CN112569959A - Preparation method of manganese-modified carbon nanotube-loaded cobalt oxide, product and application thereof - Google Patents
Preparation method of manganese-modified carbon nanotube-loaded cobalt oxide, product and application thereof Download PDFInfo
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- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 33
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 51
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 22
- -1 manganese modified carbon nanotube Chemical class 0.000 claims abstract description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 17
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 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 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 238000007605 air drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 150000001721 carbon Chemical class 0.000 claims description 7
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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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
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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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
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention discloses a preparation method of manganese modified carbon nanotube loaded cobalt oxide, a product and application thereof. Limiting the molar ratio of the cobalt nitrate to the manganese nitrate to (10-35): 1, the molar ratio of cobalt nitrate to CTAB is (73-75): 1, the molar ratio of cobalt nitrate to 2-methylimidazole is 1: 50-3: 100, the total metal molar concentration of cobalt nitrate and manganese nitrate is 0.05-0.08 mol/L, and the molar concentration of 2-methylimidazole is 0.60-0.70 mol/L. The metal organic framework promotes the cobalt and the manganese not to agglomerate under high-temperature treatment, and shows excellent catalytic performance on catalytic combustion of benzene.
Description
Technical Field
The invention belongs to the technical field of catalytic environmental protection, and particularly relates to a preparation method of manganese-modified carbon nanotube-loaded cobalt oxide, and a product and application thereof.
Background
Metal organic framework compounds (MOFs) are porous materials with a repeating network structure synthesized by self-assembly of metal ions or metal cluster compound ions and organic ligands. MOFs have abundant and changeable structures, and show excellent application prospects in the fields of gas adsorption, separation, catalysis, sensing and the like in recent years. The large porosity and specific surface area of the MOFs and the repeated periodic structure are beneficial to the uniform distribution of MOFs active sites, and the MOFs have larger application potential in the field of catalysis.
In recent years, MOF-derived porous nanomaterials have received much attention because they retain the unique structure of MOFs. For example, inorganic carbon materials with good conductivity can be obtained by roasting, and the inorganic carbon materials are applied to the fields of electrocatalysis, supercapacitors, batteries and the like, or metal oxides, metal sulfides, metal phosphides, metal carbides and the like are obtained by roasting with MOFs as precursors and are applied to the fields of catalysis, sensors and the like. In general, the most common oxides derived from MOFs are single metal oxides, binary or ternary metal oxide composites are often used in electrocatalytic applications, such as NiCo2O4、ZnFe2O4/ZnO, etc. The application of the method in the thermal catalytic oxidation reaction in the field of environmental catalysis generally requires high-temperature air atmosphere treatment, and the uniformity of product distribution is difficult to ensure. The final composition and structural morphology of the MOFs are directly influenced by the synthesis method, the raw material ratio and the like.
Disclosure of Invention
The invention provides a preparation method of manganese modified carbon nanotube loaded cobalt oxide.
Yet another object of the present invention is to: provides a manganese modified carbon nano tube loaded cobalt oxide product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of manganese modified carbon nanotube loaded cobalt oxide is characterized in that a bimetallic MOF material CoMn-MOF doped with manganese metal element is prepared by regulating and controlling a surfactant CTAB, and is taken as a sacrificial template, carbonized in a high-temperature reducing atmosphere and then roasted in an air atmosphere, and the preparation method comprises the following steps:
(1) weighing cobalt nitrate hexahydrate (Co (NO)3)2﹒6H2O), 50% manganese nitrate aqueous solution and cetyltrimethylammonium bromide (CTAB) were dissolved in deionized water; weighing 2-methylimidazole and dissolving in deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing and aging for 24 h. The precipitate was collected by centrifugation, washed with ethanol and dried in a forced air drying oven. Controlling the temperature to be 80 ℃ to obtain ZiF-67 modified by manganese;
wherein the molar ratio of the cobalt nitrate to the manganese nitrate is 10: 1-35: 1, the molar ratio of cobalt nitrate to CTAB is 73: 1-75: 1, the molar ratio of cobalt nitrate to 2-methylimidazole is 1: 50-3: 100, the total metal molar concentration of cobalt nitrate and manganese nitrate is 0.05-0.08 mol/L, and the molar ratio of 2-methylimidazole is 0.60-0.70 mol/L;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, the air is switched after the temperature is reduced to the room temperature, and the temperature is increased to 300 ℃ to continue roasting for 2 hours. Obtaining the manganese modified carbon nano tube loaded cobalt oxide.
The invention provides a manganese-modified carbon nanotube-loaded cobalt oxide prepared by the method.
The invention provides application of manganese modified carbon nano tube loaded cobalt oxide in catalytic combustion reaction of benzene.
The performance of the catalysts obtained in the examples in the catalytic oxidation of benzene: the catalyst is put in a continuous flow fixed bed device and mixed gas of benzene and air is introduced for reaction; the reaction pressure is normal pressure to 1 atm, the total gas flow is 50 mL/min, the reaction space velocity is 30000 mL/(g.h), and the initial concentration of benzene in the mixed gas is 1000 ppm.
The metal organic framework promotes cobalt and manganese not to agglomerate under high-temperature treatment, and the metal organic framework is applied to the catalytic combustion reaction of benzene and shows excellent catalytic performance.
The invention has the following characteristics:
(1) the preparation is simple and the material is novel: the manganese-modified carbon nanotube-supported cobalt catalyst is directly obtained from bimetallic CoMn-MOF, and the material is novel and the preparation method is simple.
(2) The performance is excellent: the modification of manganese improves the catalytic combustion performance of cobalt oxide on benzene.
Detailed Description
Example 1
A manganese-modified carbon nanotube-loaded cobalt oxide is prepared by preparing a bimetallic MOF material CoMn-MOF doped with a manganese metal element through regulation and control of a surfactant CTAB, taking the obtained bimetallic MOF material CoMn-MOF as a sacrificial template, carbonizing the sacrificial template in a high-temperature reducing atmosphere, and roasting the carbonized bimetallic MOF material in an air atmosphere, and is prepared by the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate Co (NO) was weighed out3)2﹒6H2O, 0.07 g of 50% aqueous manganese nitrate solution and 0.01g of CTAB (cetyltrimethylammonium bromide) were dissolved in 44 mL of deionized water; weighing 8.21 g of 2-methylimidazole and dissolving in 167 mL of deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing and aging for 24 h; centrifuging, collecting precipitate, washing with ethanol, and drying the precipitate in a forced air drying oven at 80 deg.C to obtain manganese-modified ZiF-67;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2and/Ar) roasting for 2 h at 800 ℃, switching to air after cooling to room temperature, heating to 300 ℃, and continuing roasting for 2 h to obtain the manganese modified carbon nano tube loaded cobalt oxide.
The results of the catalytic oxidation of benzene by the product catalyst of this example are shown in Table 1.
Example 2
The manganese modified carbon nanotube supported cobalt oxide is similar to the step of the embodiment 1, and is prepared by the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate (Co (NO) was weighed out3)2﹒6H2O）、0036 g of 50% aqueous manganese nitrate solution and 0.01g of cetyltrimethylammonium bromide (CTAB) were dissolved in 35 mL of deionized water; weighing 8.21 g of 2-methylimidazole and dissolving in 167 mL of deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing, aging for 24h, collecting precipitate, washing with ethanol, and drying the precipitate in a forced air drying oven at 80 deg.C to obtain manganese-modified ZiF-67;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, the air is switched after the temperature is reduced to the room temperature, and the temperature is increased to 300 ℃ to continue roasting for 2 hours. Obtaining the manganese modified carbon nano tube loaded cobalt oxide.
The results of the catalytic oxidation of benzene by the product catalyst of this example are shown in Table 1.
Example 3
The manganese modified carbon nanotube supported cobalt oxide is similar to the step of the embodiment 1, and is prepared by the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate (Co (NO) was weighed out3)2﹒6H2O), 0.024 g of 50% aqueous manganese nitrate solution and 0.01g of cetyltrimethylammonium bromide (CTAB) were dissolved in 30 mL of deionized water; weighing 8.21 g of 2-methylimidazole, and dissolving in 143 mL of deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing and aging for 24 h. Centrifuging, collecting precipitate, washing with ethanol, and drying the precipitate in a forced air drying oven at 80 deg.C to obtain manganese-modified ZiF-67;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2and/Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, switching to air after the temperature is reduced to room temperature, and heating to 300 ℃ to continue roasting for 2 hours until the manganese modified carbon nano tube loads cobalt oxide.
The results of the catalytic oxidation of benzene by the product catalyst of this example are shown in Table 1.
Example 4
The manganese modified carbon nanotube supported cobalt oxide is similar to the step of the embodiment 1, and is prepared by the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate (Co (NO) was weighed out3)2﹒6H2O), 0.02 g of 50% nitreManganese acid aqueous solution and 0.01g Cetyl Trimethyl Ammonium Bromide (CTAB) dissolved in 26 mL deionized water; weighing 8.21 g of 2-methylimidazole, and dissolving in 143 mL of deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing and aging for 24 h. Centrifuging, collecting precipitate, washing with ethanol, and drying the precipitate in a forced air drying oven at 80 deg.C to obtain manganese-modified ZiF-67;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2and/Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, switching to air after the temperature is reduced to room temperature, and heating to 300 ℃ to continue roasting for 2 hours until the manganese modified carbon nano tube loads cobalt oxide.
The results of the catalytic oxidation of benzene by the product catalyst of this example are shown in Table 1.
Comparative example 1:
preparation of MOF-derived cobalt oxide:
(1) 3.60 g of cobalt nitrate hexahydrate (Co (NO) was weighed3)2﹒6H2O) and 4.74 g of 2-methylimidazole are dissolved in 360 mL of methanol, the mixture is stirred at room temperature for 12 hours, then the precipitate is collected by centrifugation and washed by methanol for a plurality of times, and the precipitate is dried in a forced air drying oven at 60 ℃ to obtain ZiF-67;
(2) placing the sample obtained in the step (1) in a tube furnace, and introducing a hydrogen-argon mixed gas (5% H)2and/Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, switching to air after the temperature is reduced to room temperature, and heating to 500 ℃ to continue roasting for 2 hours to obtain the MOF derived cobalt oxide catalyst.
The performance of the catalysts obtained in examples 1 to 4 and comparative example 1 in the catalytic oxidation of benzene: the catalyst is put in a continuous flow fixed bed device and mixed gas of benzene and air is introduced for reaction; the reaction pressure is normal pressure to 1 atm, the total gas flow is 50 mL/min, the reaction space velocity is 30000 mL/(g.h), and the initial concentration of benzene in the mixed gas is 1000 ppm.
Table 1 shows the results of catalytic oxidation of benzene by the catalysts prepared in examples 1 to 4 and comparative example 1, wherein the temperatures T are 10%, 50% and 100% conversion, respectively10%、T50%And T100%As can be seen from Table 1, the benzene oxidation reactions catalyzed by examples 1-4 are all superior to those catalyzed by comparative example 1:
Claims (7)
1. a preparation method of manganese modified carbon nanotube loaded cobalt oxide is characterized in that a surfactant CTAB is used for regulating and controlling to prepare a metal element manganese-doped bimetallic MOF material CoMn-MOF, the metal element manganese-doped bimetallic MOF material CoMn-MOF is used as a sacrificial template, and the sacrificial template is obtained by carbonization in a high-temperature reducing atmosphere and roasting in an air atmosphere, and comprises the following steps:
(1) cobalt nitrate hexahydrate Co (NO) is weighed3)2﹒6H2Dissolving O, 50% manganese nitrate aqueous solution and Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water, wherein the molar ratio of cobalt nitrate to manganese nitrate is (10-35): 1, the molar ratio of cobalt nitrate to CTAB is (73-75): 1, the total metal molar concentration of cobalt nitrate and manganese nitrate is 0.05-0.08 mol/L; weighing 2-methylimidazole, and dissolving in deionized water, wherein the molar concentration of the 2-methylimidazole is 0.60-0.70 mol/L; mixing the two solutions, wherein the molar ratio of cobalt nitrate to 2-methylimidazole is 1: 50-3: stirring at room temperature for 1-2 h, standing and aging for 24 h; the precipitate was collected by centrifugation, washed with ethanol and dried in a forced air drying oven. Controlling the temperature to be 80 ℃ to obtain ZiF-67 modified by manganese;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2and/Ar) roasting for 2 h at 800 ℃, switching to air after cooling to room temperature, heating to 300 ℃, and continuing roasting for 2 h to obtain the manganese modified carbon nano tube loaded cobalt oxide.
2. The preparation method of the manganese-modified carbon nanotube-supported cobalt oxide according to claim 1, characterized by comprising the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate Co (NO) was weighed out3)2﹒6H2O, 0.07 g of 50% aqueous manganese nitrate solution and 0.01g of CTAB (cetyltrimethylammonium bromide) were dissolved in 44 mL of deionized water; weighing 8.21 g of 2-methylimidazole and dissolving in 167 mL of deionized water; mixing the two solutionsMixing, stirring at room temperature for 1-2 h, standing and aging for 24 h; centrifuging, collecting precipitate, washing with ethanol, and drying the precipitate in a forced air drying oven at 80 deg.C to obtain manganese-modified ZiF-67;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2and/Ar) roasting for 2 h at 800 ℃, switching to air after cooling to room temperature, heating to 300 ℃, and continuing roasting for 2 h to obtain the manganese modified carbon nano tube loaded cobalt oxide.
3. The preparation method of the manganese-modified carbon nanotube-supported cobalt oxide according to claim 1, characterized by comprising the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate (Co (NO) was weighed out3)2﹒6H2O), 0.036 g of 50% aqueous manganese nitrate solution and 0.01g of cetyltrimethylammonium bromide (CTAB) were dissolved in 35 mL of deionized water; weighing 8.21 g of 2-methylimidazole and dissolving in 167 mL of deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing, aging for 24h, collecting precipitate, washing with ethanol, and drying the precipitate in a forced air drying oven at 80 deg.C to obtain manganese-modified ZiF-67;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, the air is switched after the temperature is reduced to the room temperature, and the temperature is increased to 300 ℃ to continue roasting for 2 hours. Obtaining the manganese modified carbon nano tube loaded cobalt oxide.
4. The preparation method of the manganese-modified carbon nanotube-supported cobalt oxide according to claim 1, characterized by comprising the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate (Co (NO) was weighed out3)2﹒6H2O), 0.024 g of 50% aqueous manganese nitrate solution and 0.01g of cetyltrimethylammonium bromide (CTAB) were dissolved in 30 mL of deionized water; weighing 8.21 g of 2-methylimidazole, and dissolving in 143 mL of deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing and aging for 24 h. Centrifuging to collect precipitate, washing with ethanol, and drying in air-blast drying oven 80Drying at the temperature of DEG C to obtain ZiF-67 modified by manganese;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2and/Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, switching to air after the temperature is reduced to room temperature, and heating to 300 ℃ to continue roasting for 2 hours until the manganese modified carbon nano tube loads cobalt oxide.
5. The preparation method of the manganese-modified carbon nanotube-supported cobalt oxide according to claim 1, characterized by comprising the following steps:
(1) 0.58 g of cobalt nitrate hexahydrate (Co (NO) was weighed out3)2﹒6H2O), 0.02 g of 50% aqueous manganese nitrate solution and 0.01g of cetyltrimethylammonium bromide (CTAB) were dissolved in 26 mL of deionized water; weighing 8.21 g of 2-methylimidazole, and dissolving in 143 mL of deionized water; mixing the two solutions, stirring at room temperature for 1-2 h, standing and aging for 24 h. Centrifuging, collecting precipitate, washing with ethanol, and drying the precipitate in a forced air drying oven at 80 deg.C to obtain manganese-modified ZiF-67;
(2) the manganese-modified ZiF-67 was placed in a tube furnace and a hydrogen-argon mixture (5% H) was passed through2and/Ar) roasting for 2 hours, wherein the roasting temperature is 800 ℃, switching to air after the temperature is reduced to room temperature, and heating to 300 ℃ to continue roasting for 2 hours until the manganese modified carbon nano tube loads cobalt oxide.
6. Manganese-modified carbon nanotube-supported cobalt oxide, characterized in that it is prepared according to the method of any one of claims 1 to 5.
7. Use of the manganese-modified carbon nanotube-supported cobalt oxide of claim 6 in the catalytic combustion reaction of benzene.
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