CN110694629A - Monolithic catalyst taking metal organic framework as sacrificial template and preparation and application thereof - Google Patents

Monolithic catalyst taking metal organic framework as sacrificial template and preparation and application thereof Download PDF

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CN110694629A
CN110694629A CN201911027342.1A CN201911027342A CN110694629A CN 110694629 A CN110694629 A CN 110694629A CN 201911027342 A CN201911027342 A CN 201911027342A CN 110694629 A CN110694629 A CN 110694629A
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temperature
catalyst
cobalt
organic framework
sacrificial template
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钟金平
叶代启
曾译葵
付名利
吴军良
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South China University of Technology SCUT
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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
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g

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Abstract

An integral catalyst with a metal organic framework as a sacrificial template and preparation and application thereof. Uniformly stirring and dissolving cobalt salt, ammonium fluoride, urea and a solvent, transferring the mixture into a reaction kettle, adding clean foam nickel, and preserving heat under the solvothermal condition to obtain a precursor of cobalt hydroxide loaded on the foam nickel; transferring the product into a reaction solution containing metal cobalt salt and an organic bridging ligand, standing or keeping for a period of time under solvothermal conditions, washing the obtained product with distilled water and an absolute ethyl alcohol solvent for a plurality of times, drying overnight, and then obtaining the metal-organic framework-sacrificial template framework monolithic catalyst through two-stage calcination. The amount of the foam nickel loaded metal organic framework compound prepared by the method is greatly increased, the coverage area is more uniform, and the prepared appearance is more uniform; the catalyst has stronger capability of catalyzing and oxidizing VOCs; the water resistance is obviously improved; can still maintain good catalytic activity after multiple catalytic oxidation cycles.

Description

Monolithic catalyst taking metal organic framework as sacrificial template and preparation and application thereof
Technical Field
The invention belongs to the technical field of material chemistry and atmospheric pollution control, relates to a technology for catalytic oxidation of volatile organic waste gases (VOCs), and particularly relates to an integral catalyst taking a metal organic framework as a sacrificial template, and preparation and application thereof.
Background
The emission of Volatile Organic Compounds (VOCs) is one of the major environmental problems facing today, and has a serious impact on the natural environment and human health. Catalytic oxidation is one of the most extensive processing techniques for processing VOCs, where catalyst preparation is critical to catalytic oxidation. The high-efficiency catalyst is required to have the characteristics of large surface area, high stability, strong water resistance, easy regeneration and the like. The existing commonly used industrial catalyst has the defects of small specific surface area, poor water resistance and short service life, so that the research and development of a catalyst which is more efficient and can rapidly realize the degradation of VOCs is urgently needed. Compared with the traditional powder catalyst, the metal-organic framework-based monolithic catalyst has larger specific surface area, strong integrity, large contact area and higher adsorption capacity, and the comprehensive performance of the catalyst can be improved in order to obtain the monolithic catalytic degradation VOCs catalytic material with higher activity.
The organic framework compound shows different pore sizes due to different bridging ligands, so that the metal organic framework compound has better selectivity to gas, and the preparation of the porous metal organic framework with different pore sizes is also favorable for improving the adsorption performance. The organic bridged ligand has different functional groups and thus different selective adsorption to gas. More importantly, the adsorption heat of the organic waste gas in the metal organic framework compound is lower, the temperature required in the adsorption process is lower, and the structure of the organic waste gas is stable, so that the organic waste gas is one of the potential adsorption materials of the organic waste gas.
Disclosure of Invention
The invention aims to overcome the defects of small specific surface area, low loading capacity, poor stability, relatively low activity and the like in the prior art, and provides a brand-new preparation method of the monolithic catalyst with the metal-organic frame as the sacrificial template frame, and the prepared monolithic catalyst has good adsorption catalytic degradation performance on VOCs.
In order to realize the purpose, the invention adopts porous three-dimensional reticular foam nickel as a substrate, obtains the precursors with different morphologies and cobalt hydroxide loaded on the surface of the foam nickel by regulating and controlling the solvent-thermal conditions of metal salt and urea in equal proportion, and then prepares a brand-new metal organic framework monolithic catalyst by introducing an organic bridging ligand surface and etching in situ under the normal temperature or solvent-thermal conditions.
The technical scheme of the invention is as follows:
a preparation method of monolithic catalyst with metal organic framework as sacrificial template comprises stirring cobalt salt, ammonium fluoride, urea and solvent for uniform dissolution, transferring into a reaction kettle, adding clean foam nickel, and keeping temperature under solvothermal condition to obtain precursor with cobalt hydroxide loaded on the foam nickel; and then transferring the prepared precursor with cobalt hydroxide loaded on the foamed nickel into a reaction solution containing metal cobalt salt and an organic bridging ligand, standing or keeping for a period of time under solvothermal conditions, washing the obtained product with distilled water and an absolute ethyl alcohol solvent for several times, drying overnight, and then obtaining the metal-organic framework-sacrificial template framework monolithic catalyst through two-stage calcination.
The method comprises the following two steps:
(1) preparation of a precursor with cobalt hydroxide loaded on the foamed nickel:
weighing cobalt salt, dissolving the cobalt salt in a reaction solution, adding urea and ammonium fluoride, stirring and dissolving at room temperature, transferring the solution to a liner of a polytetrafluoroethylene reaction kettle when the solution is light red, then placing foamed nickel cleaned by dilute hydrochloric acid into the reaction kettle, carrying out hydrothermal reaction, naturally cooling to room temperature, cleaning the foamed nickel by distilled water, and drying for later use to obtain a precursor;
(2) preparing monolithic catalysts with different metal organic frameworks as sacrificial templates:
weighing an organic bridging ligand in a beaker, adding reaction liquid and metal cobalt salt, stirring and dissolving uniformly, transferring to an inner container of a polytetrafluoroethylene reaction kettle, then adding the precursor prepared in the step (1), covering a kettle cover for carrying out static or hydrothermal reaction, naturally cooling to room temperature, washing with distilled water and absolute ethyl alcohol, carrying out vacuum drying, and obtaining the preparation of the integral catalyst with a metal organic framework as a sacrificial template through two-stage calcination.
In the above method, in the step (1), the cobalt salt is cobalt nitrate hexahydrate, cobalt sulfate hexahydrate or cobalt chloride hexahydrate; the mass of the cobalt salt is 2.5-3.0 g; the reaction solution is water and ethanol, the volume of the water is 20-40 mL, the volume of the absolute ethanol is 20-40 mL, and the mixing volume ratio of the water to the absolute ethanol is 1: 1; the mass of the ammonium fluoride is 0.34-0.98 g; the mass of the urea is 1.08-2.16 g.
In the method, in the step (1), the stirring temperature at room temperature is 28-36 ℃, and the stirring speed is 150-300 r/min; the stirring time is 0.5-1 h, and the temperature of the hydrothermal reaction is 120-140 ℃; the time of the hydrothermal reaction is 12-24 h; the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
In the above method, in the step (2), the metal cobalt salt is cobalt nitrate hexahydrate, cobalt sulfate hexahydrate, cobalt chloride hexahydrate or cobalt acetate tetrahydrate; the mass of the metal cobalt salt is 0.5-1.2 g; the organic bridging ligand is 2-methylimidazole, 2 ' 5-dihydroxyterephthalic acid, terephthalic acid or 1 ' 3 ' 5-benzenetricarboxylic acid; the mass of the organic bridging ligand is 2.5-3 g; the hydrothermal reaction temperature is 30-160 ℃; the hydrothermal reaction time is 12-24 h; the reaction solution is more than one of water, methanol and N', N-dimethylformamide; the addition amount of the reaction solution is 40-60 mL.
In the method, in the step (2), the drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
In the above method, in the step (2), the two-stage calcination method comprises: raising the temperature from room temperature to 320-450 ℃ at the speed of 2-5 ℃/min by a temperature raising program under the condition of nitrogen, keeping the temperature for 3-5 h, then closing nitrogen and introducing air, reducing the temperature to 300-350 ℃ at the speed of 5-10 ℃/min, keeping the temperature for 3-4 h, and finally reducing the temperature to room temperature at the speed of 1-10 ℃/min.
The catalyst is an integral supported catalyst, and has a large specific surface area of 85.5-282.8 cm-2g-1(ii) a Has the performance of efficiently degrading VOCs and the conversion rate T of toluene90About 210-250 ℃; the water resistance is high, and the conversion rate of toluene can be kept at about 85-98% in the presence of 1-5% of water vapor; and good stability, and the conversion rate of the toluene can still be maintained at about 95-99% after the continuous reaction for 48 hours.
An integral catalyst using metal organic frame as sacrificial template is used in the field of air pollution control.
Compared with the prior art, the invention has the following advantages:
1. by loading the metal organic framework compound on the foamed nickel in situ, compared with a powder catalyst, the specific surface area of the catalyst material is greatly improved, and the loaded metal organic framework compound is obviously increased.
2. The prepared metal-organic framework is a sacrificial template framework monolithic catalyst and shows stronger water resistance, stronger VOCs adsorption capacity and higher catalytic oxidation activity.
3. The prepared metal-organic framework is a sacrificial template framework monolithic catalyst and shows higher selective adsorption capacity on VOCs.
4. The good stability performance can be still kept after the VOCs is subjected to multiple cycles of catalytic oxidation.
5. The preparation process is simple and easy to implement, and the preparation conditions are mild.
6. Compared with the traditional conventional synthesis method, the metal organic framework monolithic catalyst prepared by the method has larger specific surface area; the amount of the foam nickel loaded metal organic framework compound prepared by the method is greatly increased, the coverage area is more uniform, and the prepared appearance is more uniform; the catalyst has stronger capability of catalyzing and oxidizing VOCs; the water resistance is obviously improved; can still maintain good catalytic activity after multiple catalytic oxidation cycles. The preparation process of the metal organic framework-sacrificial template monolithic catalyst is simple, convenient and feasible, has mild conditions, and has wide application prospect.
Drawings
Fig. 1 is a scanning electron microscope image of a precursor of cobalt hydroxide loaded on the surface of nickel foam prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of a precursor of cobalt hydroxide loaded on the surface of nickel foam prepared in example 5 of the present invention.
FIG. 3 shows Co obtained in examples 1 and 6 of the present invention3O4-Co(OH)2@ NF and Co3O4-MOF-74@ NF monolithic catalyst nitrogen sorption and desorption profile.
FIG. 4 shows Co obtained after calcination in examples 1 and 6, prepared according to the invention3O4-Co(OH)2@ NF and Co3O4-MOF-74@ NF monolithic catalyst for toluene.
FIG. 5 shows Co obtained in example 6 of the present invention3O4-MOF-74@ NF agent monolithic catalyst scanning electron micrographs.
FIG. 6 shows Co obtained in example 7 of the present invention3O4-MOF-74@ NF monolithic catalyst foam nickel monolithic catalyst scanning electron micrographs.
Detailed Description
Example 1
0.9 g of cobalt nitrate hexahydrate, 0.68 g of ammonium fluoride and 2.16 g of urea were weighed out and dispersed in 30 mLStirring and dissolving in a mixed solution of ethanol and 30 mL of deionized water at room temperature, then adding 1 piece of 2 x 5 cm porous three-dimensional reticular foamed nickel, then transferring to a reaction kettle, preserving the temperature at 120 ℃ for 12 h, cooling to room temperature, filtering to obtain pink precipitate, washing with clean water for 3 times, washing with ethanol for 3 times, and drying at 60 ℃ overnight to obtain a precursor of cobalt hydroxide loaded on the surface of the foamed nickel for later use. Weighing 3 g of 2-methylimidazole in a beaker, adding 60 mL of methanol and 0.5g of cobalt nitrate hexahydrate, stirring for dissolving, placing a precursor with prepared cobalt hydroxide loaded on the surface of foamed nickel in the beaker for standing for 12 h to obtain a product, washing the product with distilled water and ethanol for multiple times, drying at 60 ℃ for overnight, and performing two-stage calcination, namely, increasing the temperature of a heating program under the condition of nitrogen at a rate of 5 ℃/min from room temperature to 400 ℃, keeping the temperature for 3.5 h, closing nitrogen, introducing air, reducing the temperature to 350 ℃ at a rate of 10 ℃/min, keeping the temperature for 3.5 h, and finally reducing the temperature to room temperature at a rate of 10 ℃/min to obtain Co3O4-ZIF-67@ NF monolith catalyst.
As can be seen from FIG. 1, Co was successfully prepared3O4-Co(OH)2@ NF precursor monolithic catalysts. As can be seen from FIG. 3, Co3O4-Co(OH)2@ NF Nitrogen adsorption Curve with a surface area of 27.5 cm-2g-1It is stated that the surface area before the organic framework compound is not supported is significantly smaller than before the organic framework compound is supported.
Example 2
The specific procedure of example 2 is substantially the same as that of example 1, except that 3 g of terephthalic acid and 1.0 g of cobalt acetate are weighed in a beaker, 30 mL of methanol and 30 mL of N' N-dimethylformamide are added, stirred and dissolved, transferred to a reaction kettle, the prepared cobalt hydroxide-loaded precursor on the surface of the foamed nickel is placed in the reaction kettle and kept at 120 ℃ for 24h, the obtained product is washed with distilled water and ethanol for multiple times, dried overnight at 60 ℃, calcined in two stages, i.e. the temperature rising procedure is firstly increased from room temperature to 400 ℃ at the speed of 5 ℃/min under the condition of nitrogen, kept at the constant temperature for 3.5 h, then the nitrogen is closed and air is blown in at the speed of 10 ℃/min, and then the temperature is kept at the constant temperature for 3.5 h, and the mostThen cooling to room temperature at the speed of 10 ℃/min to obtain Co3O4-MOF-5@ NF monolith catalyst.
Example 3
The specific steps of example 3 are substantially the same as those of example 1, except that the reaction temperature is 140 ℃, the temperature is kept for 24h, the temperature is cooled to room temperature, pink precipitates are obtained by filtration, the precipitates are washed by clean water for 3 times and ethanol for 3 times, and the precipitates are dried at 60 ℃ overnight to obtain a precursor of cobalt hydroxide loaded on the surface of foamed nickel. Weighing 3 g of 2 ', 5-dihydroxyterephthalic acid and 1.0 g of cobalt acetate tetrahydrate in a beaker, adding 20mL of methanol, 20mL of water and 20mL of N' N-dimethylformamide, stirring for dissolving, transferring the mixture into a reaction kettle, placing a precursor of the prepared cobalt hydroxide loaded on the surface of foamed nickel in the reaction kettle for heat preservation at 120 ℃ for 24 hours to obtain a product, washing the product with distilled water and ethanol for multiple times, drying the product at 60 ℃ for overnight, performing two-stage calcination, namely, increasing the temperature of the precursor from room temperature to 400 ℃ at the speed of 5 ℃/min under the condition of nitrogen, keeping the temperature for 3.5 hours, then closing nitrogen, introducing air, reducing the temperature to 350 ℃ at the speed of 10 ℃/min, keeping the temperature for 3.5 hours, and finally reducing the temperature to the room temperature at the speed of 10 ℃/min to obtain Co3O4-MOF-74@ NF monolith catalyst.
Example 4
The specific procedure of example 4 is substantially the same as in example 1. The difference is that 3 g of 1,3, 5-benzenetricarboxylic acid ligand and 1 g of cobalt nitrate hexahydrate are weighed in a beaker, 60 mL of methanol is added, the mixture is stirred and dissolved and transferred to a reaction kettle, a precursor of the prepared cobalt hydroxide loaded on the surface of foamed nickel is placed in the reaction kettle and kept at 160 ℃ for 24 hours, the obtained product is washed by distilled water and washed by ethanol for a plurality of times, dried and kept overnight at 60 ℃, the temperature is raised to 400 ℃ through two-stage calcination, namely, the temperature raising program is firstly raised from room temperature to 400 ℃ at the speed of 5 ℃/min under the condition of nitrogen, the temperature is kept for 3.5 hours, then the nitrogen is closed, air is introduced to be reduced to 350 ℃ at the speed of 10 ℃/min, the temperature is kept for 3.5 hours, and finally the temperature is reduced to room temperature at3O4-HKUST @ NF monolithic catalyst.
Example 5
Example 5 specific procedureBasically the same as in example 1, except that 0.9 g of cobalt chloride hexahydrate was weighed to obtain a precursor with cobalt hydroxide loaded on the surface of the nickel foam. Weighing 3 g of 2-methylimidazole in a beaker, adding 60 mL of methanol and 0.5g of cobalt nitrate, stirring for dissolving, placing a precursor with prepared cobalt hydroxide loaded on the surface of foamed nickel in the beaker for standing for 12 h to obtain a product, washing with distilled water and ethanol for multiple times, drying at 60 ℃ for overnight, and performing two-stage calcination, namely, increasing the temperature of a heating program under the condition of nitrogen at a rate of 5 ℃/min from room temperature to 400 ℃, keeping the temperature for 3.5 h, closing nitrogen, introducing air, reducing the temperature to 350 ℃ at a rate of 10 ℃/min, keeping the temperature for 3.5 h, and finally reducing the temperature to room temperature at a rate of 10 ℃/min to obtain Co3O4-ZIF-67@ NF monolith catalyst.
As can be seen from FIG. 2, Co having cobalt hydroxide supported on nickel foam was successfully prepared3O4-Co(OH)2@ NF monolithic catalysts.
Example 6
The specific procedure of example 6 is substantially the same as that of example 1, except that 0.68 g of ammonium fluoride and 1.08 g of urea are weighed and dispersed in a mixture of 30 mL of methanol and 30 mL of deionized water, stirred at room temperature for dissolution, then 1 piece of 2 x 5 cm porous three-dimensional reticulated nickel foam is added, and then the mixture is transferred into a reaction kettle and kept at 140 ℃ for 24h, cooled to room temperature, filtered to obtain pink precipitate, washed with clean water for 3 times, washed with ethanol for 3 times, and dried at 60 ℃ overnight to obtain a precursor with cobalt hydroxide supported on the surface of the nickel foam. Weighing 3 g of 2 ', 5-dihydroxyterephthalic acid and 0.5g of cobalt acetate tetrahydrate in a beaker, adding 20mL of methanol, 20mL of water and 20mL of N' N-dimethylformamide, stirring for dissolving, transferring the mixture into a reaction kettle, placing a precursor of the prepared cobalt hydroxide loaded on the surface of foamed nickel in the reaction kettle for heat preservation at 120 ℃ for 24 hours to obtain a product, washing the product with distilled water and ethanol for multiple times, drying the product at 60 ℃ for overnight, performing two-stage calcination, namely, increasing the temperature of the precursor from room temperature to 400 ℃ at the speed of 5 ℃/min under the condition of nitrogen, keeping the temperature for 3.5 hours, then closing nitrogen, introducing air, reducing the temperature to 350 ℃ at the speed of 10 ℃/min, keeping the temperature for 3.5 hours, and finally, reducing the temperature at the speed of 10 ℃/minCooling to room temperature to obtain Co3O4-MOF-74@ NF monolith catalyst.
As can be seen from FIG. 5, Co with a metal-organic framework compound supported on nickel foam was successfully prepared3O4-MOF-74@ NF monolith catalyst. As can be seen from FIG. 3, Co3O4Nitrogen adsorption curve of MOF-74@ NF, surface area 207.5 cm-2g-1It is stated that the surface area of the precursor prior to loading the organic framework compound is significantly greater than that prior to not loading the organic framework compound.
Example 7
The specific procedure of example 7 is substantially the same as that of example 1, except that 0.34 g of ammonium fluoride and 1.08 g of urea are weighed and dispersed in a mixture of 30 mL of methanol and 30 mL of deionized water, stirred at room temperature for dissolution, then 1 piece of 2 x 5 cm porous three-dimensional reticulated nickel foam is added, and then transferred to a reaction kettle and kept at 140 ℃ for 24h, cooled to room temperature, filtered to obtain pink precipitate, washed with clean water for 3 times, washed with ethanol for 3 times, and dried at 60 ℃ overnight to obtain a cobalt hydroxide supported precursor on the surface of the nickel foam. Weighing 3 g of 2 ', 5-dihydroxyterephthalic acid and 0.5g of cobalt acetate tetrahydrate in a beaker, adding 20mL of methanol, 20mL of water and 20mL of N' N-dimethylformamide, stirring for dissolving, transferring the mixture into a reaction kettle, placing a precursor of the prepared cobalt hydroxide loaded on the surface of foamed nickel in the reaction kettle for heat preservation at 120 ℃ for 24 hours to obtain a product, washing the product with distilled water and ethanol for multiple times, drying the product at 60 ℃ for overnight, performing two-stage calcination, namely, increasing the temperature of the precursor from room temperature to 400 ℃ at the speed of 5 ℃/min under the condition of nitrogen, keeping the temperature for 3.5 hours, then closing nitrogen, introducing air, reducing the temperature to 350 ℃ at the speed of 10 ℃/min, keeping the temperature for 3.5 hours, and finally reducing the temperature to room temperature at the speed of 10 ℃/min to obtain Co3O4-MOF-74@ NF monolith catalyst.
As can be seen from FIG. 6, Co in which an organic framework compound was supported on nickel foam was successfully prepared3O4-MOF-74@ NF monolith catalyst.
Example 8
Example 8 specific procedure: nail alignment by test sampleThe activity of benzene was evaluated by the degradation rate of benzene using a quartz tube (ɸ 6 mm) as a reactor. Before the experiment, 0.1 g of sample and 0.4 g of quartz sand are weighed and uniformly mixed and filled in a quartz tube reactor for fixation, and then 1000 ppm of toluene (O/O) 20 percent is introduced into the reactor2/N2) The nitrogen is oxygenated into balance gas, and the weight hourly space velocity is 60000 mL g-1h-1And performing activity evaluation at 180-280 ℃. The concentration change of toluene in the reaction process is finally detected on line by Online GC. Wherein, the calculation formula of the catalytic oxidation degradation rate of the toluene is as follows:
toluene degradation rate = [ (toluene) inlet- (toluene) outlet ]/(toluene) inlet;
the results are shown in FIG. 4, which shows the Co catalyst prepared in example 13O4-Co(OH)2@ NF and Co catalyst prepared in example 63O4-MOF-74@ NF Activity diagram for catalytic Oxidation of para-toluene, T thereof50And T 90221, 244 and 227 and 264 c, respectively. The later stage shows that the organic framework compound is loaded on the precursor, and the catalytic degradation performance of the organic framework compound is obviously improved.

Claims (9)

1. A preparation method of monolithic catalyst with metal organic frame as sacrificial template is characterized in that,
uniformly stirring and dissolving cobalt salt, ammonium fluoride, urea and a solvent, transferring the cobalt salt, the ammonium fluoride, the urea and the solvent into a reaction kettle, adding clean foam nickel, and preserving heat under the solvothermal condition to obtain a precursor of cobalt hydroxide loaded on the foam nickel; and then transferring the prepared precursor with cobalt hydroxide loaded on the foamed nickel into a reaction solution containing metal cobalt salt and an organic bridging ligand, standing or keeping for a period of time under solvothermal conditions, washing the obtained product with distilled water and an absolute ethyl alcohol solvent for several times, drying overnight, and then obtaining the metal-organic framework-sacrificial template framework monolithic catalyst through two-stage calcination.
2. The preparation method of the monolithic catalyst with the metal organic framework as the sacrificial template according to claim 1, which is characterized by comprising the following two steps:
(1) preparation of a precursor with cobalt hydroxide loaded on the foamed nickel:
weighing cobalt salt, dissolving the cobalt salt in a reaction solution, adding urea and ammonium fluoride, stirring and dissolving at room temperature, transferring the solution to a liner of a polytetrafluoroethylene reaction kettle when the solution is light red, then placing foamed nickel cleaned by dilute hydrochloric acid into the reaction kettle, carrying out hydrothermal reaction, naturally cooling to room temperature, cleaning the foamed nickel by distilled water, and drying for later use to obtain a precursor;
(2) preparing monolithic catalysts with different metal organic frameworks as sacrificial templates:
weighing an organic bridging ligand in a beaker, adding reaction liquid and metal cobalt salt, stirring and dissolving uniformly, transferring to an inner container of a polytetrafluoroethylene reaction kettle, then adding the precursor prepared in the step (1), covering a kettle cover for carrying out static or hydrothermal reaction, naturally cooling to room temperature, washing with distilled water and absolute ethyl alcohol, carrying out vacuum drying, and obtaining the preparation of the integral catalyst with a metal organic framework as a sacrificial template through two-stage calcination.
3. The method for preparing the monolithic catalyst with the metal organic framework as the sacrificial template according to claim 2, wherein in the step (1), the cobalt salt is cobalt nitrate hexahydrate, cobalt sulfate hexahydrate or cobalt chloride hexahydrate; the mass of the cobalt salt is 2.5-3.0 g; the reaction solution is water and ethanol, the volume of the water is 20-40 mL, the volume of the absolute ethanol is 20-40 mL, and the mixing volume ratio of the water to the absolute ethanol is 1: 1; the mass of the ammonium fluoride is 0.34-0.98 g; the mass of the urea is 1.08-2.16 g.
4. The preparation method of the monolithic catalyst with the metal organic framework as the sacrificial template according to claim 2, characterized in that in the step (1), the stirring temperature at room temperature is 28-36 ℃, and the stirring speed is 150-300 r/min; the stirring time is 0.5-1 h, and the temperature of the hydrothermal reaction is 120-140 ℃; the time of the hydrothermal reaction is 12-24 h; the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
5. The method for preparing the monolithic catalyst with the metal organic framework as the sacrificial template according to claim 2, wherein in the step (2), the metal cobalt salt is cobalt nitrate hexahydrate, cobalt sulfate hexahydrate, cobalt chloride hexahydrate or cobalt acetate tetrahydrate; the mass of the metal cobalt salt is 0.5-1.2 g; the organic bridging ligand is 2-methylimidazole, 2 ' 5-dihydroxyterephthalic acid, terephthalic acid or 1 ' 3 ' 5-benzenetricarboxylic acid; the mass of the organic bridging ligand is 2.5-3 g; the hydrothermal reaction temperature is 30-160 ℃; the hydrothermal reaction time is 12-24 h; the reaction solution is more than one of water, methanol and N', N-dimethylformamide; the addition amount of the reaction solution is 40-60 mL.
6. The preparation method of the monolithic catalyst with the metal organic framework as the sacrificial template according to claim 2, wherein in the step (2), the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
7. The method for preparing the monolithic catalyst with the metal organic framework as the sacrificial template according to claim 2, wherein in the step (2), the two-stage calcination method comprises the following steps: raising the temperature from room temperature to 320-450 ℃ at the speed of 2-5 ℃/min by a temperature raising program under the condition of nitrogen, keeping the temperature for 3-5 h, then closing nitrogen and introducing air, reducing the temperature to 300-350 ℃ at the speed of 5-10 ℃/min, keeping the temperature for 3-4 h, and finally reducing the temperature to room temperature at the speed of 1-10 ℃/min.
8. The preparation method of claims 1-7, wherein the metal organic framework is used as a sacrificial template, and the catalyst is an integral supported catalyst with a surface area of 85.5-282.8 cm-2g-1(ii) a Conversion rate T of toluene of the catalyst90The temperature is 210-250 ℃; the conversion rate of toluene can be kept at 85-98% in the presence of 1-5% of water vapor in the catalyst; the catalyst is used in continuous reactionAnd the conversion rate of the toluene can be still maintained at 95-99% within 48 h.
9. The preparation method of claim 8, wherein the monolithic catalyst prepared by the preparation method of the metal organic framework is used as a sacrificial template in the field of atmospheric pollution control.
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