CN111804297B - Hafnium oxide composite material, preparation method and application thereof - Google Patents

Hafnium oxide composite material, preparation method and application thereof Download PDF

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CN111804297B
CN111804297B CN202010706183.4A CN202010706183A CN111804297B CN 111804297 B CN111804297 B CN 111804297B CN 202010706183 A CN202010706183 A CN 202010706183A CN 111804297 B CN111804297 B CN 111804297B
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hafnium oxide
modification layer
composite material
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noble metal
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CN111804297A (en
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李文志
李存朔
洪紫薇
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University of Science and Technology of China USTC
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes

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Abstract

The invention provides a hafnium oxide composite material, which comprises a hafnium oxide carrier, a non-metal oxide modification layer and noble metal particles; the non-metal oxide modification layer is coated on the surface of the hafnium oxide carrier, and the noble metal particles are loaded on the surface of the hafnium oxide carrier. The application also provides a preparation method of the hafnium oxide composite material. The application also provides a combustion method of low-concentration methane. According to the application, the non-metal oxide modification layer is introduced, so that the noble metal particles have high dispersibility on the surface of the hafnium oxide carrier, and the catalyst has excellent catalytic activity and stability for catalytic combustion reaction of low-concentration methane under low noble metal loading.

Description

Hafnium oxide composite material, preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a hafnium oxide composite material, and a preparation method and application thereof.
Background
Hydrocarbons are one of the major atmospheric pollutants, and small molecular weight alkanes are important players in the formation of photochemical smog. Where methane is also a recognized greenhouse gas, with over twenty times greater capacity to cause greenhouse effects than carbon dioxide, the large methane emissions will cause immeasurable damage to the ecosystem. The exhaust gas emissions from mine ventilation gas and natural gas internal combustion engines are the main source of methane gas, which is a significant emission and has a low methane concentration.
With the increasing importance of the country on ecological civilization construction and the implementation of more environmental regulations, methane purification under mild conditions faces more opportunities and challenges. However, the n-tetrahedron type methane molecule is highly symmetrical, has no electron affinity and permanent dipole moment, has extremely stable carbon-hydrogen bond, has the bond energy as high as 434kJ/mol, and is difficult to activate under mild conditions. Therefore, the effective treatment of the low-concentration methane discharged into the atmosphere has important significance for environmental protection and ecological civilization construction.
The catalytic combustion of methane is a promising technology for purifying low-concentration methane, wherein the palladium-based catalyst can effectively activate the C-H bond of methane under low-temperature conditions, and is the most efficient methane catalytic combustion catalyst at present. However, palladium is very expensive and has a very low global storage capacity, and its oxide is easily decomposed and sintered under high temperature conditions. Therefore, the load capacity of noble metal in the palladium-based catalyst is reduced, the utilization efficiency and stability of active center palladium are improved, and the realization of high catalytic activity becomes a hotspot direction of methane catalytic combustion research.
Disclosure of Invention
The invention aims to provide a hafnium oxide composite material, which has excellent catalytic activity and stability as a catalyst for low-concentration methane combustion.
In view of the above, the present application provides a hafnium oxide composite material, which includes a hafnium oxide carrier, a non-metal oxide modification layer, and noble metal particles; the non-metal oxide modification layer is coated on the surface of the hafnium oxide carrier, and the noble metal particles are loaded on the surface of the hafnium oxide carrier.
Preferably, the non-metal oxide modification layer is an amorphous silicon dioxide layer, and the noble metal particles are palladium particles.
Preferably, the mass ratio of the hafnium oxide carrier, the non-metal oxide modification layer and the noble metal particles is 100: (1-10): (0.5-2.0).
The application also provides a preparation method of the hafnium oxide composite material, which comprises the following steps:
carrying out reflux reaction on a non-metal oxide source and hafnium oxide in an organic solvent, and drying to obtain the hafnium oxide coated with a non-metal oxide modification layer on the surface;
and mixing and dipping the noble metal source and the hafnium oxide coated with the non-metal oxide modification layer on the surface in a solvent, drying and calcining to obtain the hafnium oxide composite material.
Preferably, the non-metal oxide source is organosilane, and the organosilane is n-octyltriethoxysilane; the noble metal source is a palladium source, and the palladium source is palladium acetate.
Preferably, in the step of obtaining the hafnium oxide coated with the non-metal oxide modification layer on the surface, the organic solvent is toluene, the drying is performed in a vacuum manner, the drying temperature is 50-100 ℃, and the drying time is 2-12 hours.
Preferably, in the step of obtaining the hafnium oxide composite material, the organic solvent is toluene, the drying mode is vacuum drying, the drying temperature is 50-100 ℃, the drying time is 2-12 hours, the calcining temperature is 300-900 ℃, and the calcining time is 3-6 hours.
The application provides a combustion method of low-concentration methane, which comprises the following steps:
mixing the mixed gas with a catalyst, activating, cooling, heating and combusting; the mixed gas comprises 1-5% of methane and the balance of air by volume fraction, and the catalyst is the hafnium oxide composite material or the hafnium oxide composite material prepared by the preparation method in the scheme.
Preferably, the temperature of the activation treatment is 400-600 ℃, and the temperature of the combustion is 300-400 ℃.
The application provides a hafnium oxide composite material, which comprises a hafnium oxide carrier, a non-metal oxide modification layer and noble metal particles; the non-metal oxide modification layer is coated on the surface of the hafnium oxide carrier, and the noble metal particles are loaded on the surface of the hafnium oxide carrier. The application provides a hafnium oxide composite material is through the dispersion effect of cladding at the non-metallic oxide layer on hafnium oxide carrier surface to noble metal active component for noble metal can form the nano-particle of high dispersion type, and simultaneously, non-metallic oxide modification layer passes through the electron transfer and adjusts the electronic structure of hafnium oxide carrier and active component, more reasonable electronic structure makes the oxygen molecule in the gaseous phase obtain more efficient absorption and activation, thereby improved its catalytic activity as the catalyst, furthermore, non-metallic oxide modification layer can also prevent the poisoning of the hydrone of reaction production to active component noble metal particle through the transfer of hydroxyl species, thereby improved its high temperature stability as the catalyst.
Drawings
FIG. 1 shows the Pd/M-HfO catalyst prepared in example 1 and having highly dispersed nano-particles2Scanning electron microscope images of (a);
FIG. 2 shows the Pd/M-HfO catalyst prepared in example 1 and having highly dispersed nano-particles2Transmission electron microscope images of (a);
FIG. 3 shows the Pd/M-HfO catalyst prepared in example 12A catalytic activity map of low concentration methane conversion with temperature;
FIG. 4 shows the Pd/M-HfO catalyst prepared in example 12The experiment on the catalytic combustion life of the low-concentration methane.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the requirement of low-concentration methane combustion at present, the application provides a hafnium oxide composite material, and the composite material has higher catalytic activity and high-temperature stability as a catalyst for low-concentration methane combustion due to the modification of the hafnium oxide carrier by the non-metal oxide modification layer. Specifically, the embodiment of the invention discloses a hafnium oxide composite material, which comprises a hafnium oxide carrier, a non-metal oxide modification layer and noble metal particles; the non-metal oxide modification layer is coated on the surface of the hafnium oxide carrier, and the noble metal particles are loaded on the surface of the hafnium oxide carrier.
In the hafnium oxide composite material provided by the application, the hafnium oxide is used as a carrier, is a monoclinic hafnium oxide, has high-temperature stability, and cannot undergo phase change and sintering under reaction conditions.
The surface of the hafnium oxide carrier is coated with a non-metal oxide modification layer, and more specifically, the non-metal oxide modification layer is a silicon dioxide modification layer; the silicon dioxide modification layer can disperse the active component noble metal particles, so that the noble metal particles are highly dispersed on the surface of the hafnium dioxide carrier, meanwhile, 4f state electrons of the hafnium and 3d state electrons of the noble metal are changed through electron transfer in the silicon dioxide modification layer, and meanwhile, the electrons are better transferred to a 0-to-1 s state, so that the adsorption and activation of oxygen molecules are facilitated, meanwhile, silicon hydroxyl in the silicon dioxide modification layer transfers hydroxyl for inactivating palladium oxide, and poisoning of water molecules generated by combustion to palladium is prevented, therefore, the addition of the silicon dioxide modification layer in the application not only improves the stability of the composite material as a catalyst, but also can improve the activity.
The noble metal particles loaded on the surface of the hafnium oxide carrier are used as active components, and are highly dispersed on the surface of the hafnium oxide carrier under the action of the non-metallic oxide modification layer, so that the dispersion is more uniform; and the hafnium oxide carrier and the active component noble metal particles have strong metal-carrier interaction, and the active component can be stably kept in a high-activity positive divalent valence state with the assistance of the modification layer, so that the stability and the catalytic activity of the composite material as a catalyst are further improved. Specifically, the noble metal particles are palladium particles.
In this application, the mass ratio of the hafnium oxide carrier, the non-noble metal oxide modification layer, and the noble metal particles is 100: (1-10): (0.5-2.0).
The application also provides a preparation method of the hafnium oxide composite material, which comprises the following steps:
carrying out reflux reaction on a non-metal oxide source and hafnium oxide in an organic solvent, and drying to obtain the hafnium oxide coated with a non-metal oxide modification layer on the surface;
and mixing and dipping the noble metal source and the hafnium oxide coated with the non-metal oxide modification layer on the surface in a solvent, drying and calcining to obtain the hafnium oxide composite material.
In the preparation process of the hafnium oxide composite material, firstly, a nonmetal oxide source and the hafnium oxide are subjected to reflux reaction in an organic solvent, and the hafnium oxide coated with the non-noble metal oxide modification layer on the surface is obtained after drying. In this process, the source of non-metallic oxide is chosen in particular from organosilanes, well known to the person skilled in the art, to which the present application is not particularly limited, in particular embodiments chosen from n-octyltriethoxysilane; the organic solvent is selected from organic solvents known to those skilled in the art to be capable of dissolving the organosilane and hafnium oxide, for which no other particular limitation is imposed on the application, and more specifically, the organic solvent is selected from toluene, acetone, ethanol, n-heptane or n-octane; the temperature of the reflux reaction is 60-200 ℃, and the time of the reflux reaction is 1-10 h; the drying temperature is 50-100 ℃, and the drying time is 2-12 h. In the above process, the reflux reaction makes the surface of the hafnium oxide coated with long chains of silane molecules.
The method comprises the steps of mixing a noble metal source and hafnium oxide with the surface coated with a non-noble metal oxide modification layer in a solvent, soaking, drying and calcining to obtain the hafnium oxide composite material. In the above process, the noble metal source is a palladium source, more specifically, the palladium source is selected from palladium acetate; the organic solvent is selected from toluene, acetone, ethanol, n-heptane or n-octane; the calcination is carried out in an air atmosphere at the temperature of 300-900 ℃ for 3-6 h. After calcination, the long chain of silane molecules is decomposed and oxidized into an amorphous silicon dioxide modification layer, and a palladium source forms high-dispersity palladium nanoparticles; the palisade structure formed by the long chain of the silane molecule and the palladium source butterfly type tripolymer structure form double steric hindrance, so that the dispersity of the palladium source is effectively improved, and the utilization efficiency of the active site is further improved.
The application also provides a combustion method of low-concentration methane, which comprises the following steps:
mixing the mixed gas with a catalyst, activating, cooling, heating and combusting; the mixed gas comprises 1-5% of methane and the balance of air by volume fraction, and the catalyst is the hafnium oxide composite material in the scheme.
The low concentration combustion method described above is well known to those skilled in the art, except that the present application employs a hafnium oxide composite as a catalyst for the combustion of low concentration methane. In the process, the temperature of the activation treatment is 400-600 ℃, and the time of the activation treatment is 1-2 hours. The combustion temperature is 300-400 ℃, and the conversion rate of methane can reach 100% in the temperature range by adopting the catalyst.
For further understanding of the present invention, the following examples are provided to illustrate the hafnium oxide composite material, its preparation method and its application, and the scope of the present invention is not limited by the following examples.
Example 1
Dissolving 5g of hafnium oxide and 2.75ml of n-octyltriethoxysilane in toluene, refluxing at 110 ℃ for 3h, centrifugally separating, and drying in a vacuum drying oven for 12h to obtain surface-modified hafnium oxide M-HfO2(ii) a Dissolving the modified hafnium dioxide and palladium acetate in toluene, wherein the mass fraction of a palladium source in a catalyst is 1.0%, performing ultrasonic treatment at room temperature for 30min, uniformly mixing the modified hafnium dioxide and the palladium source, soaking at room temperature for 2h, drying in a vacuum drying oven for 12h, transferring a sample into a quartz crucible, calcining in a muffle furnace at 500 ℃ for 3h in air atmosphere, naturally cooling to room temperature, and grinding to obtain 20g of light yellow powdery hafnium dioxide composite material Pd/M-HfO2。
Referring to fig. 1 and fig. 2, fig. 1 is a scanning electron micrograph of the hafnium oxide composite material prepared in example 1, and it can be seen from fig. 1 that the hafnium oxide composite material prepared in this example is a highly dispersed nanoparticle; FIG. 2 shows the high dispersion type nano-particle Pd/M-HfO prepared in example 12Wherein, the particles indicated by the circles in fig. 2 are the palladium nanoparticles, and the amorphous phase on the surface of the carrier is the silica modification layer.
High-dispersion nano-particle Pd/M-HfO2As a catalyst, the activity evaluation:
the method is carried out in a fixed bed quartz tube type microreactor (the inner diameter is 3mm), the loading amount of a catalyst is 20mg, a raw material gas is methane with the volume fraction of 1%, the rest gas is a mixed gas of air, the gas flow rate is 20ml/min, the corresponding air flow space velocity is 60,000 ml/(h.g), the activation treatment is carried out for 1h in a reaction atmosphere at 500 ℃, after the temperature is cooled to the room temperature, the temperature in the reactor is gradually increased at the speed of 10 ℃/min, in the temperature increasing process, the reactor is kept for 15 minutes at a plurality of selected temperature points to enable the reaction to reach a stable state, the methane in a product gas is analyzed on line by a GC-1690 gas chromatograph provided with a hydrogen flame detector, and the reaction activity is expressed by the conversion rate of the methane.
The activity test shows that 1.0 wt% Pd/M-HfO prepared by the method2The catalyst (the load of Pd is 1.0 wt%) can completely convert low-concentration methane (1 vol% methane, and the balance air) into carbon dioxide and water at 340 ℃, has a good methane catalytic combustion effect, the conversion rate is 100%, and the activity of the catalyst is unchanged after the catalyst is used for 60 hours.
Referring to FIGS. 3 and 4, FIG. 3 shows the Pd/M-HfO catalyst prepared in example 1 and containing highly dispersed nano-particles2The catalytic activity diagram of the low-concentration methane conversion with temperature is shown in figure 3, and compared with a palladium-based catalyst without a silicon dioxide modification layer (other conditions are consistent), the high-dispersion nano-particle palladium-based catalyst Pd/M-HfO prepared by the method is high in dispersion2Higher catalytic activity at low temperature; FIG. 4 is a life test chart of the catalyst at 300 ℃ and 600 ℃, and it can be seen from FIG. 4 that the catalyst prepared in this example stably maintains the methane conversion rate after reacting at 300 ℃ and 600 ℃ for 60 h.
Example 2
The preparation process according to the invention of example 1 is distinguished by: the loading amount of the active component palladium is 0.5 wt%.
The catalyst was evaluated in the same manner as in example 1. The activity test shows that: 0.5 wt% Pd/M-HfO prepared using the present method2The catalyst has methane conversion rate of 100% at 380 deg.c and activity unchanged after 60 hr.
Example 3
The preparation process according to the invention of example 1 is distinguished by: the loading amount of the active component palladium was 1.5 wt%.
The catalyst was evaluated in the same manner as in example 1. Activity tests showed that 1 was prepared using this method.5wt％Pd/M-HfO2The catalyst has methane conversion rate of 100% at 330 deg.c and activity unchanged after 60 hr.
Example 4
The preparation process according to the invention of example 1 is distinguished by: the loading amount of the active component palladium is 2.0 wt%.
The catalyst was evaluated in the same manner as in example 1. The activity test shows that the 2.0 wt% Pd/M-HfO prepared by the method2The catalyst has methane conversion rate of 100% at 320 deg.c and activity unchanged after 60 hr.
Comparative example 1
To compare the catalytic performance of the samples, palladium-based catalysts supported on untreated hafnia were prepared for comparison, which were prepared in the same manner as described above in example 1 for preparing highly dispersed nanoparticle palladium-based catalysts, except that untreated hafnia was used as the support, to finally obtain Pd/HfO2A composite material.
The catalyst was evaluated in the same manner as in example 1. Activity testing indicated that 1.0 wt% Pd/HfO prepared using the present method2The catalyst has methane conversion rate of 100% at 500 deg.c.
Comparative example 2
According to the preparation method of comparative example 1, the loading amount of palladium as an active component was changed to 0.5 wt%.
The catalyst was evaluated in the same manner as in example 1. Activity testing shows 0.5 wt% Pd/HfO prepared using the present method2The catalyst has methane conversion rate of 100% at 550 ℃.
Comparative example 3
According to the preparation method of comparative example 1, the loading amount of palladium as an active component was changed to 1.5 wt%.
The catalyst was evaluated in the same manner as in example 1. Activity testing indicated that 1.5 wt% Pd/HfO prepared using the present method2The catalyst has methane conversion rate of 100% at 475 deg.c.
Comparative example 4
According to the preparation method of comparative example 1, the loading amount of palladium as an active component was changed to 2.0 wt%.
The catalyst was evaluated in the same manner as in example 1. Activity testing shows 2.0 wt% Pd/HfO prepared using the present method2The catalyst has methane conversion rate of 100% at 450 deg.c.
The catalytic performance of the catalysts prepared in examples 1 to 4 and comparative examples 1 to 4 are shown in tables 1 and 2.
TABLE 1M-HfO according to the invention in examples 1 to 42Data table of catalytic performance of high-dispersion nano-particle palladium-based catalyst using carrier
Figure BDA0002594779370000081
Figure BDA0002594779370000091
TABLE 2 HfO according to the invention as described in comparative examples 1 to 42Data table of catalytic performance of nano palladium-based catalyst as carrier
Figure BDA0002594779370000092
As can be seen from tables 1 and 2, the ratio of Pd/HfO to Pd/HfO2Catalyst, Pd/M-HfO prepared by taking hafnium oxide with surface modification as carrier2The catalyst greatly reduces the complete catalytic combustion temperature of low-concentration methane, and has better catalytic activity.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (4)

1. A method of combusting a low concentration of methane, comprising:
mixing the mixed gas with a catalyst, activating, cooling, heating and combusting; the mixed gas comprises 1-5% of methane and the balance of air by volume fraction, and the catalyst is a hafnium oxide composite material; the combustion temperature is 300-400 ℃;
the hafnium oxide composite material comprises a hafnium oxide carrier, a non-metal oxide modification layer and noble metal particles; the non-metal oxide modification layer is coated on the surface of the hafnium oxide carrier, and the noble metal particles are loaded on the surface of the hafnium oxide carrier;
the non-metal oxide modification layer is an amorphous silicon dioxide layer, and the noble metal particles are palladium particles; the mass ratio of the hafnium oxide carrier to the non-metal oxide modification layer to the noble metal particles is 100: (1-10): (0.5 to 2.0);
the preparation method of the hafnium oxide composite material comprises the following steps:
carrying out reflux reaction on a non-metal oxide source and hafnium oxide in an organic solvent, and drying to obtain the hafnium oxide coated with a non-metal oxide modification layer on the surface;
mixing a noble metal source and hafnium oxide coated with a non-metallic oxide modification layer on the surface in a solvent, soaking, drying and calcining to obtain a hafnium oxide composite material;
the non-metal oxide source is organosilane, and the organosilane is n-octyl triethoxysilane; the noble metal source is a palladium source, and the palladium source is palladium acetate;
the temperature of the reflux reaction is 60-200 ℃, and the time is 1-10 h;
the calcining temperature is 300-900 ℃, and the time is 3-6 h.
2. The combustion method as claimed in claim 1, wherein in the step of obtaining the hafnium oxide coated with the non-metal oxide modification layer, the organic solvent is toluene, the drying is performed in a vacuum manner, the drying temperature is 50-100 ℃, and the drying time is 2-12 hours.
3. The combustion method as claimed in claim 1, wherein in the step of obtaining the hafnium oxide composite material, the organic solvent is toluene, the drying manner is vacuum drying, the drying temperature is 50-100 ℃, and the drying time is 2-12 h.
4. The combustion method according to claim 1, wherein the temperature of the activation treatment is 400 to 600 ℃.
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