CN111974396B - Preparation method and application of cobalt-based catalyst-loaded graphene aerogel - Google Patents
Preparation method and application of cobalt-based catalyst-loaded graphene aerogel Download PDFInfo
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- CN111974396B CN111974396B CN202010721451.XA CN202010721451A CN111974396B CN 111974396 B CN111974396 B CN 111974396B CN 202010721451 A CN202010721451 A CN 202010721451A CN 111974396 B CN111974396 B CN 111974396B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 239000004964 aerogel Substances 0.000 title claims abstract description 57
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000017 hydrogel Substances 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 150000001868 cobalt Chemical class 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
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- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000008101 lactose Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000003053 toxin Substances 0.000 claims description 5
- 231100000765 toxin Toxicity 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 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
- 238000006213 oxygenation reaction Methods 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
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 231100000614 poison Toxicity 0.000 abstract description 9
- 239000002574 poison Substances 0.000 abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000003426 co-catalyst Substances 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 48
- 229910002091 carbon monoxide Inorganic materials 0.000 description 48
- 239000007789 gas Substances 0.000 description 11
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 5
- 150000004676 glycans Chemical class 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229920001282 polysaccharide Polymers 0.000 description 5
- 239000005017 polysaccharide Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- -1 cobalt carbonate-cerium carbonate Chemical compound 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- 102000001554 Hemoglobins Human genes 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- 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 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 238000010146 3D printing Methods 0.000 description 1
- 108010003320 Carboxyhemoglobin Proteins 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- 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
-
- 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
- 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
- B01J23/76—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
-
- 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
- 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
- B01J23/76—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
-
- B01J35/23—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
A preparation method of a graphene aerogel loaded with a cobalt-based catalyst and application thereof belong to the technical field of chemical synthesis, and can solve the problems that the cobalt-based catalyst, the iron-based catalyst and the nickel-based catalyst cannot be directly applied to CO removal in air, the catalytic performance of a granular cobalt-based catalyst is reduced, and the catalyst prepared by the method is not in a fine powder form, is an aerogel-type massive integral material, is easy to package into filtering devices in various shapes, and does not leak. 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 normal temperature and has O 2 Catalytic conversion of CO to CO in the presence of 2 Can bear low-concentration moisture in filtered gas and is applied to the CO poison filtering material of a gas mask or other air filtering fields. The used catalyst composite material can be regenerated and reused after being treated at 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 cobalt-based catalyst-loaded graphene aerogel.
Background
Carbon monoxide (CO) is one of the common pollutants in the atmosphere, commonly known as coal gas, and is colorless, odorless, tasteless, free of irritating gases and not easy to liquefy and solidify. The main source of CO is the products of incomplete combustion of carbon-containing substances, for example, the dense smoke in the case of fire contains high concentration of CO; in the production of industrial industries such as chemical industry and coal mine, high-concentration CO can be leaked to the production environment due to gas leakage. The human body is exposed to CO and is serious in health and life danger, CO with low concentration is extremely easy to combine 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, tissue choking can be caused in a short time, and the tissue is seriously dead, so that CO is a highly toxic gas. Effective protection and elimination of CO are particularly important for emergency rescue under the conditions of fire and the like at normal temperature.
The current widely used ambient temperature CO abatement technology is catalytic oxidation, with a catalyst that is primarily a proportional (about 2:1) mixture of oxides of two metals mn—cu, which was invented by the university of john-hopkins and california, usa, earlier than 1919, together, also known as "hopcalite catalyst". The catalyst is usually made into 1-3mm granule, and filled into the poison filtering box of gas mask or other gas filtering device, and CO contained in air reacts on the surface of the catalyst when passing through the poison filtering box, and is converted into less harmful CO 2 . The disadvantages of the Hogarter catalyst are also obvious that (1) the Hogarter catalyst is easy to absorb moisture and lose efficacy, (2) the catalyst after use is difficult to regenerate and reuse, (3) the filtering device filled with the catalyst is heavy and has large volume and is uncomfortable to wear for a long time, the weight of the Hogarter catalyst poison filtering box of a plurality of brands at home and abroad reaches 450-480 g, (4) alkali liquor and waste water containing heavy metal are discharged in the production process of the catalyst, and environmental pollution is caused. In addition, noble metals such as Pt, pd and the like are added into the Hoglate catalyst, so that the catalytic performance is improved to a certain extent, but the defects of overhigh use cost, high recovery difficulty of the noble metals and the like are caused.
In recent years, some researches and new technologies use cobalt-based, iron-based and nickel-based catalystsCatalytic CO, wherein a higher cobalt-based metal oxide (CO 3 O 4 ) The catalyst shows excellent conversion performance to CO, and the catalytic conversion reaction temperature can be even as low as minus 90 ℃. At the same time, oxides of elements such as cerium (Ce) (e.g. Ce 2 O 3 ) The addition of the cobalt-based catalyst is favorable for improving the water resistance and the regeneration and recycling performance of the catalyst, thereby being obviously superior to iron-based, nickel-based and other catalysts. This is due to the fact that when Co is expensive 3 O 4 Oxidative conversion of CO to CO 2 After losing O element to become unstable Co 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The addition of Ce element can strengthen the O in the inlet air 2 Is transferred to Co 2 O 3 Reconvert it into Co 3 O 4 Thereby achieving continuous catalytic conversion of CO.
However, in practical applications, these catalysts still have a series of problems: the method comprises the steps of (1) preparing common cobalt-based catalyst, iron-based catalyst and other catalyst into powder, micron or nano particle materials, wherein the fine powder materials cannot be packaged and cannot be directly applied to CO removal in air, (2) preparing the cobalt-based catalyst into particles, and then reducing the specific surface area, so that the catalytic performance is reduced, (3) using the cobalt-based catalyst with the same amount, namely a Yu Huojia-bit catalyst, remarkably high price, and not using a large amount of cobalt-based catalyst like a Hoglade catalyst because the cobalt catalyst is high in price, and (4) testing the CO removal performance of the cobalt-based catalyst by the existing research is limited to laboratory research, wherein the catalyst is in a powder accumulation state, and the gas flow rate is low (less than 2L/min), so that the method lacks in the catalytic conversion test and application under the conditions of high CO concentration and large gas flow rate under the actual application condition. The study shows that the respiration rate of normal people is more than 20L/min under the medium labor intensity. Thus, existing cobalt-based catalysts cannot be successfully used in filter products such as respirators for fire rescue or CO leakage events.
Disclosure of Invention
The invention provides a supported cobalt-based catalyst, aiming at solving the problems that 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 likeAccording to the preparation method of the graphene aerogel, the catalyst prepared by the method is not in a fine powder shape, is an aerogel type massive integral material, is easy to package into various shapes of filtering devices, and does not leak. 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 normal temperature and has O 2 Catalytic conversion of CO to CO in the presence of 2 Can bear low-concentration moisture in filtered gas and is applied to the CO poison filtering material of a gas mask or other air filtering fields. The used catalyst composite material can be regenerated and reused after being treated at 300 ℃. Can be applied to the low-temperature catalytic oxidation of carbon monoxide and is suitable for the fields of emergency rescue and relief in the occasions such as fire disaster or carbon monoxide leakage and the like. 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 a cobalt-based catalyst-loaded graphene aerogel comprises the following steps:
firstly, 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 solution II with the concentration of less than 0.2mol/L by using a precipitator, heating the solution II to 60-80 ℃ and keeping the temperature, and 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, wherein the mixed solution gradually turns purple or brown to generate purple or brown nano-particle precipitates;
secondly, adding NaOH into the mixed solution to adjust to be weak alkaline, continuously reacting for 1-3 hours, and then adding sodium hydroxide or hydrogen peroxide solution to continuously react for 1 hour;
thirdly, after the reaction is finished, cooling the reaction solution 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 graphene oxide, a cross-linking agent and an organic solvent, or roasting the precipitate at 300-400 ℃ for 3-4 hours to obtain a cobalt-based catalyst of black powder, and 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 liner, and reacting for 3 hours at 120-140 ℃ to obtain elastic frozen graphene hydrogel;
and fifthly, placing the graphene hydrogel in a temperature of minus 20 ℃ for 6-8 hours, then performing freeze drying for 8 hours to obtain the graphene aerogel loaded with the cobalt-based catalyst, and performing microwave annealing treatment for 60-180 seconds with the power of 300-600W to further reduce polar groups in the aerogel, so that the graphene aerogel final product loaded with the cobalt-based catalyst and with the enhanced structural strength is obtained.
The cobalt salt in the first step comprises a water-soluble cobalt salt.
The cobalt salt in the first step comprises any one of cobalt nitrate, cobalt chloride and cobalt acetate.
The oxygen increasing agent in the first step comprises water-soluble cerium salt or water-soluble bismuth salt.
The oxygen increasing agent in the first step comprises any one of cerium nitrate, cerium chloride, bismuth nitrate and bismuth chloride.
The precipitant in the first step comprises sodium hydroxide or sodium carbonate.
The crosslinking agent in the third step comprises a polyhydroxy compound containing no nitrogen atom or amino group.
The cross-linking agent in the third step comprises any one of oligomeric starch, water-soluble starch, lactose and ascorbic acid.
The organic solvent in the third step comprises ethanol or tetrahydrofuran with the purity of more than 95 percent.
In the third step, the graphene oxide is calculated by the mass of graphite, the concentration is higher than 6mg/mL, the adding amount of the cross-linking agent is 0.2-0.5g/100mL of the mixture, and the adding amount of the organic solvent is 10-20mL/100mL of the mixture.
A graphene aerogel loaded with a cobalt-based catalyst is applied to CO removal.
The beneficial effects of the invention are as follows:
in the method, water-soluble starch or lactose is adopted as the crosslinking agent of the graphene oxide, and other crosslinking 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 cross-linking agent, and the reaction activity is high;
(2) The polysaccharide has larger molecular size and is a flexible long-chain molecule, so that graphite oxide sheets with different sizes can be efficiently polymerized and crosslinked;
(3) The polymerization reaction sites are more, the influence of steric hindrance of catalyst particles is small, and the catalyst particles with different particle diameters are more stably loaded;
(4) The complex action of other cross-linking agents or reducing agents (ethylenediamine and the like) containing nitrogen atoms and the catalyst is avoided, so that the aerogel is unstable in structure and the catalyst is prevented from being lost to the outside of the aerogel.
(5) The synthesis time of the aerogel composite material is obviously shortened, and the hydrogel with complete structure and smooth appearance can be obtained by hydrothermal reaction for 2-3 hours at 120-140 ℃ due to the efficient crosslinking reaction characteristic of the polysaccharide, wherein the reaction time is obviously less than 11-50 hours reported by other methods. The strength of the hydrogels was good and they could be placed vertically without solution soaking (fig. 6).
In the method reported in the invention, the addition of a certain amount of organic solvent has 2 major advantages:
(1) The freeze-drying time of the composite material is shortened because the organic solvent molecules have lower melting points and volatile properties, the organic solvent and water are added to form a uniform binary solvent, after freezing, the organic solvent molecules quickly volatilize away from the pores of the aerogel in the freeze-drying process, and the rest ice obtains huge specific surface area due to the loss of the occupation of the organic solvent molecules and leaves the aerogel at a faster sublimation speed. Thereby greatly shortening the drying time from the traditional time of more than 48 hours to less than 8 hours;
(2) The addition of the organic solvent molecules reduces the volume of the generated ice crystals after the water molecules are frozen, so that the structural damage degree of the frozen ice to the aerogel is reduced, a more complete aerogel material is obtained, the difference of the aerogel added with the organic solvent and the pure water reaction system on the appearance surface can be distinguished through human eyes (figure 7), the aerogel synthesized by the pure water solvent is easy to generate surface cracks and structure shrinkage, and the aerogel synthesized by the binary solvent system is full in shape and smoother in appearance.
In summary, the invention reports a rapid and stable synthesis method of the graphene aerogel composite integral material loaded with the cobalt-based catalyst, and the obtained graphene aerogel composite material can be used for eliminating CO in air.
Drawings
FIG. 1 is a graph of graphene aerogel @ Co prepared according to the present invention 3 O 4 /Ce 2 O 3 Composite catalyst monolith.
FIG. 2 is a Co produced by the present invention 3 O 4 /Ce 2 O 3 Scanning electron microscopy of nanocatalyst particles.
FIG. 3 is a graph of graphene aerogel @ Co prepared according to the present invention 3 O 4 /Ce 2 O 3 Scanning electron microscopy of composite catalyst monolith.
Fig. 4 is a scanning electron microscope image of a pure graphene aerogel without a catalyst supported thereon.
FIG. 5 shows the Co-supported catalyst prepared according to the present invention 3 O 4 -Ce 2 O 3 X-ray diffraction pattern of graphene aerogel.
FIG. 6 is a Co produced by the present invention 3 O 4 -Ce 2 O 3 -graphene hydrogel vertically placed physical map.
Fig. 7 is a graph comparing graphene aerogel prepared by the invention with graphene aerogel prepared by the pure water solvent reaction system, wherein a is graphene aerogel prepared by the pure water solvent reaction system, and B is graphene aerogel prepared by adding an organic solvent.
Fig. 8 is a catalytic conversion diagram of carbon monoxide CO by graphene aerogel loaded with a cobalt-based catalyst prepared according to the present invention.
Detailed Description
Of composite materials of the inventionThe specific synthetic route includes two methods. The first is a stepwise synthesis, first, a cobalt-based catalyst is prepared: cobalt salt (water soluble salts such as cobalt chloride, cobalt nitrate, cobalt acetate and the like) is dissolved in deionized water to prepare a solution; then, dissolving sodium carbonate in deionized water to prepare a low-concentration (less than 0.2 mol/L) solution; 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 precipitate; adding NaOH to make it slightly alkaline (pH 9), continuously reacting for 1-3 hr, dropwise adding hydrogen peroxide solution with the same amount as cobalt salt, turning the precipitate into dark brown, continuously reacting for 1 hr, cooling to room temperature, centrifuging, cleaning for more than 3 times to remove Na + And anions (NO) 3 - 、Cl - Etc.), the obtained brown or purple precipitate is dried at 60-100 ℃ and can be directly used for the next step of the composite reaction with graphene oxide; or calcining the precipitate at 300deg.C for 3-4 hr to obtain black cobaltosic oxide (Co) 3 O 4 ) The catalyst powder is used for the next step of the composite reaction with the graphene oxide.
In the above process, cerium salt (such as water-soluble salt of cerium nitrate and cerium chloride) or bismuth salt (such as water-soluble salt of bismuth nitrate) and cobalt salt (Co: ce or Bi=10:1-6:1) can be added into sodium carbonate solution with low concentration (less than 0.2 mol/L) and 60 ℃ and mechanical stirring at a speed to generate precipitate, naOH is added to adjust to alkalescence (pH is about 9), after continuing to react for 1-3 hours, hydrogen peroxide with the amount of 1.5 times of metal salt substance is added dropwise, the precipitate turns into dark brown, and then continues to react for 1 hour, cooling to room temperature, centrifuging and cleaning the precipitate for 3 times to remove Na or more + And anions (NO) 3 - 、Cl - Etc.), drying the precipitate, and calcining at 300 deg.C for 3-4 hr to obtain black powder Co 3 O 4 /Ce 2 O 3 Or Co 3 O 4 /Bi 2 O 3 The enhanced binary catalyst is stored in a sealing way for standby. Wherein Co is 3 O 4 /Ce 2 O 3 The material can be scanned byCharacterization tests were performed by scanning electron microscopy, as shown in FIG. 2, co 3 O 4 /Ce 2 O 3 The morphology of the particles is 20-80 and nm.
And secondly, rapidly synthesizing the graphene aerogel composite material loaded with the catalyst. The Co obtained in the last step with a certain quality 3 O 4 Or Co 3 O 4 /Ce 2 O 3 Or Co 3 O 4 /Bi 2 O 3 Mixing with Graphene Oxide (GO), water-soluble polysaccharide (water-soluble starch or lactose) and organic solvent (ethanol or tetrahydrofuran), wherein GO concentration is higher than 6mg/mL (calculated by graphite mass), polysaccharide addition amount is 0.2-0.5g/100mL of the mixture, and organic solvent addition amount is 10-20mL/100mL of the mixture. And (3) fully stirring and ultrasonically treating the mixture for 30min, transferring the mixture into a stainless steel reaction kettle with a tetrafluoroethylene inner container, carrying out hydrothermal reaction at 120-140 ℃ for 2-3 h to obtain cylindrical high-strength catalyst-loaded graphene hydrogel, placing the hydrogel into a freeze dryer after freezing for 6 h at a temperature below ̵ ℃, drying for 8h to obtain catalyst-loaded graphene aerogel composite, placing the composite into a microwave reactor, and heating for 60-180 s at a power of 300-600W to carry out annealing treatment to obtain the final cobalt-based catalyst-loaded graphene aerogel composite. As shown in fig. 3, after the obtained aerogel composite material is amplified by a scanning electron microscope, co loaded on the surface of the graphene sheet layer is visible 3 O 4 /Ce 2 O 3 Particles, in sharp contrast to the morphology of 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 mass ratio of the sodium carbonate and the deionized water is n Cobalt nitrate ：n Sodium carbonate Equal 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 precipitate. Adding NaOH to make it weakly alkaline (p)H is about 9), continuously reacting for 1-3 hours, dropwise adding hydrogen peroxide solution with the same amount as cobalt salt, turning the precipitate into dark brown, 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 Co 3 O 4 A catalyst. (2) 8g of Co 3 O 4 Mixing with 90mL of GO with concentration of 8mg/mL, 0.5g of lactose and 20mL of ethanol, fully stirring and ultrasonically treating the mixture for 30min, transferring into a stainless steel reaction kettle with a tetrafluoroethylene liner, and performing hydrothermal reaction at 130 ℃ for 3 hours to obtain cylindrical high-strength loaded Co 3 O 4 The graphene hydrogel (figure 6) of the catalyst is frozen for 6 hours at the temperature of ̵ -20 ℃ below zero, then the hydrogel is frozen, dried and treated for 8 hours to obtain the graphene aerogel composite material of the supported catalyst, the composite material is placed in a microwave reactor and heated for 120 seconds under the power of 400W to carry out annealing treatment to obtain the final supported Co 3 O 4 Graphene aerogel composites of the catalyst.
Example 2
(1) 23.8g of cobalt chloride hexahydrate and 4.4g of cerium nitrate hexahydrate were each dissolved in deionized water to prepare a solution having a concentration of 2 mol/L. Then, 17.5g of sodium carbonate was dissolved in 800mL of deionized water to prepare a solution, and the solution was heated to 60℃and kept at a constant temperature. Under the condition of high-speed mechanical stirring, cobalt nitrate solution and cerium nitrate solution are respectively added into sodium carbonate solution drop by drop at a constant speed, and purple and uniform precipitate is gradually generated. Adding NaOH to make it slightly alkaline (pH 9) and continuously reacting for 3 hr, adding 30mL hydrogen peroxide (content 33%) to make the solution brown, continuously reacting for 1 hr, cooling to room temperature, centrifuging the precipitate, and cleaning to remove Na + And anions, adding deionized water again to obtain brown high-valence Co-Ce hydroxide nano material dispersion liquid. (2) Mixing the dispersion liquid of the previous 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 into a stainless steel reaction kettle with a tetrafluoroethylene liner, performing hydrothermal reaction at 130 ℃ for 3 hours to obtain cylindrical high-strength graphene hydrogel loaded with Co-Ce hydroxide, freezing the hydrogel at-20 ℃ for 8 hours, performing freeze drying treatment for 8 hours to obtain graphene aerogel loaded with Co-Ce hydroxide, and heating at 300 ℃ for 240 minutes to perform annealing treatment to obtain the final Co-loaded graphene aerogel 3 O 4 -Ce 2 O 3 Graphene aerogel composites of the catalyst.
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, 17.5g of sodium carbonate was dissolved in 800mL of deionized water to prepare a solution, and the solution was heated to 60℃and kept at a constant temperature. Under the condition of high-speed mechanical stirring, co 2+ And Bi (Bi) 3+ The solution was added dropwise to the sodium carbonate solution at a constant rate to gradually produce a purple and uniform precipitate. Continuing the reaction for 3 hours, cooling to room temperature, centrifuging and cleaning the precipitate for more than 3 times to remove Na + And an anion, drying the precipitate at 60 ℃ overnight to obtain the purple cobalt carbonate-cerium carbonate nanoparticle 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 into a stainless steel reaction kettle with a tetrafluoroethylene inner container, carrying out hydrothermal reaction at 130 ℃ for 3 hours to obtain cylindrical high-strength graphene hydrogel loaded with cobalt carbonate-cerium carbonate catalyst, placing the hydrogel below ̵ ℃ for 8 hours, carrying out freeze drying treatment for 8 hours, obtaining graphene aerogel loaded with cobalt carbonate-cerium carbonate, and carrying out annealing treatment at 300 ℃ for 240 minutes to obtain the final Co-loaded graphene aerogel 3 O 4 -Ce 2 O 3 Graphene aerogel composites of the catalyst.
Application of the invention
The graphene aerogel composite material loaded with the cobalt-based catalyst is filled into a cylindrical poison filtering box with the inner cavity diameter of 76mm and the height of 60mm, and then the carbon monoxide poison filtering box is manufactured. The toxin filtering box shell is formed by 3D printing of polylactic acid materials, 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.
Specific test conditions: the poison filtering box is arranged in a fixed bed tester, the tightness is checked, the testing temperature is set to 25 ℃, air is taken as carrier gas to enter a testing system through a drying tower filled with silica gel drying agent, 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. The concentration of CO before and after passing through the filter cartridge was detected by using an Agilent 8890GC gas chromatograph equipped with a Flame Ionization Detector (FID), and the gas sampling and sampling were performed by using high-precision syringes, with sampling time of every 5 min. According to the relevant regulations in the national standard GB2892-2009, when the concentration of CO passing through the toxin filter box is higher than 50ppm, the concentration of CO is determined to be higher than the warning concentration, the toxin filter box is penetrated, and the experiment is stopped. The length of time until the toxic cartridge is penetrated when the CO starts to pass through the toxic cartridge is the effective protection time of the toxic cartridge against CO.
As can be seen from fig. 8, the CoO-loaded graphene aerogel composite is capable of effectively reducing the CO concentration in air from 660ppm (mL/L) to less than 1ppm at normal temperature. Along with the progress of the CO catalytic conversion reaction, at 380min, the concentration of CO passing through the toxin filtering box is higher than 50ppm, namely the protection time of the graphene aerogel loaded with CoO on CO is 410 min. When the test objects are loaded with CoO-CeO and CoO-BiO, the protection time of the poison filtering box on CO reaches 520 minutes and 580 minutes respectively, which shows that the addition of Ce and Bi in the cobalt-based catalyst can effectively enhance the catalytic conversion reaction activity of the catalyst on CO. Therefore, the graphene aerogel composite material loaded with the cobalt-based catalyst and the additive thereof can realize effective protection for low-concentration CO in 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 (1)
1. A preparation method of the graphene aerogel loaded with the cobalt-based catalyst comprises the following steps: firstly, 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 solution II with the concentration of less than 0.2mol/L by using a precipitator, heating the solution II to 60-80 ℃ and keeping the temperature, and 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, wherein the mixed solution gradually turns purple or brown to generate purple or brown nano-particle precipitates;
secondly, adding NaOH into the mixed solution to adjust to be weak alkaline, continuously reacting for 1-3 hours, and then adding sodium hydroxide or hydrogen peroxide solution to continuously react for 1 hour;
thirdly, after the reaction is finished, cooling the reaction solution to room temperature, centrifuging and cleaning the precipitate for more than 3 times, drying the precipitate at 110 ℃ for 2 hours to obtain powder, and directly mixing the powder with graphene oxide, a cross-linking agent and an organic solvent; or roasting the precipitate at 300-400 ℃ for 3-4 hours to obtain a cobalt-based catalyst of black powder, and mixing the cobalt-based catalyst with graphene oxide, a cross-linking agent and an organic solvent to obtain a mixture;
the cross-linking agent is a polyhydroxy compound without nitrogen atoms or amino groups, and comprises any one of oligomeric starch, water-soluble starch, lactose and ascorbic acid; the organic solvent comprises ethanol or tetrahydrofuran with the purity of more than 95%;
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 liner, and reacting for 3 hours at 120-140 ℃ to obtain elastic frozen graphene hydrogel;
fifthly, placing the graphene hydrogel in a temperature of minus 20 ℃ for 6-8 hours, then performing freeze drying for 8 hours to obtain graphene aerogel loaded with the cobalt-based catalyst, and performing microwave annealing treatment for 60-180 seconds with the power of 300-600W to further reduce polar groups in the aerogel, so as to obtain a graphene aerogel final product with the structure strength enhanced and loaded with the cobalt-based catalyst;
the cobalt salt in the first step comprises any one of cobalt nitrate, cobalt chloride and cobalt acetate;
the oxygenation agent in the first step comprises any one of cerium nitrate, cerium chloride, bismuth nitrate and bismuth chloride;
the precipitant in the first step comprises sodium hydroxide or sodium carbonate;
the graphene oxide in the third step is calculated according to the mass of graphite, the concentration is higher than 6mg/mL, the adding amount of the cross-linking agent is 0.2-0.5g/100mL of the mixture, and the adding amount of the organic solvent is 10-20mL/100mL of the mixture;
the method is characterized in that: the graphene aerogel is applied to removal of the CO in the toxin filtration box.
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| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
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| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
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| 石墨烯负载Co3O4、CuO催化剂的制备及催化CO氧化性能;李高杰;《河南理工大学硕士学位论文》;20161231;第25-40页 * |
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