CN112553639A - Preparation method of high-stability methanol fuel decomposition catalyst - Google Patents
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Abstract
The application relates to the field of catalyst materials, and particularly discloses a preparation method of a high-stability methanol fuel decomposition catalyst. Comprises the following preparation steps: s1, respectively adding copper nitrate, magnesium nitrate and aluminum nitrate into deionized water, and stirring and mixing with a sodium carbonate solution to obtain a base fluid; s2, adjusting the pH value of the matrix liquid, standing and aging, taking the lower layer precipitate and carrying out crystallization treatment, and carrying out heat preservation and roasting to obtain matrix particles; s3, respectively weighing 45-50 parts by weight of solvent, 0.5-1.0 part by weight of modified graphite particles and 3-5 parts by weight of chloroplatinic acid, and stirring and mixing to obtain reaction liquid; s4, carrying out hydrothermal treatment in an argon atmosphere, adjusting the pH value to 2.5, filtering, taking the precipitate, washing, drying, crushing and sieving. According to the method, the hydrotalcite substrate is prepared firstly, and then the graphite surface loaded with the reduced platinum simple substance is compounded with the hydrotalcite substrate, so that the activity of the methanol decomposition catalyst in the catalytic decomposition reaction is improved, and the stability of the catalyst is improved.
Description
Technical Field
The application relates to the field of catalyst materials, in particular to a preparation method of a high-stability methanol fuel decomposition catalyst.
Background
The chemisorption and decomposition of methanol on various metal surfaces has been extensively studied in recent years because methanol can serve as a new liquid energy carrier and is readily synthesized from biomass, coal and natural gas, which are all ore resources richer than crude oil and one of the most promising feedstocks due to its low cost, ease of handling and high energy. Methanol as a raw material has the following advantages:
methanol decomposition only needs methanol as a raw material and can utilize the waste heat of an engine;
secondly, the liquid methanol is more convenient to transport for a long distance;
③ can be converted into CO and H only by having an economic and effective catalyst2And can be used to recover waste heat from industry;
hydrogen generated by methanol decomposition is widely applied, is directly used as fuel of an internal combustion engine or indirectly provides power through a fuel cell, is clean in nature and can be high-energy-efficiency fuel, and methanol is decomposed into H2And CO is an endothermic reaction, and when the catalyst is applied to an internal combustion engine, the heat discharged by the engine can be fully utilized, so that the fuel economy is improved;
the decomposed methanol is cleaner fuel, and the efficiency is 60% higher than that of gasoline and 34% higher than that of undecomposed methanol.
In view of the above-mentioned related technologies, the inventors believe that in the scheme of catalyzing the methanol decomposition by the catalyst, the particles doped in the catalyst are thermally sintered in the methanol decomposition catalyst to cause agglomeration, so that the activity in the methanol decomposition reaction is rapidly reduced, the catalytic activity is affected, and the stability of the catalyst is reduced.
Disclosure of Invention
In order to improve the activity of the methanol decomposition catalyst in the catalytic decomposition reaction and improve the stability of the catalyst, the application provides a high-stability methanol fuel decomposition catalyst, and the preparation steps of the high-stability methanol fuel decomposition catalyst comprise: s1, respectively mixing copper nitrate, magnesium nitrate and aluminum nitrate, adding the mixture into deionized water, stirring, mixing and collecting to obtain a dissolved solution, adding the dissolved solution into a sodium carbonate solution according to the volume ratio of 1:1, and stirring and mixing to obtain a base fluid; s2, adjusting the pH value of the matrix liquid to 9-10, standing and aging, taking the lower layer precipitate and carrying out crystallization treatment to obtain crystallized particles, washing, drying, crushing, sieving with a 500-mesh sieve, carrying out temperature programming and carrying out heat preservation roasting to obtain matrix particles; s3, respectively weighing 45-50 parts by weight of solvent, 0.5-1.0 part by weight of modified graphite particles and 3-5 parts by weight of chloroplatinic acid, stirring, mixing and dropwise adjusting the pH value to 10.5 to obtain a reaction solution; s4, adding the matrix particles into the reaction liquid, stirring, mixing, grinding and dispersing, sieving, taking the dispersed slurry, placing the dispersed slurry into a reaction kettle, performing hydrothermal treatment in an argon atmosphere, standing, cooling to room temperature, dropwise adding nitric acid, adjusting the pH to 2.5, filtering, taking the precipitate, washing, drying, crushing and sieving to obtain the high-stability methanol fuel decomposition catalyst.
By adopting the technical scheme, as the catalyst is prepared by taking copper nitrate, magnesium nitrate and aluminum nitrate as raw materials, and crystallization and calcination treatment are carried out after dissolution to prepare the brucite pillared compound with positive charge, and the brucite pillared compound is taken as the matrix material of the catalyst, because the surface area and the reducibility of the matrix material are excellent, the conversion rate and the gas yield of methanol decomposition can be effectively improved, and the generation of liquid phase byproducts is inhibited, on the basis, the catalyst is prepared by selecting graphite and chloroplatinic acid, the graphite is uniformly dispersed in an ethylene glycol solvent, the chloroplatinic acid is reduced to obtain a Pt elementary substance by heating, the reduced Pt elementary substance is effectively deposited on the surface of the graphite and is effectively filled into the matrix particles, so that the structural performance of the matrix particles is improved and fixed, and the agglomeration phenomenon of active particles caused by sintering can not occur in the actual use process, thereby improving the catalytic decomposition activity and stability of the methanol decomposition catalyst.
Further, in step S1, the mixing ratio of copper nitrate, magnesium nitrate, and aluminum nitrate is, Cu: mg: molar ratio of Al = 1: 2-3: 1.
by adopting the technical scheme, the mixing proportion of copper nitrate, magnesium nitrate and aluminum nitrate is optimized, copper is an active center of the methanol cracking hydrogen production reaction, the alkaline center of the catalyst can inhibit the generation of formic acid and methyl formate in a liquid-phase product, and the alkalinity of the catalyst is reduced along with the increase of the mole fraction of copper, so that the mass fraction of a liquid-phase byproduct is in an increasing trend along with the increase of the mole fraction of copper, when the mole ratio of copper and magnesium is lower, the active center is less, the activity of the catalyst is lower, and therefore, along with the increase of the mole ratio of copper and magnesium, the specific surface area of the catalyst is increased, the activity is also continuously increased, the catalytic performance of catalyst matrix particles is effectively improved, the activity of the methanol decomposition catalyst in the catalytic decomposition reaction is improved, and the stability of the catalyst is improved.
Further, the crystallization temperature in step S2 is 75-80 ℃.
By adopting the technical scheme, the crystallization temperature is optimized, so that the precipitation and crystallization rates are effectively improved at the temperature, the efficiency of the catalyst matrix particle preparation process is improved, the preparation time of the catalyst matrix particles is shortened, the time cost is further reduced, and the catalyst preparation efficiency is improved.
Further, the temperature programming in step S2 is to heat the temperature to 450-460 ℃ at a rate of 10 ℃/min.
Through adopting above-mentioned technical scheme, because this application improves the intensification rate of calcination through even program heating's scheme, simultaneously, optimize the calcination temperature after keeping warm, can effectively improve and form the even pore structure that link up after the calcination, simultaneously again because this application has adopted comparatively even stable intensification rate, make the preparation in-process, the inside hole of catalyst matrix granule that the calcination was handled is preserved intact, has improved its structural performance to the stability performance of catalyst matrix granule has been improved, further improved the stability performance of catalyst.
Further, the solvent in step S3 is any one of ethylene glycol or formaldehyde solution.
By adopting the technical scheme, because the ethylene glycol or the formaldehyde solution is selected as the solvent for treatment, the formaldehyde and the ethylene glycol can carry out reduction reaction on chloroplatinic acid, the chloroplatinic acid is reduced to form the simple substance platinum, the simple substance platinum is effectively dispersed and loaded on the surface of the catalyst material, on the basis, the simple substance platinum catalyzes the ethylene glycol to decompose and generate active hydrogen under the help of water molecules, the active hydrogen further accelerates the reduction of platinum ions and starts to reduce graphite oxide, the simple substance platinum is completely reduced and deposited on the surface of the partially reduced catalyst material along with the extension of the reaction time, the pi-pi action between graphite materials is gradually strengthened, the reduced graphite is stacked together in parallel, other reduced graphite is stacked together in parallel at another angle, and a plurality of communicated pore channel structures are formed due to different orientations between the reduced graphite, as the interaction between the graphites becomes stronger along with the reaction, a compact three-dimensional structure is gradually formed, so that the surface structure and the activity performance of the catalyst material are further improved, and the stability of the catalyst is further improved.
Further, the modified graphite particles of step S3 are oxidized modified graphite oxide particles.
By adopting the technical scheme, the graphite oxide particles are preferably selected as the material, and the graphite oxide can be uniformly dispersed in the solvent through a large number of hydrophilic oxygen-containing functional groups on the surface of the graphite oxide and electrostatic repulsion among the graphite oxide, so that a good dispersion system can be formed in the subsequent catalyst surface structure modification process, the surface structure and the activity performance of the catalyst material are further improved, and the stability performance of the catalyst is further improved.
Further, the hydrothermal treatment temperature in the step S4 is 155-165 ℃.
By adopting the technical scheme, the temperature of hydrothermal treatment is optimized, so that the catalyst can form good coating performance on the surface of the catalyst substrate at the temperature, and can also perform good crystallization coating on the internal type of the pores of the catalyst to support and improve the structural strength of the catalyst substrate.
Further, the aperture of the screen mesh in the step S4 is 0.25-0.28 μm.
By adopting the technical scheme, because the fineness of the grinding slurry is optimized, the grain size of the crystallized film is reduced in the subsequent crystallization process, and the compactness of the coating layer of the matrix grains is improved, on the basis, the structure of the coated matrix grains is more stable and uniform, and the stability of the catalyst is further improved.
In summary, the present application includes at least one of the following beneficial technical effects:
firstly, copper nitrate, magnesium nitrate and aluminum nitrate are used as raw materials for preparation, positive charge brucite layer columnar compounds are prepared through crystallization and calcination treatment after dissolution, the brucite layer columnar compounds are used as base materials of the catalyst, and the base materials have excellent surface area and reducibility, so that the conversion rate and gas yield of methanol decomposition can be effectively improved, and the generation of liquid phase byproducts is inhibited.
Secondly, the mixing proportion of copper nitrate, magnesium nitrate and aluminum nitrate is optimized, copper is an active center of a methanol cracking hydrogen production reaction, the basic center of the catalyst can inhibit the generation of formic acid and methyl formate in a liquid-phase product, and the alkalinity of the catalyst is reduced along with the increase of the mole fraction of copper, so that the mass fraction of a liquid-phase byproduct is in an increasing trend along with the increase of the mole fraction of copper, when the mole ratio of copper and magnesium is lower, the active center is less, the activity of the catalyst is lower, and therefore the specific surface area of the catalyst is increased and the activity is continuously increased along with the increase of the mole ratio of copper and magnesium, so that the catalytic performance of a catalyst matrix particle is effectively improved, the activity of the methanol decomposition catalyst in the catalytic decomposition reaction is improved, and the stability of the catalyst is improved.
Third, graphite oxide particles are preferably used as materials, and a large number of hydrophilic oxygen-containing functional groups exist on the surface of the graphite oxide and electrostatic repulsion among the graphite oxide, so that the graphite oxide can be uniformly dispersed in an ethylene glycol solvent, and a good dispersion system can be formed in the subsequent catalyst surface structure modification process, so that the surface structure and the activity performance of the catalyst material are further improved, and the stability of the catalyst is further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
In the examples of the present application, the following instruments and apparatuses are used, but not limited thereto:
the instrument comprises the following steps: a glassy carbon electrode; a saturated calomel electrode.
Examples
Example 1
According to the weight ratio of Cu: mg: molar ratio of Al 1: 2: 1, respectively taking and mixing copper nitrate, magnesium nitrate and aluminum nitrate, taking and adding the mixture into deionized water according to the mass ratio of 1:25, stirring and mixing and collecting to obtain a dissolved solution, adding the dissolved solution into a sodium carbonate solution with the mass fraction of 10% according to the volume ratio of 1:1, stirring and mixing and magnetically stirring to obtain a base body fluid, dropwise adding a sodium hydroxide solution with the mass fraction of 5% into the base body fluid, stirring and mixing and controlling the pH of the base body fluid to be 9, stirring and mixing after dropwise adding is completed, standing and aging at room temperature for 3 hours, taking the lower layer precipitate, placing the lower layer precipitate at 75 ℃ for crystallization treatment for 3 hours to obtain crystallized particles, washing the crystallized particles with deionized water until the washing solution is neutral, then carrying out vacuum freeze drying, crushing and sieving with a 500-mesh sieve, taking the sieved particles, heating to 450 ℃ according to the temperature per minute, carrying out heat preservation roasting treatment for 45 minutes, standing;
respectively weighing 45 parts of ethylene glycol, 0.5 part of graphite oxide and 3 parts of 0.8mol/L chloroplatinic acid in parts by weight, placing the materials in a magnetic stirring device, magnetically stirring and mixing the materials, dropwise adding a sodium hydroxide solution with the mass of 0.5mol/L until the pH value is 10.5, and taking a reaction solution;
adding matrix particles into a reaction solution according to the mass ratio of 1:5, stirring, mixing, grinding and dispersing, placing dispersed slurry into a reaction kettle, carrying out hydrothermal treatment for 6 hours at the temperature of 155 ℃ in the atmosphere of argon, standing and cooling to room temperature, dropwise adding nitric acid with the mass fraction of 0.5% until the pH value is 2.5, filtering, taking a precipitate, washing with deionized water until a washing solution is neutral, and carrying out freeze drying and crushing to 200-mesh sieve to obtain the high-stability methanol fuel decomposition catalyst.
Example 2
According to the weight ratio of Cu: mg: molar ratio of Al 1: 2.5: 1, respectively taking and mixing copper nitrate, magnesium nitrate and aluminum nitrate, taking and adding the mixture into deionized water according to the mass ratio of 1:25, stirring and mixing and collecting to obtain a dissolved solution, adding the dissolved solution into a sodium carbonate solution with the mass fraction of 10% according to the volume ratio of 1:1, stirring and mixing and magnetically stirring to obtain a base body fluid, dropwise adding a sodium hydroxide solution with the mass fraction of 5% into the base body fluid, stirring and mixing and controlling the pH of the base body fluid to be 9, stirring and mixing after dropwise adding is completed, standing and aging at room temperature for 4 hours, taking a lower layer precipitate, placing the lower layer precipitate at 77 ℃ for crystallization treatment for 4 hours to obtain crystallized particles, washing the crystallized particles with deionized water until the washing solution is neutral, then carrying out vacuum freeze drying, crushing and sieving with a 500-mesh sieve, taking the sieved particles, heating to 455 ℃ according to 10 ℃/min, carrying out heat preservation roasting treatment for 53min, standing and;
respectively weighing 47 parts by weight of ethylene glycol, 0.6 part by weight of graphite oxide and 4 parts by weight of 0.8mol/L chloroplatinic acid, placing the materials in a magnetic stirring device, magnetically stirring and mixing the materials, dropwise adding a sodium hydroxide solution with the mass of 0.5mol/L until the pH value is 10.5, and taking a reaction solution;
adding matrix particles into a reaction solution according to the mass ratio of 1:5, stirring, mixing, grinding and dispersing, placing dispersed slurry into a reaction kettle, performing hydrothermal treatment for 7 hours at 160 ℃ in an argon atmosphere, standing and cooling to room temperature, dropwise adding nitric acid with the mass fraction of 0.5% until the pH value is 2.5, filtering, taking a precipitate, washing with deionized water until a washing solution is neutral, and performing freeze drying and crushing to 200-mesh sieve to obtain the high-stability methanol fuel decomposition catalyst.
Example 3
According to the weight ratio of Cu: mg: molar ratio of Al 1: 3: 1, respectively taking and mixing copper nitrate, magnesium nitrate and aluminum nitrate, taking and adding the mixture into deionized water according to the mass ratio of 1:25, stirring and mixing and collecting to obtain a dissolved solution, adding the dissolved solution into a sodium carbonate solution with the mass fraction of 10% according to the volume ratio of 1:1, stirring and mixing and magnetically stirring to obtain a base body fluid, dropwise adding a sodium hydroxide solution with the mass fraction of 5% into the base body fluid, stirring and mixing to control the pH of the base body fluid to be 10, stirring and mixing after dropwise adding is completed, standing and aging at room temperature for 3-5 h, taking the lower layer precipitate, placing the lower layer precipitate at 80 ℃ for crystallization treatment for 5h to obtain crystallized particles, washing the crystallized particles with deionized water until the washing liquid is neutral, then carrying out vacuum freeze drying, crushing and sieving with a 500-mesh sieve, taking the sieved particles, heating to 460 ℃, carrying out heat preservation and roasting treatment for 60min, standing and cooling to room temperature to;
respectively weighing 50 parts by weight of ethylene glycol, 1.0 part by weight of graphite oxide and 5 parts by weight of 0.8mol/L chloroplatinic acid, placing the materials in a magnetic stirring device, magnetically stirring and mixing the materials, dropwise adding a sodium hydroxide solution with the mass of 0.5mol/L until the pH value is 10.5, and taking a reaction solution;
adding matrix particles into a reaction solution according to the mass ratio of 1:5, stirring, mixing, grinding and dispersing, placing dispersed slurry into a reaction kettle, performing hydrothermal treatment for 8 hours at 165 ℃ in an argon atmosphere, standing and cooling to room temperature, dropwise adding nitric acid with the mass fraction of 0.5% until the pH value is 2.5, filtering, taking a precipitate, washing with deionized water until a washing solution is neutral, and performing freeze drying and crushing to 200-mesh sieve to obtain the high-stability methanol fuel decomposition catalyst.
Examples 4 to 6
In examples 4 to 6, in the preparation process of the high-stability methanol fuel decomposition catalyst, the mixing ratio of copper nitrate, magnesium nitrate and aluminum nitrate was adjusted to be, Cu: mg: molar ratio of Al = 1: 1:1, other conditions and component ratios were the same as in example 1.
Examples 7 to 9
In examples 7 to 9, in the preparation process of the high-stability methanol fuel decomposition catalyst, the mixing ratio of copper nitrate, magnesium nitrate and aluminum nitrate was adjusted to be, Cu: mg: molar ratio of Al = 1: 4: 1, other conditions and component ratios were the same as in example 1.
Performance test
The performance tests of examples 1 to 9 were performed, and the catalytic performance and the life of the catalysts for methanol decomposition and heating prepared in examples 1 to 9 were measured.
Detection method/test method
Electrochemical testing: the test is carried out under a three-electrode system with the temperature of 30 ℃ and the normal pressure. Wherein, the glassy carbon electrode coated with the catalyst slurry is used as a working electrode, a Pt wire electrode (phi =0.5mm) is used as an auxiliary electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode; nitrogen was introduced into the solution for half an hour before all electrochemical tests were performed to remove oxygen interference from the solution. The voltage range is-0.242 to 0.958V (vsSCE). The electrolyte solution used for the electrochemical test was 0.5mol ∙ L-1H2SO4+1.0mol∙L- 1CH3OH, wherein methanol oxidation test is performed at 50mV ∙ s-1Is performed at the scanning rate of (1). The timing current test is carried out at the potential of 0.4V, and the test time is 1 h;
the specific detection results are shown in the following table 1:
TABLE 1 Performance test Table
Referring to the comparison of the performance tests of table 1, it can be found that:
the performances of the examples 1 to 3 are compared, wherein the performances of the catalytic activity and the catalytic circulation rate (the oxidation peak potential value of the intermediate poison) in the example 3 are the best, and the addition ratio of each component is the highest in the example 3 compared with the examples 1 and 2, so that the technical scheme of the application can be implemented.
Comparing the performances of examples 1 to 3 with those of examples 4 to 6 with those of examples 7 to 9, in examples 4 to 6, the mixing ratio of copper nitrate, magnesium nitrate and aluminum nitrate was adjusted to be, Cu: mg: molar ratio of Al = 1: 1:1, in examples 7 to 9, in the preparation process of the high-stability methanol fuel decomposition catalyst, the mixing ratio of copper nitrate, magnesium nitrate and aluminum nitrate was adjusted to be, Cu: mg: molar ratio of Al = 1: 4: 1, as can be seen from table 1, the catalytic activity is reduced more and the cycle life is also reduced significantly in examples 4 to 6 and examples 7 to 9, which indicates that the present application optimizes the mixing ratio of copper nitrate, magnesium nitrate and aluminum nitrate, thereby effectively improving the catalytic performance of the catalyst matrix particles, improving the activity of the methanol decomposition catalyst in the catalytic decomposition reaction, and improving the stability of the catalyst.
Comparative example
Comparative examples 1 to 3
In comparative examples 1 to 3, chloroplatinic acid was directly used without adding graphite in the preparation of the reaction solution, and the other conditions and the component ratios were the same as in examples 1 to 3.
Comparative examples 4 to 6
Comparative examples 4 to 6 use porous zeolite instead of the matrix particles prepared in the present application, and the other conditions and component ratios were the same as in examples 1 to 3.
Comparative examples 7 to 9
In comparative examples 7 to 9, in the preparation process of the matrix particles, the treatment is carried out by adopting a scheme of raising the temperature at a high speed by 2 ℃/s, and the rest conditions and the component ratio are the same as those in examples 1 to 3.
Performance test
The catalytic performance and the service life of the methanol decomposition heating catalyst prepared in the comparative examples 1-9 are respectively tested.
Detection method/test method
Electrochemical testing: the test is carried out under a three-electrode system with the temperature of 30 ℃ and the normal pressure. Wherein, the glassy carbon electrode coated with the catalyst slurry is used as a working electrode, a Pt wire electrode (phi =0.5mm) is used as an auxiliary electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode; nitrogen was introduced into the solution for half an hour before all electrochemical tests were performed to remove oxygen interference from the solution. The voltage range is-0.242 to 0.958V (vsSCE). The electrolyte solution used for the electrochemical test was 0.5mol ∙ L-1H2SO4+1.0mol∙L- 1CH3OH, wherein methanol oxidation test is performed at 50mV ∙ s-1Is performed at the scanning rate of (1). The timing current test is carried out at the potential of 0.4V, and the test time is 1 h;
the specific detection results are shown in the following table 2:
TABLE 2 Performance test Table
Referring to the comparison of the performance tests of table 2, it can be found that:
comparing the comparative examples 1-3 with the examples 1-3, the reaction solution prepared in the comparative examples 1-3 is directly prepared by adopting chloroplatinic acid without adding graphite, and as can be seen from table 2, the catalytic activity and the service life of the catalyst are remarkably reduced, which shows that the catalyst is prepared by selecting graphite and chloroplatinic acid, the structural performance of matrix particles is improved and fixed, and the active particle agglomeration phenomenon caused by sintering can not be generated in the actual use process, so that the activity of the methanol decomposition catalyst in the catalytic decomposition reaction is improved, and the stability of the catalyst is improved.
Comparing comparative examples 4-6 with examples 1-3, comparative examples 4-6 only adopt porous zeolite to replace the matrix particles prepared by the method, and as can be seen from table 2, the catalytic activity and the service life of the catalyst are remarkably reduced, which indicates that the catalyst is prepared by using copper nitrate, magnesium nitrate and aluminum nitrate as raw materials, and the brucite pillared compound with positive charge is prepared by crystallization and calcination treatment after dissolution, and is used as the matrix material of the catalyst, so that the generation of liquid phase by-products is inhibited, the activity of the methanol decomposition catalyst in catalytic decomposition reaction is improved, and the stability of the catalyst is improved.
Comparing the comparative examples 7-9 with the examples 1-3, the comparative examples 7-9 adopt a scheme of high-speed temperature rise of 2 ℃/s to process in the preparation process of the matrix particles, so that the catalytic activity and the service life of the matrix particles are obviously reduced, which shows that the crystallization temperature is optimized, so that the optimized precipitation and crystallization rate is improved at the temperature, the stability of the internal structure of the clean matrix particles is improved, and the stability of the catalyst is improved while the efficiency of the catalyst in the preparation process of the matrix particles is improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A method for preparing a high-stability methanol fuel decomposition catalyst, the method comprising the steps of:
s1, respectively mixing copper nitrate, magnesium nitrate and aluminum nitrate, adding the mixture into deionized water, stirring, mixing and collecting to obtain a dissolved solution, adding the dissolved solution into a sodium carbonate solution according to the volume ratio of 1:1, and stirring and mixing to obtain a base fluid;
s2, adjusting the pH value of the matrix liquid to 9-10, standing and aging, taking the lower layer precipitate and carrying out crystallization treatment to obtain crystallized particles, washing, drying, crushing, sieving with a 500-mesh sieve, carrying out temperature programming and carrying out heat preservation roasting to obtain matrix particles;
s3, respectively weighing 45-50 parts by weight of solvent, 0.5-1.0 part by weight of modified graphite particles and 3-5 parts by weight of chloroplatinic acid, stirring, mixing and dropwise adjusting the pH value to 10.5 to obtain a reaction solution;
s4, adding the matrix particles into the reaction liquid, stirring, mixing, grinding and dispersing, sieving, taking the dispersed slurry, placing the dispersed slurry into a reaction kettle, performing hydrothermal treatment in an argon atmosphere, standing, cooling to room temperature, dropwise adding nitric acid, adjusting the pH to 2.5, filtering, taking the precipitate, washing, drying, crushing and sieving to obtain the high-stability methanol fuel decomposition catalyst.
2. The method of claim 1, wherein the mixing ratio of the copper nitrate, the magnesium nitrate and the aluminum nitrate in step S1 is Cu: mg: molar ratio of Al = 1: 2-3: 1.
3. the method as claimed in claim 1, wherein the crystallization temperature in step S2 is 75-80 ℃.
4. The method of claim 1, wherein the temperature programming in step S2 is performed at a rate of 10 ℃/min to 450-460 ℃.
5. The method of claim 1, wherein the solvent in step S3 is one of ethylene glycol and formaldehyde solution.
6. The method of claim 1, wherein the modified graphite particles of step S3 are oxidized modified graphite oxide particles.
7. The method according to claim 1, wherein the hydrothermal treatment temperature in step S4 is 155-165 ℃.
8. The method according to claim 1, wherein the sieve of step S4 has a pore size of 0.25-0.28 μm.
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| CN101745384A (en) * | 2009-12-14 | 2010-06-23 | 浙江大学 | Platinum/graphene nano electro-catalyst and preparation method thereof |
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| CN101745384A (en) * | 2009-12-14 | 2010-06-23 | 浙江大学 | Platinum/graphene nano electro-catalyst and preparation method thereof |
| CN106025293A (en) * | 2016-07-08 | 2016-10-12 | 青岛大学 | Platinum and carbon sphere@zinc-iron layered double hydroxide composite material applied to direct methanol fuel cell anode catalyst |
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