CN112701301A - Coating material, preparation method and application thereof, fuel cell electrode and fuel cell - Google Patents
Coating material, preparation method and application thereof, fuel cell electrode and fuel cell Download PDFInfo
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- CN112701301A CN112701301A CN201911014252.9A CN201911014252A CN112701301A CN 112701301 A CN112701301 A CN 112701301A CN 201911014252 A CN201911014252 A CN 201911014252A CN 112701301 A CN112701301 A CN 112701301A
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a coating material, a preparation method and application thereof, a fuel cell electrode and a fuel cell. The coating material has an ordered mesoporous structure, and has pores which are mutually at an angle of 70-110 degrees, preferably 85-95 degrees. According to the unique properties of the template agent and the surfactant, the invention adopts a hard template method to firstly fill precursors of platinum metals and metal oxides into the template agent, and remove the template agent after roasting, so as to finally obtain the electrode coating material with special appearance, large specific surface area and good dehydrogenation activity, and effectively improve the power density of the direct fuel cell.
Description
Technical Field
The invention belongs to the field of dehydrogenation materials, and relates to a coating material, a preparation method and application thereof, a fuel cell electrode and a fuel cell.
Background
With the development of economy, the consumption of energy is continuously increased, and while green renewable energy is developed, the production capacity of energy and the energy conversion efficiency are required to be improved. Over the last decade, a great deal of research has been devoted to finding low pollution, low cost alternative power solutions. In this context, fuel cell technology is an attractive technology, and the characteristics of high conversion efficiency and no pollution of emission of fuel cells make it a strong competitor to interconversion technology among various energy sources.
Despite the many advantages of fuel cells, the supply of hydrogen sources, i.e., hydrogen storage technology, is generally considered to be the biggest bottleneck in its industrial application. Currently, high pressure other hydrogen storage is the most mature technology that is also closest to the U.S. department of energy and the european union's standards, but this technology also has some disadvantages: gaseous hydrogen storage requires a large-volume hydrogen storage tank, and the higher the hydrogen storage pressure is, the higher the cost and weight of the hydrogen storage tank are, and the worse the safety is. Low temperature liquid hydrogen storage is more suitable for large scale hydrogen storage and the vaporization loss and liquefaction cost of liquid hydrogen are too high for small scale on-board applications. The solid-state hydrogen storage technology is still different from the vehicle-mounted hydrogen storage technology at present. The hydrogen storage technology of organic liquid (methyl cyclohexane, perhydronaphthalene, dodecahydroazoethylcarbazole, etc.) is regarded as a proper hydrogen supply technology source of the fuel cell because of the advantages of high hydrogen storage density, small required volume, reversible reaction height, recyclable hydrogen storage carrier, etc.
The existing organic liquid hydrogen storage technology needs larger device volume and weight, the energy required during dehydrogenation is also very high, and the residual heat of the low-temperature fuel cell cannot provide enough heat source. The direct fuel cell of the organic liquid hydrogen storage material can directly convert hydrogen energy in the organic liquid hydrogen storage material into electric energy on the surface of the electrode, save an additional dehydrogenation device, reduce energy required by dehydrogenation and have strong application prospect.
The traditional electrode catalyst of the hydrogen fuel cell is generally noble metal platinum, the catalytic activity of the platinum is too strong, and the basic structure of a hydrogen storage carrier is easy to damage in dehydrogenation reaction and causes carbon deposition inactivation. Therefore, a material which can open carbon-hydrogen bonds to release hydrogen energy in the hydrogen storage carrier without damaging the structure of the carrier is needed to be found for coating the surface of the electrode of the fuel cell for coupling dehydrogenation.
The oxide of a V-BETA group or VI-BETA group element has strong dehydrogenation activity, and can store and conduct protons, so that hydrogen protons separated from the hydrogen storage carrier can be directly transferred to the electrode of the fuel cell, and the dehydrogenation efficiency is improved. However, most of oxides of group V or group VI elements have a layered structure, and the specific surface area is small, so that the oxides are not beneficial to contact with reactants, and therefore, the activity is low, and the requirement of dehydrogenation cannot be met.
In recent years, the preparation technology of nano particles and ordered mesoporous materials is rapidly developed, so that the controllable synthesis of the materials becomes possible. The mesoporous oxide material has high specific surface area and pore volume, and has special properties such as variability of components and valence states, crystal network structure and the like, so that the mesoporous oxide material becomes an important research object in the aspects of surface structure, heterogeneous catalysis and the like. Therefore, the research and development of the mesoporous metal oxide with high specific surface area and the preparation method thereof have great practical value.
CN104310481A discloses porous molybdenum trioxide and a preparation method thereof, a hydrogenation catalyst and a dehydrogenation catalyst. The preparation method of the porous molybdenum trioxide comprises the following steps: s1, preparing an aqueous solution of molybdenum-containing soluble acid and/or molybdenum-containing soluble salt; s2, adding a template material with a three-dimensional cubic mesoporous structure into the aqueous solution to obtain a mixture; s3, drying and calcining the mixture to obtain a calcined product; and S4, removing the template material in the calcined product to obtain the porous molybdenum trioxide. The method adopts a template with a three-dimensional cubic mesoporous structure to perform cooling. Absorbing soluble acid containing molybdenum and/or soluble salt containing molybdenum in the three-dimensional cubic mesoporous pores, and obtaining the porous molybdenum trioxide with the template material pore structure complementary structure through subsequent treatment.
CN103515620A discloses an electrode material, its application, a direct fuel cell, and an electrochemical hydrogenation electrolyzer. The patent provides a chemical synthesis method of HnNb2O5、HnV2O5、HnMoO3Or HWO3And Nb2O5、V2O5、MoO3、Ta2O5Or WO3The electrode material for direct fuel cell is composed. The invention also provides a direct fuel cell and an electrochemical hydrogenation electrolytic cell with the electrode material. The invention can utilize hydrogen energy as follows: the hydrogenation process, the hydrogen storage process and the hydrogen utilization process are combined; the hydrogen can not be utilized in the form of hydrogen molecules in the whole process; the traditional hydrogen storage process is reduced and optimized. Compared with the traditional hydrogen energy utilization process, the brand new hydrogen energy utilization process reduces the energy consumption in the hydrogen storage and release processes and greatly improves the energy utilization rate.
CN102583545A discloses a preparation method of three-dimensional ordered mesoporous molybdenum oxide, which takes tetraethoxysilane as a raw material, triblock copolymer (EO)20(PO)70(EO)20 as a template agent and n-butyl alcohol as an auxiliary solution, synthesizes cubic phase three-dimensional mesoporous silicon oxide powder KIT-6 through hydrothermal reaction, and then synthesizes three-dimensional mesoporous carbon with high specific surface area and developed pore structure by taking the cubic phase three-dimensional mesoporous silicon oxide powder KIT-6 as a hard template agent and sucrose as a carbon source. And finally, synthesizing the three-dimensional ordered mesoporous molybdenum oxide with high specific surface area by using three-dimensional mesoporous carbon as a template agent and using ammonium heptamolybdate with different concentrations as a metal precursor by using a vacuum-assisted ultrasonic method under the irradiation of ultrasonic waves at different times and at different evaporation temperatures.
The above patents have achieved certain results in searching for suitable auxiliary dehydrogenation electrode materials and synthesizing ordered mesoporous materials, but the specific surface area of dehydrogenation or electrode materials prepared by CN104310481A and CN103515620A is relatively small, thereby affecting dehydrogenation activity. And the preparation method of CN102583545A is complicated and is not beneficial to large-scale production.
Disclosure of Invention
One of the purposes of the invention is to provide a dehydrogenation material coated on the outer surface of a fuel cell electrode with high specific surface area, which utilizes developed pore canals and crystal lattices of ordered mesoporous materials to improve the reaction activity of the hydrogen storage material during dehydrogenation.
The first aspect of the invention provides a coating material, which has an ordered mesoporous structure and has pores which are mutually at an angle of 70-110 degrees.
According to some embodiments of the invention, there are channels at an angle of 85-95 ° to each other.
According to some embodiments of the invention, the channels are cubic or quasi-cubic.
According to some embodiments of the invention, include
A component a: at least one metal selected from group VIII elements;
and (b) component b: an oxide of at least one metal from group V BETA or group VI BETA;
and (c) component: a carrier;
according to some embodiments of the invention, component a is selected from at least one of platinum, palladium, osmium, iridium, ruthenium, and rhodium.
According to some embodiments of the invention, the component a is platinum and/or iridium.
According to some embodiments of the invention, the component b is selected from at least one of chromium oxide, molybdenum oxide, tungsten oxide and vanadium oxide.
According to some embodiments of the invention, the support is selected from at least one of alumina and silica.
According to some embodiments of the invention, the support is silica.
According to some embodiments of the invention, the material has a specific surface area of 250 to 500m2Per g, pore volume of 0.500-1.000cm3G, the aperture is 8.00-12.00 nm.
According to some embodiments of the invention, the material has a specific surface area of 450 to 480m2Per g, pore volume of 0.800-0.990cm3The pore diameter is 9-11 nm.
A second aspect of the present invention provides a method for producing the material according to the first aspect, wherein a hard template method is used to first fill a precursor of a group viii metal element and a group v beta or group vi metal oxide into a template, and after firing, the template is removed.
According to some embodiments of the invention, the method comprises the steps of:
s1, preparing soluble acid or soluble salt water solution containing the component a to obtain solution 1;
s2, preparing a soluble salt water solution containing the component b to obtain a solution 2;
s3, adding the solution 1 and the solution 2 into the suspension containing the template material in batches, and mixing to obtain a mixed solution;
s4, drying and roasting the mixed solution to obtain a roasted product;
s5, removing the template material in the burnt product to obtain the material.
According to some embodiments of the invention, the template material is at least one of SBA-15, MCM-41, mesoporous alumina, and mesoporous titania.
According to some embodiments of the invention, a surfactant is further added to the suspension containing the template material.
According to some embodiments of the invention, the surfactant is selected from at least one of methanol, ethanol, sodium lauryl sulfate, ethylene glycol, cetyltrimethylammonium bromide, and polyoxyethylene monosilicate.
According to some embodiments of the invention, the surfactant is present in the suspension comprising the template material at a concentration of 20-60% by volume.
According to some embodiments of the invention, the method of removing the template material in the fired product is soaking the fired product with an acid solution.
According to some embodiments of the invention, the acid solution has a mass concentration of 1% to 5%.
According to some embodiments of the invention, the acid solution soaking process is performed in an ultrasonic environment.
According to some embodiments of the invention, the ultrasonic medium is in a liquid state during the soaking in the acid solution and is treated at a low temperature, and/or excess NaOH is added to neutralize the acid in the solution after the soaking is finished.
According to some embodiments of the invention, the soluble salt of component b is selected from at least one of ammonium chromate, ammonium molybdate, ammonium paratungstate, ammonium metatungstate, ammonium metavanadate and niobium oxalate.
According to some embodiments of the invention, the mixing is sonication.
According to some embodiments of the invention, the sonication is for 30 min.
According to some embodiments of the invention, the drying is evaporating the solvent to form a paste.
According to some embodiments of the invention, the drying is water bath heating.
According to some embodiments of the invention, the temperature of the water bath heating is 60-80 ℃.
According to some embodiments of the present invention, the temperature of the calcination is 400-.
A third aspect of the invention provides a use of a material according to the first aspect in hydrogen storage.
A fourth aspect of the invention provides a fuel cell electrode, the outer surface of which is coated with a material according to the first aspect.
A fifth aspect of the invention is to provide a fuel cell including the fuel cell electrode according to the fourth aspect.
The invention has the beneficial effects that:
according to the unique properties of the template agent and the surfactant, the invention adopts a hard template method to firstly fill precursors of platinum metals and metal oxides into the template agent, and remove the template agent after roasting, so as to finally obtain the electrode coating material with special appearance, large specific surface area and good dehydrogenation activity, and effectively improve the power density of the direct fuel cell.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1 is a transmission electron microscope photograph of a coating material prepared in example 3 of the present invention. It can be seen from fig. 1 that ordered mesopores exist in the sample, and the channels formed by the two components are perpendicular to each other.
FIG. 2 is a plot of the intensity of the small angle X-ray diffraction pattern of the coating material prepared in example 3 of the present invention, wherein: the ordinate is diffraction intensity, and the abscissa is diffraction angle 2 θ. The material shows a sharp characteristic peak near 2 theta of about 1 degrees, which indicates that the material has an ordered cubic mesoporous structure, and in addition, a wider characteristic peak near 2 theta of about 1.6 degrees, which indicates that the mesoporous structure of the material is highly ordered.
FIG. 3 is a wide angle X-ray diffraction intensity profile of a coating material prepared in accordance with example 3 of the present invention, wherein: the ordinate is diffraction intensity, and the abscissa is diffraction angle 2 θ. The diffraction peak positions in the figure are highly consistent with that of the JCPDS 35-0609 standard card, which shows that the product forms channels with cubic phases.
FIG. 4 is an adsorption-desorption isotherm diagram of the coating material prepared in example 3 of the present invention. As can be seen from the figure, the absorption-desorption isotherm has an H1 type hysteresis loop, which can be observed in the ordered mesoporous material.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the examples.
Unless otherwise stated, the concentration of the solution is wt/v.
[ example 1 ]
200ml of 10% ammonium metavanadate solution and 100ml of 0.2% chloroplatinic acid solution were prepared and added dropwise to 100ml of a suspension containing 5g MCM-41. Adding 80ml sodium dodecyl sulfate, carrying out ultrasonic treatment for 30min, stirring, heating and evaporating the solvent to dryness, and roasting in a muffle furnace at 550 ℃ for 4 h.
Preparing 100ml of hydrofluoric acid solution with the concentration of 1%, adding the obtained roasted product into the solution, carrying out ultrasonic treatment for 2 hours, adding ice blocks into an ultrasonic medium in the ultrasonic process, and controlling the temperature to be 3 ℃. And then adding excessive NaOH to neutralize hydrofluoric acid, centrifuging, washing for a plurality of times by using deionized water, and drying to obtain the coating material. The surface area, pore volume and average pore diameter are shown in Table 1.
Methylcyclohexane is taken as a representative raw material of an organic liquid hydrogen storage carrier. 1g of coating material is taken, 8g of methylcyclohexane is weighed and evaluated in a tank reactor under the following evaluation conditions: initial pressure of reaction: 3MPa, reaction temperature of 250 ℃, reaction time: and 6 h. After the reaction is finished and the reaction product is naturally cooled, 1.5ml of reacted liquid is taken for detection, and the organic matters attached to the material are removed by centrifugal washing for 3 times by using ethanol. The obtained blue-black solid was dried in a vacuum oven at 50 ℃ for 24 h.
The content of protons in the coating material after reaction is measured by adopting a silver amount method, and the specific mode is as follows: oxidizing the low-valence tungsten into high-valence tungsten by using a silver nitrate solution, preparing a silver nitrate solution with a certain concentration, adding the reacted coating material by using ferric nitrate as an indicator, stirring for 10min, and titrating by using a KSCN solution to determine the content of the residual silver nitrate. And finally, calculating through an equivalent relation to obtain the proton content in the reacted coating material.
The evaluation results are shown in Table 2.
[ example 2 ]
200ml of 10% ammonium molybdate solution and 100ml of 0.2% chloroplatinic acid solution were prepared and added dropwise to 100ml of a suspension containing 5g MCM-41. Adding 80ml sodium dodecyl sulfate, carrying out ultrasonic treatment for 30min, stirring, heating and evaporating the solvent to dryness, and roasting in a muffle furnace at 550 ℃ for 4 h.
Preparing 100ml of hydrofluoric acid solution with the concentration of 1%, adding the obtained roasted product into the solution, carrying out ultrasonic treatment for 2 hours, adding ice blocks into an ultrasonic medium in the ultrasonic process, and controlling the temperature to be 3 ℃. Adding excessive NaOH to neutralize hydrofluoric acid, centrifuging, washing for several times by using deionized water, and drying to obtain the coating material. The surface area, pore volume and average pore diameter are shown in Table 1.
1g of the coating material was taken out and evaluated in a tank reactor under the same conditions as in example 1, and the results are shown in Table 2.
[ example 3 ]
200ml of 10% ammonium molybdate solution and 100ml of 0.2% chloroplatinic acid solution were prepared and added dropwise to 100ml of a suspension containing 5g of SBA-15. Adding 80ml sodium dodecyl sulfate, carrying out ultrasonic treatment for 30min, stirring, heating and evaporating the solvent to dryness, and roasting in a muffle furnace at 550 ℃ for 4 h.
Preparing 100ml of hydrofluoric acid solution with the concentration of 1%, adding the obtained roasted product into the solution, carrying out ultrasonic treatment for 2 hours, adding ice blocks into an ultrasonic medium in the ultrasonic process, and controlling the temperature to be 3 ℃. Adding excessive NaOH to neutralize hydrofluoric acid, centrifuging, washing for several times by using deionized water, and drying to obtain the coating material. The surface area, pore volume and average pore diameter are shown in Table 1.
1g of the coating material was taken out and evaluated in a tank reactor under the same conditions as in example 1, and the results are shown in Table 2.
[ example 4 ]
200ml of 10% ammonium molybdate solution and 100ml of 0.2% chloroplatinic acid solution were prepared and added dropwise to 100ml of a suspension containing 5g of SBA-15. Adding 80ml sodium dodecyl sulfate, carrying out ultrasonic treatment for 30min, stirring, heating and evaporating the solvent to dryness, and roasting in a muffle furnace at 550 ℃ for 4 h.
Preparing 100ml of hydrofluoric acid solution with the concentration of 5%, adding the obtained roasted product into the solution, carrying out ultrasonic treatment for 2 hours, adding ice blocks into an ultrasonic medium in the ultrasonic process, and controlling the temperature to be 3 ℃. Adding excessive NaOH to neutralize hydrofluoric acid, centrifuging, washing for several times by using deionized water, and drying to obtain the coating material. The surface area, pore volume and average pore diameter are shown in Table 1.
1g of the coating material was taken out and evaluated in a tank reactor under the same conditions as in example 1, and the results are shown in Table 2.
Comparative example 1
200ml of 10% ammonium molybdate solution and 100ml of 0.2% chloroplatinic acid solution were prepared and added dropwise to 100ml of a suspension containing 5g of SBA-15. Performing ultrasonic treatment for 30min, stirring, heating, evaporating to remove solvent, and calcining in muffle furnace at 550 deg.C for 4 h.
Preparing 100ml of hydrofluoric acid solution with the concentration of 1%, adding the obtained roasted product into the solution, carrying out ultrasonic treatment for 2 hours, adding ice blocks into an ultrasonic medium in the ultrasonic process, and controlling the temperature to be 3 ℃. Adding excessive NaOH to neutralize hydrofluoric acid, centrifuging, washing for several times by using deionized water, and drying to obtain the coating material. The surface area, pore volume and average pore diameter are shown in Table 1.
1g of the coating material was taken out and evaluated in a tank reactor under the same conditions as in example 1, and the results are shown in Table 2.
Comparative example 2
200ml of 10% ammonium molybdate solution and 100ml of 0.2% chloroplatinic acid solution were prepared and added dropwise to 100ml of a suspension containing 5g of SBA-15. Adding 80ml sodium dodecyl sulfate, carrying out ultrasonic treatment for 30min, stirring, heating and evaporating the solvent to dryness, and roasting in a muffle furnace at 550 ℃ for 4 h.
100ml of hydrofluoric acid solution with the concentration of 1% is prepared, and the obtained roasted product is added into the solution and is subjected to ultrasonic treatment for 2 hours. Adding excessive NaOH to neutralize hydrofluoric acid, centrifuging, washing for several times by using deionized water, and drying to obtain the coating material. The surface area, pore volume and average pore diameter are shown in Table 1.
1g of the coating material was taken out and evaluated in a tank reactor under the same conditions as in example 1, and the results are shown in Table 2.
Comparative example 3
200ml of 10% ammonium molybdate solution and 100ml of 0.2% chloroplatinic acid solution were prepared and added dropwise to 100ml of a suspension containing 5g of SBA-15. Adding 80ml polyoxyethylene monosilicate, performing ultrasonic treatment for 30min, stirring, heating, evaporating to remove the solvent, and roasting in a muffle furnace at 550 ℃ for 4 h.
Preparing 100ml of hydrofluoric acid solution with the concentration of 1%, adding the obtained roasted product into the solution, carrying out ultrasonic treatment for 2 hours, adding ice blocks into an ultrasonic medium in the ultrasonic process, and controlling the temperature to be 3 ℃. Adding excessive NaOH to neutralize hydrofluoric acid, centrifuging, washing for several times by using deionized water, and drying to obtain the coating material. The surface area, pore volume and average pore diameter are shown in Table 1.
1g of the coating material was taken out and evaluated in a tank reactor under the same conditions as in example 1, and the results are shown in Table 2.
Comparative example 4
10g of ammonium molybdate is taken and put into a muffle furnace to be roasted for 4 hours at the temperature of 550 ℃ to obtain MoO3. The surface area, pore volume and average pore diameter are shown in Table 1.
Take 1g MoO3The evaluation was carried out in a tank reactor under the same conditions as in example 1, and the results are shown in Table 2.
TABLE 1
| Specific surface area m2/g | Pore volume cm3/g | Pore size nm | |
| Example 1 | 298 | 0.652 | 8.42 |
| Example 2 | 354 | 0.776 | 8.98 |
| Example 3 | 462 | 0.971 | 10.65 |
| Example 4 | 287 | 0.647 | 8.21 |
| Comparative example 1 | 151 | 0.307 | 5.75 |
| Comparative example 2 | 224 | 0.463 | 7.68 |
| Comparative example 3 | 164 | 0.344 | 6.23 |
| Comparative example 4 | 6 | 0.026 | 2.43 |
Examples 1 and 2 differ from example 3 in terms of elements and structure (addition of different templates), and examples 1 and 2 are the same as example 3 shown in fig. 1 to 4, and the obtained coating materials both have ordered mesoporous structures and have pores at 90 degrees to each other.
Example 4 when the template agent is removed, a higher concentration hydrofluoric acid is added, and the obtained coating material also has an ordered mesoporous structure and has pores that are 90 degrees to each other. However, compared with examples 1 to 3, the molybdenum oxide was dissolved more seriously, the proportion of the molybdenum oxide in the coating material was decreased, and the pore structure was broken and the degree of order was decreased.
The coating material obtained by the comparative example 1 without adding the surfactant and the comparative example 3 with adding different surfactants can form ordered mesoporous channels, but the channels of the molybdenum oxide and the silicon oxide are parallel to each other, namely are not 90 degrees.
Comparative example 2 no temperature control was performed when the template was removed, and the channels of the resulting coating material were severely damaged and had no ordered structure.
Comparative example 4 ammonium molybdate was directly calcined to obtain a coating material with significantly smaller specific surface area, pore volume and pore size.
TABLE 2
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. The coating material has an ordered mesoporous structure and has pore channels which are mutually at an angle of 70-110 degrees, preferably 85-95 degrees;
preferably, the channels are cubic or quasi-cubic.
2. The material as claimed in claim 1, comprising
A component a: at least one metal selected from group VIII elements;
and (b) component b: an oxide of at least one metal from group V BETA or group VI BETA;
and (c) component: a carrier;
preferably, the component a is selected from at least one of platinum, palladium, osmium, iridium, ruthenium and rhodium, and is further preferably platinum and/or iridium;
preferably, the component b is selected from at least one of chromium oxide, molybdenum oxide, tungsten oxide and vanadium oxide;
preferably, the support is selected from at least one of alumina and silica, and more preferably silica.
3. The material according to claim 1 or 2, wherein the specific surface area of the material is 250-500 m2Per g, pore volume of 0.500-1.000cm3G, the aperture is 8.00-12.00 nm;
preferably, the specific surface area of the material is 450-480 m2Per g, pore volume of 0.800-0.990cm3The pore diameter is 9-11 nm.
4. A process for the preparation of a material according to any one of claims 1 to 3, wherein a precursor of the group VIII metal element and the group V or group VI metal oxide is first filled into a template by the hard template method, and the template is removed after firing.
5. The method according to claim 4, characterized in that it comprises the following steps:
s1, preparing soluble acid or soluble salt water solution containing the component a to obtain solution 1;
s2, preparing a soluble salt water solution containing the component b to obtain a solution 2;
s3, adding the solution 1 and the solution 2 into the suspension containing the template material in batches, and mixing to obtain a mixed solution;
s4, drying and roasting the mixed solution to obtain a roasted product;
s5, removing the template material in the burnt product to obtain the material;
preferably, the template material is at least one of SBA-15, MCM-41, mesoporous alumina and mesoporous titania;
preferably, a surfactant is further added to the template material-containing suspension, and further preferably, the surfactant is at least one of methanol, ethanol, sodium dodecyl sulfate, ethylene glycol, cetyl trimethyl ammonium bromide and polyoxyethylene monosilicate, and/or, in the template material-containing suspension, the concentration of the surfactant is 20-60% by volume;
preferably, the method for removing the template material in the burned product comprises soaking the roasted product with an acid solution, further preferably, the mass concentration of the acid solution is 1% -5%, and/or the acid solution soaking process is performed under an ultrasonic environment, and/or an ultrasonic medium is in a liquid state during the acid solution soaking process and is treated under a low temperature condition, and/or excess NaOH is added after the soaking process is finished to neutralize the acid in the solution.
6. The method of claim 4 or 5, wherein the soluble salt of component b is selected from at least one of ammonium chromate, ammonium molybdate, ammonium paratungstate, ammonium metatungstate, ammonium metavanadate and niobium oxalate;
and/or, the mixing is ultrasonic treatment, preferably ultrasonic treatment for 30 min;
and/or, the drying is evaporating the solvent to form a paste;
and/or the drying is water bath heating, and the temperature of the water bath heating is preferably 60-80 ℃;
and/or the roasting temperature is 400-500 ℃, and the temperature rising speed is 5-10 ℃/min.
7. Use of a material according to any one of claims 1-3 for storing hydrogen.
8. The use according to claim 7, wherein the reaction occurs upon contact with an organic liquid hydrogen storage material to produce hydrogen protons and corresponding aromatic hydrocarbons;
preferably, the pressure of the reaction is 1-4MPa, and the temperature is 180-300 ℃;
preferably, the organic liquid hydrogen storage material is selected from at least one of methylcyclohexane, cyclohexane, perhydro N-ethylcarbazole, and decahydronaphthalene.
9. A fuel cell electrode having an outer surface coated with a material according to any one of claims 1 to 3.
10. A fuel cell comprising the fuel cell electrode according to claim 9.
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