CN108579761B - Preparation method of Pt-Ir/FeOx multi-metal single-atom catalyst - Google Patents
Preparation method of Pt-Ir/FeOx multi-metal single-atom catalyst Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 49
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B01J35/399—
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
Abstract
The invention discloses Pt-Ir/FeOxThe preparation method of the multi-metal single-atom catalyst comprises the following steps: step one, preparing a catalyst by microwave coupling coprecipitation reaction; step two, washing and filtering the solid product; step three, drying and calcining the solid product to prepare Pt-Ir/FeOxA multi-metal monatomic catalyst. On the basis of the single-metal single-atom catalysis theory, the invention successfully prepares the multi-metal multi-atom catalyst and realizes the stable dispersion of multi-metal single atoms. Compared with the common CO selective oxidation catalyst, each metal atom is highly dispersed on the carrier, so that the metal utilization rate is improved, and the cost is reduced. Compared with other monatomic catalysts used for CO selective oxidation, the monatomic catalyst has higher catalytic activity due to the synergistic effect of the double metals, and the loading capacity and the stability of the monatomic catalyst are improved.
Description
Technical Field
The invention belongs to the field of catalysts, and relates to a catalyst containing FeOxA catalyst in which Pt and Ir are supported on a carrier in the form of a single atom.
Background
The monatomic catalyst is a novel catalyst. The structural characteristics are that the single atoms are uniformly distributed on the carrier. Compared with nano catalysis and sub-nano catalysis, the catalyst has many new characteristics, such as quantum size effect, huge surface free energy, interaction of a carrier and metal, unsaturated coordination environment and the like. Compared with the nano catalyst, each atom on the monatomic catalyst is an active center for catalytic reaction, so that the catalytic efficiency and the reaction selectivity are greatly improved, and the cost is reduced.
The preparation method of the monatomic catalyst includes a coprecipitation method, an atomic deposition method, an impregnation method, a step-by-step reduction method, a reverse Ostwald ripening method, a step-by-step reduction method and a solid-phase melting method.
The coprecipitation method is that the solution contains 2 or more than 2 cations which are distributed homogeneously in the solution, and after the precipitant is added, the precipitate with various components can be obtained.
Monatomic catalysts have been used for CO oxidation, hydrogenation, NO reduction and hydrogenation, water gas shift, organic synthesis, methanol steam reforming, fuel cells, photoelectrocatalysis, formaldehyde oxidation, and the like. However, due to its huge surface free energy, the monatomic catalyst is easily coupled into huge clusters during preparation, thereby causing catalyst deactivation. To prevent this, the loading on the monatomic catalyst tends to be low, which limits the practical applications of the monatomic catalyst.
The prior monatomic catalyst only has 1 metal supported on a carrier in a monatomic form. Compared with a pure metal catalyst, the stability of the common multi-metal catalyst is greatly improved. As in the oil industry, the stability of Pt-Ir catalysts for light oil reforming is greatly improved over that of pure Pt. Therefore, the development of the multi-metal single-atom catalyst can enhance the stability of the catalyst and improve the loading capacity.
In addition, the general multi-metal catalyst has higher reaction activity and selectivity compared with the pure metal catalyst. The cost can also be reduced. For example, the Pd-Ni catalyst has better reaction activity than pure Ni, and the Cu-Pd catalyst has better activity than Pd in the selective hydrogenation reaction of acetylene, and because Pd is a rare noble metal and is expensive, and the cost can be reduced by adding Cu, the multi-metal single-atom catalyst may have the excellent performances, and in the conversion of cyclohexane, the Ni catalyst can produce benzene in the dehydrogenation reaction, and the by-product can also produce methane and the like. While the use of a Ni-Cu catalyst will greatly improve dehydrogenation selectivity. In addition, some catalytic reactions require coordinated catalysis by multiple metals. The preparation of the multi-metal monatomic catalyst greatly expands the research range of the monatomic catalyst.
The hydrogen in the fuel cell usually contains 0.5% to 2% of CO, and because the anode electrocatalyst of the fuel cell is usually Pt, CO is very easily adsorbed on the surface of the catalyst, thereby hindering the catalytic oxidation of the fuel, and researches show that only a trace amount of CO can cause the deactivation of the Pt anode catalyst due to CO poisoning. Making the fuel cell unusable. The existing chemical methods for removing CO mainly comprise anode oxygen injection, a low-temperature shift reaction method, a methanation reaction method and a selective catalytic oxidation method. Of which selective catalytic oxidation is the most efficient method. In the selective catalytic oxidation method, metals such as Pt, Ru and Pd are used as catalysts to selectively oxidize CO in the hydrogen-rich gas.
The Xiao' gang and the like prepare an integral catalyst (patent number: ZL200810301388.3) for selectively oxidizing CO in hydrogen-rich reformed gas, and the catalytic active component of the catalyst is Ru, and the content of the catalytic active component is 0.1-2 wt% calculated by Ru; the catalytic promoter is one or more of alkali metal oxide or/and alkaline earth metal oxide; the molar ratio of Ru to alkali metal oxide or/and metal elements in the alkali metal oxide is 1-20: 1; the rest is cordierite carrier coated with alumina gel, wherein the content of the alumina gel accounts for 2-10 wt% of the catalyst content. Complex structure, high price and low reaction activity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide FeOxThe preparation method of the Pt-Ir/FeOx multi-metal single-atom catalyst is a carrier, can load the single-atom catalyst of Pt and Ir in a single-atom form at the same time, and improves the metal load capacity, the catalytic activity and the selectivity of the catalyst.
The invention relates to Pt-Ir/FeOxThe preparation method of the multi-metal single-atom catalyst comprises the following steps:
step one, preparing a catalyst by microwave coupling coprecipitation reaction, which comprises the following specific steps:
equal volume of H with the concentration of 0.02-1.2mol/L2PtCl6Solution, solution,H with a concentration of 0.02-1.2mol/L2IrCl6Mixing the solution with a water-soluble ferric salt solution with the concentration of 1mol/L, then adding an alkaline substance solution with the concentration of 1mol/L into the mixed solution, adjusting the pH value of the mixed solution to 8, carrying out coprecipitation reaction at the temperature of 20-80 ℃, then putting the obtained solution into a microwave reactor for heating, and leading the catalyst Pt and Ir to be on a carrier Fe (OH)3The upper part is uniformly distributed;
step two, washing and filtering the solid product, which comprises the following specific steps:
washing the obtained solid product with distilled water, and then filtering the solid product by using a vacuum pump to remove residual ions in the solid product;
step three, drying and calcining the solid product, which comprises the following specific steps:
uniformly spreading the filtered and washed product on a quartz plate, drying in a microwave dryer to remove water, wherein the thickness of the material spread on the quartz plate is less than 2mm, and calcining the dried product at 400 ℃ for 4-5 hours, thus obtaining a carrier Fe (OH)3Conversion to FeOxTo prepare Pt-Ir/FeOxA multi-metal monatomic catalyst.
The invention has the beneficial effects that:
on the basis of the single-metal single-atom catalysis theory, the invention successfully prepares the multi-metal multi-atom catalyst and realizes the stable dispersion of multi-metal single atoms. Compared with the common CO selective oxidation catalyst, each metal atom is highly dispersed on the carrier, so that the metal utilization rate is improved, and the cost is reduced. Compared with other monatomic catalysts used for CO selective oxidation, the monatomic catalyst has higher catalytic activity due to the synergistic effect of the double metals, and the loading capacity and the stability of the monatomic catalyst are improved.
Drawings
FIG. 1 is a graph of the reaction rates for CO oxidation and CO preferential oxidation as a function of the temperature of the coprecipitation reaction in the preparation of the catalyst in example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples
The invention relates toAnd Pt-Ir/FeOxThe preparation method of the multi-metal single-atom catalyst comprises the following steps:
step one, preparing a catalyst by microwave coupling coprecipitation reaction, which comprises the following specific steps:
equal volume of H with the concentration of 0.02-1.2mol/L2PtCl6Solution, H with concentration of 0.02-1.2mol/L2IrCl6The solution is mixed with a water-soluble ferric salt solution with the concentration of 1mol/L, then an alkaline substance solution with the concentration of 1mol/L is added into the mixed solution, the pH value of the mixed solution is adjusted to 8, and the coprecipitation reaction is carried out at the temperature of 20-80 ℃ (the preferable coprecipitation reaction lasts for 8-24 hours). Then putting the obtained solution into a microwave reactor, heating for 2-10 minutes at 100-200 ℃ to ensure that the catalyst Pt and Ir are supported on Fe (OH)3The upper distribution is uniform. The reaction temperature is selected under the condition that the coprecipitation reaction is not influenced. The trivalent iron salt is not limited to Fe (NO)3)3Containing Fe3+The iron salt of (2) can be used for preparing the catalyst; the alkaline substance is not limited to Na2CO3All alkaline substances for adjusting the pH can be used.
Step two, washing and filtering the solid product, which comprises the following specific steps:
the obtained solid product was washed with distilled water and then filtered with a vacuum pump to remove ions remaining in the solid product.
Step three, drying and calcining the solid product, which comprises the following specific steps:
uniformly spreading the filtered and washed product on a quartz plate, placing the quartz plate in a microwave dryer for drying, removing water, wherein the thickness of the material spread on the quartz plate is less than 2mm, and then calcining the dried product at 400 ℃ for 4-5 hours to obtain Pt-Ir/FeOxA multi-metal monatomic catalyst.
The vacuum pump may be replaced with other filtration apparatus.
Example 1
Step one, preparing a catalyst by microwave coupling coprecipitation reaction
500ml of H2PtCl6(0.06mol/L)、500ml H2IrCl6(0.02mol/L) solution with 500ml Fe (NO)3)3(1mol/L) mixing, passing through Na2CO3(1mol/L) the solution pH was adjusted to 8, and the coprecipitation reaction was carried out at 20 ℃ for 8 hours. Then putting the obtained solution into a microwave reactor, heating to 100 ℃ and reacting for 2 minutes to ensure that the catalyst Pt and Ir are supported on Fe (OH)3The upper distribution is uniform.
Step two, washing and filtering the solid product
The obtained solid product was washed with distilled water and then filtered with a vacuum pump to remove ions remaining in the solid product.
Step three, drying and calcining the solid product
Uniformly spreading the filtered and washed product on a quartz plate, placing the quartz plate in a microwave dryer for drying to remove water, wherein the thickness of the material spread on the quartz plate is 1.9mm, calcining the dried product at 400 ℃ for 4 hours, and carrying out Fe (OH) carrier3Conversion to FeOxTo prepare Pt-Ir/FeOxA multi-metal monatomic catalyst.
For prepared Pt-Ir/FeOxThe activity and selectivity evaluation of the multi-metal monatomic catalyst comprises the following specific steps:
CO oxidation reaction: the reactivity of the catalyst was determined by oxidation of CO in a fixed bed and preferential oxidation of CO. Firstly, forming a catalyst into granules, then weighing about 80mg of the catalyst, putting the catalyst into a U-shaped quartz reactor, introducing He with the volume proportion of 10% at the temperature of 200 ℃ for pretreatment for 0.5 hour, and introducing test gas at the speed of 25ml per minute, wherein the volume proportions of the test gas are respectively CO 1% and O21% and He is balance gas. The gas composition discharged is detected on line by gas chromatography and a thermal conductivity detector.
Preferential oxidation of CO is similarly carried out by passing H into the test gas 240％，CO1％，O21% and He is balance gas, and other steps are the same.
The results show that the prepared catalyst has Pt loading of 0.15 wt% and Ir loading of 0.04 wt%, and the reaction rate is 6020mol in the CO oxidation reactionco h-1gmetal -1In the preferential oxidation reaction of CO, the reaction rate is 9930molco h- 1gmetal -1. The selectivity was 50%. FIG. 1 is a graph of the relationship between the temperature of the co-precipitation reaction and the catalyst reactivity in the catalyst preparation, and it can be seen that as the temperature increases, both the catalytic activity and the selectivity of the catalyst increase.
Example 2
Step one, preparing a catalyst by microwave coupling coprecipitation reaction
500ml of H2PtCl6(0.02mol/L)、500ml H2IrCl6(0.06mol/L) solution with 500ml Fe2(SO4)3(1mol/L) mixing, passing through Na2CO3(1mol/L) the solution pH was adjusted to 8, and the coprecipitation reaction was carried out at 80 ℃ for 11 hours. Then putting the obtained solution into a microwave reactor, heating to 200 ℃ and reacting for 2 minutes to ensure that the catalyst Pt and Ir are supported on Fe (OH)3The upper distribution is uniform.
Step two, washing and filtering the solid product
The obtained solid product was washed with distilled water and then filtered with a vacuum pump to remove ions remaining in the solid product.
Step three, drying and calcining the solid product
Uniformly spreading the filtered and washed product on a quartz plate, placing the quartz plate on a microwave dryer to dry and remove water, wherein the thickness of the material spread on the quartz plate is 1.8mm, calcining the dried product at 400 ℃ for 4.5 hours, and carrying Fe (OH)3Conversion to FeOxTo prepare Pt-Ir/FeOxA multi-metal monatomic catalyst.
The method comprises the following steps:
CO oxidation reaction: the reactivity of the catalyst was determined by oxidation of CO in a fixed bed and preferential oxidation of CO. Firstly, the catalyst is formed into granules, then about 80mg of the catalyst is weighed and put into a U-shaped quartz reactor, and H is introduced under the condition that the temperature is 200 DEG C2He pretreatment of 10% volume ratio for 0.5 hour at a rate of 25ml per minuteTest gas is introduced, wherein the volume ratio of the test gas is CO1 percent and O21% and He is balance gas. The gas composition discharged is detected on line by gas chromatography and a thermal conductivity detector.
Preferential oxidation of CO is similarly carried out by passing H into the test gas 240％，CO1％，O21% and He is balance gas, and other steps are the same.
The result shows that the prepared catalyst has Pt loading of 0.04 wt% and Ir loading of 1.5 wt%, and the reaction rate is 6520mol in the CO oxidation reactionco h-1gmetal -1In the preferential oxidation reaction of CO, the reaction rate is 8720molco h-1gmetal -1. The selectivity was 50%.
Example 3
Step one, preparing a catalyst by microwave coupling coprecipitation reaction
500ml of H2PtCl6(0.2mol/L)、500ml H2IrCl6(1.2mol/L) solution with Fe (NO)3(1mol/L) of the solutions were mixed, the pH of the solution was adjusted to 8 by NaOH (1mol/L), and a coprecipitation reaction was carried out at 80 ℃ for 16 hours. Then putting the obtained solution into a microwave reactor, heating to 170 ℃ and reacting for 5 minutes to ensure that the catalyst Pt and Ir are supported on Fe (OH)3The upper distribution is uniform.
Step two, washing and filtering the solid product
The obtained solid product was washed with distilled water and then filtered with a vacuum pump to remove ions remaining in the solid product.
Step three, drying and calcining the solid product
Uniformly spreading the filtered and washed product on a quartz plate, placing the quartz plate on a microwave dryer to dry and remove water, wherein the thickness of the material spread on the quartz plate is 1mm, calcining the dried product at 400 ℃ for 5 hours, and carrying Fe (OH)3Conversion to FeOxTo prepare Pt-Ir/FeOxA multi-metal monatomic catalyst.
The method comprises the following steps:
COand (3) oxidation reaction: the reactivity of the catalyst was determined by oxidation of CO in a fixed bed and preferential oxidation of CO. Firstly, the catalyst is formed into granules, then about 80mg of the catalyst is weighed and put into a U-shaped quartz reactor, and H is introduced under the condition that the temperature is 200 DEG C2He with volume ratio of 10% is pretreated for 0.5 hour, and then test gas with volume ratio of CO 1% and O is introduced at a speed of 25 ml/min21% and He is balance gas. The gas composition discharged is detected on line by gas chromatography and a thermal conductivity detector.
Preferential oxidation of CO is similarly carried out by passing H into the test gas 240％，CO1％，O21% and He is balance gas, and other steps are the same.
The result shows that the prepared catalyst has Pt loading of 0.41 wt% and Ir loading of 3.0 wt%, and the reaction rate is 81230mol in the CO oxidation reactionco h-1gmetal -1In the preferential oxidation reaction of CO, the reaction rate is 163920molco h- 1gmetal -1. The selectivity was 56%.
Example 4
Step one, preparing a catalyst by microwave coupling coprecipitation reaction
500ml of H2PtCl6(1.2mol/L)、500ml H2IrCl6(0.4mol/L) solution with 500ml Fe (NO)3(1mol/L) the solutions were mixed and passed through Na2CO3(1mol/L) the solution pH was adjusted to 8, and the coprecipitation reaction was carried out at 60 ℃ for 24 hours. Then putting the obtained solution into a microwave reactor, heating to 200 ℃ and reacting for 10 minutes to ensure that the catalyst Pt and Ir are supported on Fe (OH)3The upper distribution is uniform.
Step two, washing and filtering the solid product
The obtained solid product was washed with distilled water and then filtered with a vacuum pump to remove ions remaining in the solid product.
Step three, drying and calcining the solid product
The product after filtration and washing is evenly spread on a quartz plate and placed in a micro-chamberDrying in a wave dryer to remove water, spreading on a quartz plate to a thickness of 0.5mm, calcining the dried product at 400 deg.C for 5 hr, and supporting Fe (OH)3Conversion to FeOxTo prepare Pt-Ir/FeOxA multi-metal monatomic catalyst.
The method comprises the following steps:
CO oxidation reaction: the reactivity of the catalyst was determined by oxidation of CO in a fixed bed and preferential oxidation of CO. Firstly, the catalyst is formed into granules, then about 80mg of the catalyst is weighed and put into a U-shaped quartz reactor, and H is introduced under the condition that the temperature is 200 DEG C2He with volume ratio of 10% is pretreated for 0.5 hour, and then test gas with volume ratio of CO 1% and O is introduced at a speed of 25 ml/min21% and He is balance gas. The gas composition discharged is detected on line by gas chromatography and a thermal conductivity detector.
Preferential oxidation of CO is similarly carried out by passing H into the test gas 240％，CO1％，O21% and He is balance gas, and other steps are the same.
The result shows that the prepared catalyst has Pt loading of 3.1 wt% and Ir loading of 0.81 wt%, and the reaction rate is 99830mol in the CO oxidation reactionco h-1gmetal -1In the preferential oxidation reaction of CO, the reaction rate is 198320molco h- 1gmetal -1. The selectivity was 56%.
Claims (2)
1. Pt-Ir/FeOxThe preparation method of the multi-metal single-atom catalyst is characterized by comprising the following steps:
step one, preparing a catalyst by microwave coupling coprecipitation reaction, which comprises the following specific steps:
equal volume of H with the concentration of 0.02-1.2mol/L2PtCl6Solution, H with concentration of 0.02-1.2mol/L2IrCl6The solution is mixed with 1mol/L water-soluble ferric salt solution, then 1mol/L alkaline substance solution is added into the mixed solution,adjusting the pH value of the mixed solution to 8, carrying out coprecipitation reaction at the temperature of 20-80 ℃, then putting the obtained solution into a microwave reactor, heating at the temperature of 100-200 ℃ for 2-10 minutes to enable the catalyst Pt and Ir to be on a carrier Fe (OH)3The upper part is uniformly distributed;
step two, washing and filtering the solid product, which comprises the following specific steps:
washing the obtained solid product with distilled water, and then filtering the solid product by using a vacuum pump to remove residual ions in the solid product;
step three, drying and calcining the solid product, which comprises the following specific steps:
uniformly spreading the filtered and washed product on a quartz plate, drying in a microwave dryer to remove water, wherein the thickness of the material spread on the quartz plate is less than 2mm, and calcining the dried product at 400 ℃ for 4-5 hours, thus obtaining a carrier Fe (OH)3Conversion to FeOxTo prepare Pt-Ir/FeOxA multi-metal monatomic catalyst.
2. Pt-Ir/FeO according to claim 1xThe preparation method of the multi-metal single-atom catalyst is characterized by comprising the following steps: the coprecipitation reaction is carried out for 8 to 24 hours.
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