as carrier gas to enter a testing system through a drying tower filled with silica gel desiccant, high-purity CO (99.9%) gas is connected into the testing system through a pressure reducing valve, and the testing concentration of CO is controlled to be 430 ppm. A gas chromatograph Agilent 8890GC equipped with a Flame Ionization Detector (FID) is used for detecting the CO concentration before and after passing through the toxin filter box, a high-precision injector is used for gas sampling and sample injection, and sampling is carried out once every 5min within the sampling time. According to the relevant regulations in the national standard GB2892-2009, when the CO concentration passing through the canister is higher than 50ppm, it is assumed that the CO concentration is higher than the warning concentration, the canister is penetrated and the experiment is stopped. The length of time until the canister is penetrated when the CO begins to pass through the canister is the effective protection time of the canister against the CO.
As can be seen from fig. 8, the CoO-loaded graphene aerogel composite can effectively reduce the CO concentration in the air from 660ppm (mL/L) to less than 1ppm at normal temperature. With the progress of the CO catalytic conversion reaction, at 380min, the CO concentration passing through the toxicity filtering box is higher than 50ppm, namely the CO protection time of the CoO-loaded graphene aerogel is 410 minutes. When the test objects are load CoO-CeO and CoO-BiO, the protection time of the toxicity filtering box to CO reaches 520 minutes and 580 minutes respectively, and the fact that the Ce and the Bi are added into the cobalt-based catalyst can effectively enhance the catalytic conversion reaction activity of the catalyst to CO is shown. Therefore, the graphene aerogel composite material loaded with the cobalt-based catalyst and the additive thereof can effectively protect low-concentration CO in the air, so that the graphene aerogel composite material is applied to emergency rescue in fire or other occasions and other CO removal and protection occasions.
Claims (10)
1. A preparation method of graphene aerogel loaded with a cobalt-based catalyst is characterized by comprising the following steps: the method comprises the following steps:
dissolving water-soluble cobalt salt or water-soluble cobalt salt and an oxygenation auxiliary agent thereof in deionized water to prepare a solution I with the concentration of 1-5 mol/L, preparing a precipitator into a solution II with the concentration of less than 0.2mol/L by using the deionized water, heating the solution II to 60-80 ℃, keeping the temperature, adding the solution I into the solution II at a constant speed under the condition of high-speed mechanical stirring to obtain a mixed solution, and gradually changing the mixed solution into purple or brown to generate purple or brown nanoparticle precipitates;
secondly, adding NaOH into the mixed solution to adjust the mixed solution to be alkalescent, continuing to react for 1-3h, adding sodium hydroxide or hydrogen peroxide solution, and continuing to react for 1 h;
thirdly, after the reaction is finished, cooling the reaction liquid to room temperature, centrifuging and cleaning the precipitate for more than 3 times, drying the precipitate at 110 ℃ for 2 hours to obtain powder, directly mixing the powder with the graphene oxide, the cross-linking agent and the organic solvent, or roasting the precipitate at 300-400 ℃ for 3-4 hours to obtain a cobalt-based catalyst of black powder, and then mixing the cobalt-based catalyst with the graphene oxide, the cross-linking agent and the organic solvent to obtain a mixture;
fourthly, stirring and ultrasonically treating the mixture for more than 30 minutes to obtain uniform mixed dispersion liquid, pouring the mixed dispersion liquid into a high-pressure reaction kettle with a tetrafluoroethylene inner container, and reacting for 3 hours at 120-140 ℃ to obtain the elastic frozen graphene hydrogel;
and fifthly, freezing the graphene hydrogel at the temperature of-20 ℃ for 6-8h, then carrying out freeze drying for 8h to obtain the graphene aerogel loaded with the cobalt-based catalyst, and then carrying out microwave annealing treatment on the graphene aerogel loaded with the cobalt-based catalyst for 60-180 seconds at the power of 300-600W to further reduce polar groups in the aerogel, thereby obtaining the final product of the graphene aerogel loaded with the cobalt-based catalyst with enhanced structural strength.
2. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: in the first step the cobalt salt comprises a water soluble cobalt salt.
3. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: in the first step, the cobalt salt comprises any one of cobalt nitrate, cobalt chloride and cobalt acetate.
4. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: in the first step, the oxygen increasing agent comprises water-soluble cerium salt or water-soluble bismuth salt.
5. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: in the first step, the oxygenation agent comprises any one of cerium nitrate, cerium chloride, bismuth nitrate and bismuth chloride.
6. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: in the first step the precipitating agent comprises sodium hydroxide or sodium carbonate.
7. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: the crosslinking agent in the third step comprises a polyol containing no nitrogen atom or amino group.
8. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: the cross-linking agent in the third step comprises any one of oligomeric starch, water-soluble starch, lactose and ascorbic acid; and in the third step, the organic solvent comprises ethanol or tetrahydrofuran with the purity of more than 95%.
9. The preparation method of the cobalt-based catalyst-supported graphene aerogel according to claim 1, wherein the preparation method comprises the following steps: in the third step, the concentration of the graphene oxide is higher than 6mg/mL calculated by the mass of graphite, the addition amount of the cross-linking agent is 0.2-0.5g/100mL of the mixture, and the addition amount of the organic solvent is 10-20mL/100mL of the mixture.
10. The graphene aerogel loaded with the cobalt-based catalyst is applied to removal of CO.
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