CN111686774A - High-stability monatomic platinum-based catalytic material, preparation method and application in purification of oxygen-containing volatile hydrocarbon - Google Patents
High-stability monatomic platinum-based catalytic material, preparation method and application in purification of oxygen-containing volatile hydrocarbon Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 63
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 53
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
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- 238000000746 purification Methods 0.000 title claims abstract description 20
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- 239000000243 solution Substances 0.000 claims description 77
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- 239000007787 solid Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 35
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- 239000000843 powder Substances 0.000 claims description 22
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B01J35/615—
-
- B01J35/633—
-
- 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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
A high-stability monatomic platinum-based catalytic material, a preparation method and an application in purification of oxygen-containing volatile hydrocarbon are disclosed, wherein high-stability molybdenum carbide is used as a carrier, and abundant surface hydroxyl groups are constructed on the surface of the carrier through a hydrothermal alkaline leaching method. So that the monoatomic platinum active phase is stably dispersed on the surface of the molybdenum carbide carrier through strong interaction with surface hydroxyl. The monoatomic platinum-based catalytic material prepared by the invention has excellent low-temperature catalytic activity and stabilityThe reaction can be carried out at the temperature of 100 ℃ plus 135 ℃ and the reaction space velocity of 36000h plus 45000h‑1And the oxygen concentration is 10-20 vol.% to realize deep purification of volatile oxygen-containing hydrocarbon discharged from industrial sources. The invention greatly improves the low-temperature catalysis efficiency of the monatomic catalytic material. The problem of high cost of the load type noble metal is solved to a certain extent, and the method has better application universality.
Description
Technical Field
The invention belongs to the technical field of air pollution treatment, and particularly relates to a high-stability monatomic platinum-based catalytic material, a preparation method and application thereof in purification of oxygen-containing volatile hydrocarbon.
Background
Volatile Organic Compounds (VOCs) are a generic term for all Organic Compounds that have a boiling point below 260 ℃ at atmospheric pressure or have a saturated vapor pressure above 133.32Pa at room temperature (25 ℃) and are emitted into the air in gaseous molecular form. VOCs are in various types, and mainly comprise aliphatic hydrocarbons, oxygen-containing hydrocarbons, aromatic hydrocarbons and derivatives thereof, halogen-containing hydrocarbons, nitrogen-containing hydrocarbons, sulfur-containing hydrocarbons and the like. VOCs have high atmospheric chemical reaction activity and are a key factor for enhancing atmospheric oxidation. In recent years, the total amount of VOCs discharged in China is gradually increased, and the problems of photochemical smog, urban dust haze and other composite atmospheric pollution caused by the VOCs are increasingly serious. The emission of a large amount of VOCs not only causes the atmospheric quality to be reduced, but also produces great harm to the functions of the immune system, the kidney and the respiratory system of the human body, and increases the carcinogenic risk of the tissues and organs of the human body (brain, pancreas, lymph, hematopoiesis, stomach and the like). After dust removal, desulfurization, denitration and motor vehicle exhaust pollution treatment, VOCs pollution control becomes one of the priority directions of atmospheric pollution control in China. According to related requirements, the reduction and emission reduction of volatile hydrocarbons emitted by key industries (parks) are currently carried out in China, emission reduction measures in the emission process combined with sources are emphasized and developed, and efficient control technology and process equipment are formed. Therefore, the efficient emission reduction control of the VOCs has important significance for improving the quality of the atmospheric environment in China. Oxygen-containing volatile organic pollutants (such as formaldehyde, acetone, ethyl acetate and the like) which are taken as representatives of heteroatom hydrocarbons can be discharged into the environment by various ways such as furniture decoration, coating, packaging printing, electronic chemical industry and the like, and cause extremely serious negative effects on the production and the life of human beings. The catalytic oxidation technology has the advantages of high efficiency, energy conservation, environmental protection and the like, and is one of the most effective means for purifying low-concentration volatile hydrocarbons at present. The supported noble metal catalyst has good activity and strong regenerability, and is widely used for removing oxygen-containing hydrocarbons. However, the noble metal is expensive, and the active center is easy to agglomerate and is easy to inactivate, so that the prospect of further industrial application is limited. Therefore, there is an urgent need to develop a monatomic catalyst with high activity and high stability according to the emission characteristics and molecular characteristics of volatile oxygen-containing hydrocarbons so as to improve the conversion rate of pollutants on a unit platinum atom, reduce the cost of catalytic materials and maintain higher activity and stability. The invention has important application prospect in the field of low-temperature purification of volatile organic pollutants.
Disclosure of Invention
The invention aims to provide a high-stability monatomic platinum-based catalytic material, a preparation method and application in purification of oxygen-containing volatile hydrocarbon.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-stability monatomic platinum-based catalytic material comprises the steps of adding a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer into an ammonium molybdate tetrahydrate aqueous solution, stirring uniformly, then dropwise adding cis-oil-based primary amine, and stirring uniformly to form a light yellow transparent solution; then adjusting the pH value to 3.5-4, continuously stirring to obtain a mixed solution, carrying out heating reflux reaction on the mixed solution in a microwave generator, centrifuging after complete reaction, and roasting for one time to obtain powder; putting the powder into a potassium hydroxide solution, uniformly stirring, and then putting the powder into a hydrothermal reaction kettle for crystallization to obtain a solid; dispersing the solid in ethanol, adding polyvinylpyrrolidone, stirring uniformly, then dropwise adding a chloroplatinic acid hexahydrate-ethanol solution, heating, stirring, filtering, washing, drying, and roasting for the second time to obtain the high-stability monatomic platinum-based catalytic material.
In a further improvement of the invention, the aqueous ammonium molybdate tetrahydrate solution is prepared by dissolving ammonium molybdate tetrahydrate in deionized water, wherein the ratio of ammonium molybdate tetrahydrate to deionized water is 15-35 mmoL: 75-95 mL.
A further improvement of the invention is that the ratio of ammonium molybdate tetrahydrate, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to cis-oleyl primary amine is 15 to 35 mmoL: 0.53-0.75 g: 15-23 mL.
The further improvement of the invention is that 1mol/L hydrochloric acid is adopted to adjust the pH value to 3.5-4, and the stirring is continued for 30 min; the power of the microwave generator is set to 850W, the temperature of the reflux reaction is 120-135 ℃, and the time is 30-45 min.
The further improvement of the invention is that the specific conditions of the primary roasting are as follows: the process is carried out in nitrogen atmosphere, the temperature of primary roasting is 600 ℃, and the time of primary roasting is 4-5 h.
The further improvement of the invention is that the concentration of the potassium hydroxide solution is 0.1-1 mol/L; the crystallization temperature is 80-100 ℃, and the crystallization time is 2.5-3.5 h; when the solid was dispersed in ethanol, the ratio of solid to polyvinylpyrrolidone was 1 g: 0.05-0.1 g.
The further improvement of the invention is that the concentration of the chloroplatinic acid hexahydrate-ethanol solution is 1.5-4.0mg Pt/mL; the specific conditions of the secondary roasting are as follows: the process is carried out in nitrogen atmosphere, the temperature of secondary roasting is 200 ℃, and the time of secondary roasting is 2-3.5 h.
The specific surface area of the high-stability monatomic platinum-based catalytic material is 236.8-275.4m2Per g, the pore volume of the micropores is 0.14-0.29cm3/g。
An application of high-stability monatomic platinum-based catalytic material in the purification of volatile oxygen-containing hydrocarbons.
The further improvement of the present invention is the use according to claim 13, wherein the high-stability monatomic platinum-based catalytic material is at a temperature of 100--1And the volume concentration of the oxygen is 10-20%, and the purification of the methanol with the volume concentration of 0.08% is realized.
A further improvement of the invention is that the volatile oxygen-containing hydrocarbon is methanol.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, ammonium molybdate tetrahydrate is hydrolyzed and then is easily subjected to rapid complexation with cis-form oil-based primary amine to form a precursor of rod-shaped molybdenum carbide, and the complexation degree of the precursor is improved and the pore volume and the specific surface area of a molybdenum carbide carrier are increased by pre-adding a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer. The formation of the high-stability crystal form of the molybdenum carbide carrier can be further promoted by dropwise adding low-concentration hydrochloric acid into the mixed solution to adjust the pH of the solution. In the invention, the molybdenum carbide carrier is further modified by a hydrothermal alkaline leaching method, so that abundant surface hydroxyl groups are constructed on the surface of the carrier. The capture and stabilization of the carrier to the monoatomic platinum precursor are realized by utilizing the non-localization effect of the hydroxyl on the surface of the high-stability carrier. Further, through the strong interaction of the monatomic platinum active phase and the surface hydroxyl, the charge balance process between the carrier and the noble metal is accelerated, and the low-temperature catalysis efficiency and the stability of the monatomic catalysis material are greatly improved. The synthesis method constructed by microwave-assisted hydrothermal alkaline leaching greatly shortens the synthesis time and energy consumption, solves the problem of high cost of the supported noble metal to a certain extent, overcomes the technical defects of complex preparation process and low yield of the existing monatomic catalytic material, and has the prospect of universal application.
The high-stability monatomic platinum-based catalytic material prepared by the invention is widely applied to the purification of volatile oxygen-containing hydrocarbon, and abundant surface hydroxyl groups are constructed on the surface of a carrier by taking high-stability molybdenum carbide as the carrier and a hydrothermal alkaline leaching method. So that the monoatomic platinum active phase is stably dispersed on the surface of the molybdenum carbide carrier through strong interaction with surface hydroxyl. The high-stability monatomic platinum-based catalytic material prepared by the invention is prepared at the temperature of 100 ℃ plus 135 ℃ at the space velocity of 36000h plus 45000h-1And the deep purification of the methanol with the volume concentration of 0.08 percent is realized under the condition that the volume concentration of the oxygen is 10 to 20 percent. The invention has important application prospect in the field of low-temperature purification of volatile organic pollutants.
Drawings
FIG. 1 is a field emission scanning electron microscope image of a highly stable single-atom platinum-based catalytic material according to the present invention; wherein (a) is high and (b) is low.
FIG. 2 is an EDS-mapping picture of a high-stability single-atom platinum-based catalytic material in a high-angle annular dark field image mode.
FIG. 3 is a spherical aberration electron microscope image of the high-stability single-atom platinum-based catalytic material of the present invention. Wherein (a) is low multiple, (b) is medium multiple, and (c) is high multiple.
FIG. 4 is a graph showing the purification efficiency of a highly stable single-atom platinum-based catalytic material for methanol in the present invention.
Fig. 5 is a water resistance test of the highly stable single-atom platinum-based catalytic material of the present invention.
FIG. 6 is an XRD spectrum of a highly stable single-atom platinum-based catalytic material according to the present invention.
FIG. 7 is a solid-phase nuclear magnetic resonance test spectrum of the high-stability single-atom platinum-based catalytic material of the invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The invention adopts a microwave-assisted synthesis method to prepare a high-stability porous molybdenum carbide carrier, utilizes the fact that ammonium molybdate tetrahydrate is hydrolyzed and then is easily rapidly complexed with cis-form oil-based primary amine to form a precursor of rod-shaped molybdenum carbide, and improves the complexation degree of the precursor and increases the pore volume and the specific surface area of the molybdenum carbide carrier by pre-adding a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer. The formation of the high-stability crystal form of the molybdenum carbide carrier can be further promoted by dropwise adding low-concentration hydrochloric acid into the mixed solution to adjust the pH of the solution. In the invention, the molybdenum carbide carrier is further modified by a hydrothermal alkaline leaching method, so that abundant surface hydroxyl groups are constructed on the surface of the carrier. The capture and stabilization of the carrier to the monoatomic platinum precursor are realized by utilizing the non-localization effect of the hydroxyl on the surface of the high-stability carrier. Further, through the strong interaction of the monatomic platinum active phase and the surface hydroxyl, the charge balance process between the carrier and the noble metal is accelerated, and the low-temperature catalysis efficiency and the stability of the monatomic catalysis material are greatly improved. The synthesis method constructed by microwave-assisted hydrothermal alkaline leaching greatly shortens the synthesis time and energy consumption, solves the problem of high cost of the supported noble metal to a certain extent, overcomes the technical defects of complex preparation process and low yield of the existing monatomic catalytic material, and has the prospect of universal application. The high-stability monatomic platinum-based catalytic material prepared by the method has abundant surface hydroxyl groups, and shows excellent stability for low-temperature purification of methanol.
The invention comprises the following steps:
(1) 15-35mmoL of ammonium molybdate tetrahydrate is dissolved in 75-95mL of deionized water, and is stirred for 10min at the rotating speed of 500-800rpm to be fully dissolved;
(2) adding 0.53-0.75g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) into the transparent solution obtained in the step (1), and stirring at the rotating speed of 800-;
(3) dropwise adding 15-23mL of cis-oil-based primary amine into the transparent solution obtained in the step (2), wherein the step is helpful for accelerating the nucleation process of rod-shaped molybdenum carbide, and then stirring at the rotating speed of 800-1000rpm for 20min to form a light yellow transparent solution;
(4) dropwise adding 1mol/L hydrochloric acid prepared in advance into the yellow transparent solution obtained in the step (3) to adjust the pH value of the solution, so that the final pH value of the solution is between 3.5 and 4, and continuously stirring the solution for 30 min;
(5) placing the mixed solution obtained in the step (4) in a microwave generator for heating reflux reaction, wherein the power of the microwave generator is set to 850W, the temperature of the reflux reaction is 120-135 ℃, and the time is 30-45 min;
(6) after the solution in the step (5) is cooled to room temperature, centrifuging at 4000-;
(7) carrying out roasting on the solid obtained in the step (6) in a nitrogen atmosphere at the roasting temperature of 600 ℃ for 4-5 h;
(8) dispersing the solid powder obtained in the step (7) in 70-100mL of 0.1-1mol/L potassium hydroxide solution, and stirring at the rotating speed of 800-1000rpm for 30min to uniformly mix the solid powder;
(9) placing the mixed solution obtained in the step (8) in a hydrothermal reaction kettle, wherein the temperature in the hydrothermal crystallization process is 80-100 ℃, and the time is 2.5-3.5 h;
(10) after the mixed solution in the step (9) is cooled to room temperature, centrifuging at 4000-;
(11) dispersing the solid obtained in the step (10) in an ethanol solution, and stirring at the rotating speed of 800-;
(12) adding 0.05-0.1g of polyvinylpyrrolidone into the solution obtained in the step (11), and stirring at the rotating speed of 1000rpm of 800-;
(13) dropwise adding 3-8mL of 1.5-4mg Pt/mL chloroplatinic acid hexahydrate-ethanol solution into the mixed solution obtained in the step (12), and stirring at the rotating speed of 800-1000rpm at the temperature of 50 ℃ for 120 min; wherein, the addition amount of the chloroplatinic acid hexahydrate is 12 mg.
(14) After the solution obtained in the step (13) is cooled to room temperature, filtering, washing with deionized water and ethanol, and drying at 80-100 ℃ to obtain black solid powder;
(15) and (4) roasting the solid powder obtained in the step (14) under the nitrogen condition, wherein the roasting temperature is 200 ℃, and the roasting time is 2-3.5 h.
The high-stability monatomic platinum-based catalytic material prepared by the invention has higher specific surface area (236.8-275.4 m)2Per gram) and pore volume (0.14-0.29 cm)3(iv)/g); the high-stability monatomic platinum-based cuprous oxide catalytic material can be applied to the purification of volatile oxygen-containing hydrocarbons. Specifically, the reaction space velocity is 36,000-45,000h at the temperature of 100-135 DEG C-1Under the condition that the oxygen concentration is 10-20%, the deep purification of the methanol with the volume concentration of 0.08% is realized; the prepared catalytic material has good stability and poisoning resistance.
The following are specific examples.
Example 1 preparation of highly stable porous molybdenum carbide support (MoC) by microwave-assisted synthesis
(1) Dissolving 30mmoL ammonium molybdate tetrahydrate in 90mL deionized water, and stirring at 700rpm for 10min to fully dissolve the ammonium molybdate tetrahydrate;
(2) subsequently, 0.65g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) was added to the clear solution obtained in step (1), and stirred at 900rpm for 10 min.
(3) Immediately after 17mL of cis-oleyl primary amine was added dropwise to the solution obtained in step (2), which helped to accelerate the nucleation of rod-shaped molybdenum carbide, it was stirred at 900rpm for 20min to form a pale yellow transparent solution.
(4) And (4) dropwise adding 1mol/L hydrochloric acid prepared in advance into the solution obtained in the step (3) to adjust the pH value of the solution so that the final pH value of the solution is between 3.5 and 4, and continuously stirring the solution for 30 min.
(5) And (5) then placing the mixed solution obtained in the step (4) in a microwave generator to carry out heating reflux reaction, wherein the power of the microwave generator is set to 850W, the temperature of the reflux reaction is 130 ℃, and the time is 40 min. And after the solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, drying to obtain a solid, roasting the solid in a nitrogen atmosphere at the roasting temperature of 600 ℃ for 4 hours, and obtaining the sample, namely the porous molybdenum carbide carrier (MoC).
Referring to FIG. 1, it can be seen from FIG. 1 that the high-stability monatomic catalytic material prepared by the present invention has a rod-like structure, a diameter of about 10nm and a length of about 6-21 μm.
Example 2 preparation of highly stable porous molybdenum carbide support (Mo) by microwave-assisted synthesis2C)
Dissolving 30mmoL ammonium molybdate tetrahydrate in 90mL deionized water, and stirring at 700rpm for 10min to fully dissolve the ammonium molybdate tetrahydrate; 0.65g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) was then added to the clear solution and stirred at 900rpm for 10 min. Immediately after the dropwise addition of 17mL of p-aniline, which helps to accelerate the nucleation of the rod-shaped molybdenum carbide, the above solution was stirred at 900rpm for 20min to form a pale yellow transparent solution. Adding 1mol/L hydrochloric acid prepared in advance dropwise into the solution to adjust the pH value of the solution so that the final pH value of the solution is between 6.5 and 8, and continuing stirring the solution for 30 min. Then the mixed solution is placed in a microwave generator for heating reflux reaction, the power of the microwave generator is set to be 850W, the temperature of the reflux reaction is 130 ℃,the time is 40 min. Cooling the solution to room temperature, centrifuging at 6000rpm, washing with ethanol and deionized water, drying, and roasting in nitrogen atmosphere at 600 deg.C for 4 hr to obtain porous molybdenum carbide carrier (Mo)2C)。
Example 3 construction of abundant surface hydroxyl groups by hydrothermal alkaline immersion
The carrier obtained in example 1 was dispersed in 80mL of 0.5mol/L potassium hydroxide solution and stirred at 800rpm for 30min to mix uniformly. Then placing the mixture into a hydrothermal reaction kettle, setting the temperature of the hydrothermal crystallization process to be 90 ℃ and setting the time to be 3 hours. And after the mixed solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, and drying to obtain black solid powder, namely the surface hydroxyl modified high-stability carrier (OH-MoC).
Example 4
The carrier obtained in example 2 was dispersed in 80mL of 0.5mol/L potassium hydroxide solution and stirred at 800rpm for 30min to mix well. Then placing the mixture into a hydrothermal reaction kettle, setting the temperature of the hydrothermal crystallization process to be 90 ℃ and setting the time to be 3 hours. Cooling the mixed solution to room temperature, centrifuging at 6000rpm, washing with ethanol and deionized water, and drying to obtain black solid powder, i.e. surface hydroxyl modified high-stability carrier (OH-Mo)2C)。
Example 3 differs from example 4 in that example 3 employs the support prepared in example 1. Example 4 the support prepared in example 2 was used.
EXAMPLE 5 Capture of monoatomic precursors by surface hydroxyl delocalization
0.5g of the solid powder of example 3 was accurately weighed and dispersed in the ethanol solution, and stirred at 1000rpm for 5min to mix it uniformly. 0.08g of polyvinylpyrrolidone is then added and stirred at 1000rpm for 5min to mix homogeneously. 8mL of a 1.5mg Pt/mL chloroplatinic acid hexahydrate-ethanol solution was added dropwise to the above mixed solution, and the mixture was stirred at 1000rpm at 50 ℃ for 120 min. After the solution had cooled to room temperature, it was filtered and washed with deionized water and ethanol, dried at 90 deg.C, and the solvent was evaporatedThen roasting under the condition of nitrogen, wherein the roasting temperature is 200 ℃, the roasting time is 2 hours, and the obtained solid is the high-stability monatomic catalytic material (Pt) prepared by the invention1-OH-MoC/Pt1-OH-Mo2C)。
Example 6
0.5g of the solid powder of example 4 was accurately weighed and dispersed in the ethanol solution, and stirred at 1000rpm for 5min to mix it uniformly. 0.08g of polyvinylpyrrolidone is then added and stirred at 1000rpm for 5min to mix homogeneously. 8mL of a 1.5mg Pt/mL chloroplatinic acid hexahydrate-ethanol solution was added dropwise to the above mixed solution, and the mixture was stirred at 1000rpm at 50 ℃ for 120 min. After the solution is cooled to room temperature, filtering, washing with deionized water and ethanol, drying at 90 ℃, and then roasting under the condition of nitrogen, wherein the roasting temperature is 200 ℃, the roasting time is 2 hours, and the obtained solid is the high-stability monatomic catalytic material (Pt) prepared by the invention1-OH-Mo2C)。
Example 5 differs from example 6 in that example 5 employs the solid powder prepared in example 3. Example 6 the solid powder prepared in example 4 was used.
Referring to fig. 2, it can be seen from fig. 2 that the surface elements (Mo, O, C, Pt) of the high-stability monatomic platinum-based catalytic material prepared by the present invention are uniformly distributed.
Referring to fig. 3, from the analysis of the results in fig. 3, it can be seen that the platinum active phase on the surface of the high-stability monatomic platinum-based catalytic material prepared by the present invention is dispersed on the surface of the high-stability molybdenum carbide carrier in an atomic scale.
Referring to fig. 6, it can be seen from the analysis of the results of fig. 6 that the high-stability monatomic catalytic material prepared by the present invention has good crystallinity and a clear crystal phase.
Referring to fig. 7, the high-stability monatomic platinum-based catalytic material prepared by the invention has abundant surface hydroxyl groups, and the purification capacity of the catalytic material to methanol is greatly improved.
Example 7
(1) Dissolving 15mmoL of ammonium molybdate tetrahydrate in 75mL of deionized water, and stirring at 700rpm for 10min to fully dissolve the ammonium molybdate tetrahydrate;
(2) subsequently, 0.53g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) was added to the clear solution obtained in step (1), and stirred at 900rpm for 10 min.
(3) Immediately after 15mL of cis-oleyl primary amine was added dropwise to the solution obtained in step (2), which helped to accelerate the nucleation of rod-shaped molybdenum carbide, it was stirred at 900rpm for 20min to form a pale yellow transparent solution.
(4) And (4) dropwise adding 1mol/L hydrochloric acid prepared in advance into the solution obtained in the step (3) to adjust the pH of the solution so that the final pH value of the solution is 3.5, and continuously stirring the solution for 30 min.
(5) And (5) then placing the mixed solution obtained in the step (4) in a microwave generator to carry out heating reflux reaction, wherein the power of the microwave generator is set to 850W, the temperature of the reflux reaction is 120 ℃, and the time is 30 min. And after the solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, drying to obtain a solid, roasting the solid in a nitrogen atmosphere at the roasting temperature of 600 ℃ for 4 hours, and obtaining the sample, namely the porous molybdenum carbide carrier (MoC).
(6) The carrier obtained above was dispersed in 90mL of 0.5mol/L potassium hydroxide solution, and stirred at 800rpm for 30min to mix it uniformly. Then placing the mixture into a hydrothermal reaction kettle, setting the temperature in the hydrothermal crystallization process to be 80 ℃, and setting the time to be 3.5 h. And after the mixed solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, and drying to obtain black solid powder, namely the surface hydroxyl modified high-stability carrier (OH-MoC).
(7) Accurately weighing 0.5g of the black solid powder, dispersing in ethanol solution, and stirring at 1000rpm for 5min to mix uniformly. 0.025g of polyvinylpyrrolidone was then added and stirred at 1000rpm for 5min to mix well. 8mL of a 1.5mg Pt/mL chloroplatinic acid hexahydrate-ethanol solution was added dropwise to the above mixed solution, and the mixture was stirred at 1000rpm at 50 ℃ for 120 min. And (3) after the solution is cooled to room temperature, filtering, washing with deionized water and ethanol, drying at 90 ℃, and then roasting under the condition of nitrogen, wherein the roasting temperature is 200 ℃, the roasting time is 2 hours, and the obtained solid is the prepared high-stability monatomic catalytic material.
Example 8
(1) Dissolving 20mmoL ammonium molybdate tetrahydrate in 95mL deionized water, and stirring at 700rpm for 10min to fully dissolve the ammonium molybdate tetrahydrate;
(2) subsequently, 0.75g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) was added to the clear solution obtained in step (1), and stirred at 900rpm for 10 min.
(3) Immediately after 20mL of cis-oleyl primary amine was added dropwise to the solution obtained in step (2), which helped to accelerate the nucleation of rod-shaped molybdenum carbide, it was stirred at 900rpm for 20min to form a pale yellow transparent solution.
(4) And (4) dropwise adding 1mol/L hydrochloric acid prepared in advance into the solution obtained in the step (3) to adjust the pH of the solution so that the final pH value of the solution is 3.7, and continuously stirring the solution for 30 min.
(5) And (5) then placing the mixed solution obtained in the step (4) in a microwave generator to carry out heating reflux reaction, wherein the power of the microwave generator is set to 850W, the temperature of the reflux reaction is 150 ℃, and the time is 35 min. And after the solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, drying to obtain a solid, roasting the solid in a nitrogen atmosphere at the roasting temperature of 600 ℃ for 4.5 hours, and obtaining the sample, namely the porous molybdenum carbide carrier (MoC).
(6) The carrier obtained above was dispersed in 110mL of 0.1mol/L potassium hydroxide solution, and stirred at 800rpm for 30min to mix it uniformly. Then placing the mixture into a hydrothermal reaction kettle, setting the temperature of the hydrothermal crystallization process to be 100 ℃ and setting the time to be 2.5 h. And after the mixed solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, and drying to obtain black solid powder, namely the surface hydroxyl modified high-stability carrier (OH-MoC).
(7) Accurately weighing 0.5g of the black solid powder, dispersing in ethanol solution, and stirring at 1000rpm for 5min to mix uniformly. 0.5g of polyvinylpyrrolidone was then added and stirred at 1000rpm for 5min to mix well. To the above mixed solution was added dropwise 3mL of a 4mg Pt/mL chloroplatinic acid hexahydrate-ethanol solution, and the mixture was stirred at 1000rpm at 50 ℃ for 120 min. And (3) after the solution is cooled to room temperature, filtering, washing with deionized water and ethanol, drying at 90 ℃, and then roasting under the condition of nitrogen, wherein the roasting temperature is 200 ℃, the roasting time is 3.5 hours, and the obtained solid is the prepared high-stability monatomic catalytic material.
Example 9
(1) Dissolving 35mmoL of ammonium molybdate tetrahydrate in 80mL of deionized water, and stirring at 700rpm for 10min to fully dissolve the ammonium molybdate tetrahydrate;
(2) subsequently, 0.6g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) was added to the clear solution obtained in step (1), and stirred at 900rpm for 10 min.
(3) Immediately after adding 23mL of cis-oleyl primary amine dropwise to the solution obtained in step (2), this step helped to accelerate the nucleation of rod-shaped molybdenum carbide, and then stirring at 900rpm for 20min to form a pale yellow transparent solution.
(4) And (4) dropwise adding 1mol/L hydrochloric acid prepared in advance into the solution obtained in the step (3) to adjust the pH of the solution so that the final pH value of the solution is 4, and continuously stirring the solution for 30 min.
(5) And (5) then placing the mixed solution obtained in the step (4) in a microwave generator to carry out heating reflux reaction, wherein the power of the microwave generator is set to 850W, the temperature of the reflux reaction is 135 ℃, and the time is 45 min. And after the solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, drying to obtain a solid, roasting the solid in a nitrogen atmosphere at the roasting temperature of 600 ℃ for 5 hours, and obtaining the sample, namely the porous molybdenum carbide carrier (MoC).
(6) The carrier obtained above was dispersed in 100mL of a 1mol/L potassium hydroxide solution, and stirred at 800rpm for 30min to mix uniformly. Then placing the mixture into a hydrothermal reaction kettle, setting the temperature of the hydrothermal crystallization process to be 90 ℃ and setting the time to be 3 hours. And after the mixed solution is cooled to room temperature, centrifuging at the rotating speed of 6000rpm, washing with ethanol and deionized water, and drying to obtain black solid powder, namely the surface hydroxyl modified high-stability carrier (OH-MoC).
(7) Accurately weighing 0.5g of the black solid powder, dispersing in ethanol solution, and stirring at 1000rpm for 5min to mix uniformly. 0.3g of polyvinylpyrrolidone is then added and stirred at 1000rpm for 5min to mix homogeneously. 4mL of a chloroplatinic acid hexahydrate-ethanol solution (3 mg Pt/mL) was added dropwise to the above mixed solution, and the mixture was stirred at 1000rpm at 50 ℃ for 120 min. And (3) after the solution is cooled to room temperature, filtering, washing with deionized water and ethanol, drying at 90 ℃, and then roasting under the condition of nitrogen, wherein the roasting temperature is 200 ℃, the roasting time is 3 hours, and the obtained solid is the prepared high-stability monatomic catalytic material.
Example 10 Activity of highly Stable monatomic platinum-based catalytic Material for catalytic degradation of methanol
The catalytic reaction is carried out in a fixed bed, the catalysts obtained in examples 5 and 6 are tableted and sieved (40-60 meshes), 0.3mL of the sieved catalytic material is accurately weighed, the catalyst is activated for 1.5h at 150 ℃, methanol (methanol) is used as a probe gas, the concentration of a reactant is controlled to be 800ppm, and the reaction space velocity is 36000-45000h-1The volume concentration of oxygen is 20%, the catalytic reaction activity of the catalyst at the temperature of 60 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ and 170 ℃ is respectively tested, and the reaction product is monitored and analyzed by gas chromatography-mass spectrometry.
Referring to FIG. 4, it can be seen from the analysis of FIG. 4 that the highly stable monatomic platinum-based catalytic material prepared in the present invention exhibits excellent low temperature degradation efficiency for methanol, and can be reacted at a temperature of 100--1And under the condition of 10-20% of oxygen concentration, the complete mineralization of methanol with volume concentration of 0.08% is realized.
Example 11 Water resistance test of highly stable monatomic platinum-based catalytic Material
The catalysts obtained in examples 5 and 6 were tableted, sieved (40-60 mesh), and 0.3mL of the sieved catalytic material was accurately weighed and placed in a fixed bed of an evaluation apparatus, and activated at 200 ℃ for 1.5 hours toMethanol (methanol) is used as probe gas, the concentration of reactants is controlled to be 800ppm, and the reaction space velocity is 36000h-1The oxygen concentration was 20%, and 3 vol.% of H was introduced after the catalytic reaction was stabilized at 100 ℃2And O water vapor, and continuously testing the catalytic reaction activity of the catalyst under the mixed component atmosphere condition. Cut off H after 40min2And O water vapor, and continuously testing the catalytic activity of the catalytic material until the catalytic activity is stable.
Referring to fig. 5, it can be seen from the analysis of fig. 5 that the highly stable monatomic platinum-based catalytic material prepared in the present invention has excellent water vapor impact resistance in the process of purifying methanol at low temperature. The introduction of low concentration water vapor only produces a short competitive adsorption effect and does not damage the structure of the monoatomic active site.
According to the invention, high-stability molybdenum carbide is used as a carrier, and abundant surface hydroxyl groups are constructed on the surface of the carrier by a hydrothermal alkaline leaching method. So that the monoatomic platinum active phase is stably dispersed on the surface of the molybdenum carbide carrier through strong interaction with surface hydroxyl. The monoatomic platinum-based catalytic material prepared by the method has excellent low-temperature catalytic activity and stability, and can react at the temperature of 100 ℃ and the space velocity of 36000 ℃ and 45000h-1And the oxygen concentration is 10-20 vol.% to realize deep purification of volatile oxygen-containing hydrocarbon (methanol) discharged from industrial sources. According to the invention, the capture and stabilization of the monoatomic platinum precursor by the carrier are realized by utilizing the non-localization effect of the hydroxyl on the surface of the high-stability carrier. Further, through the strong interaction of the monatomic active phase and the surface hydroxyl, the charge balance process between the carrier and the noble metal is accelerated, and the low-temperature catalysis efficiency of the monatomic catalytic material is greatly improved. According to the invention, by adopting the synthesis method constructed after microwave-assisted hydrothermal alkaline leaching, the synthesis time and energy consumption are greatly shortened, the problem of high cost of the supported noble metal is solved to a certain extent, the technical defects of complex preparation process and low yield of the existing single-atom catalytic material are overcome, and the method has good application universality.
Claims (10)
1. A preparation method of a high-stability monatomic platinum-based catalytic material is characterized in that a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is added into an ammonium molybdate tetrahydrate aqueous solution, after uniform stirring, cis-oil-based primary amine is added dropwise, and uniform stirring is carried out to form a light yellow transparent solution; then adjusting the pH value to 3.5-4, continuously stirring to obtain a mixed solution, carrying out heating reflux reaction on the mixed solution in a microwave generator, centrifuging after complete reaction, and roasting for one time to obtain powder; putting the powder into a potassium hydroxide solution, uniformly stirring, and then putting the powder into a hydrothermal reaction kettle for crystallization to obtain a solid; dispersing the solid in ethanol, adding polyvinylpyrrolidone, stirring uniformly, then dropwise adding a chloroplatinic acid hexahydrate-ethanol solution, heating, stirring, filtering, washing, drying, and roasting for the second time to obtain the high-stability monatomic platinum-based catalytic material.
2. The method for preparing a highly stable monatomic platinum-based catalytic material of claim 1, wherein the aqueous ammonium molybdate tetrahydrate solution is prepared by dissolving ammonium molybdate tetrahydrate in deionized water, wherein the ratio of ammonium molybdate tetrahydrate to deionized water is 15 to 35 mmoL: 75-95 mL.
3. The method for preparing a high-stability monatomic platinum-based catalytic material according to claim 1, wherein the ratio of ammonium molybdate tetrahydrate, the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and the cis-oleyl primary amine is 15 to 35 mmoL: 0.53-0.75 g: 15-23 mL.
4. The preparation method of the high-stability monatomic platinum-based catalytic material according to claim 1, characterized in that 1mol/L hydrochloric acid is adopted to adjust the pH value to 3.5-4, and the stirring is continued for 30 min; the power of the microwave generator is set to 850W, the temperature of the reflux reaction is 120-135 ℃, and the time is 30-45 min.
5. The preparation method of the high-stability monatomic platinum-based catalytic material according to claim 1, characterized in that the specific conditions of the primary calcination are as follows: the process is carried out in nitrogen atmosphere, the temperature of primary roasting is 600 ℃, and the time of primary roasting is 4-5 h.
6. The method for preparing a high-stability monatomic platinum-based catalytic material according to claim 1, wherein the concentration of the potassium hydroxide solution is 0.1 to 1 mol/L; the crystallization temperature is 80-100 ℃, and the crystallization time is 2.5-3.5 h; when the solid was dispersed in ethanol, the ratio of solid to polyvinylpyrrolidone was 1 g: 0.05-0.1 g.
7. The method for preparing a high-stability monatomic platinum-based catalytic material according to claim 1, wherein the concentration of the chloroplatinic acid hexahydrate-ethanol solution is 1.5-4.0mg Pt/mL; the specific conditions of the secondary roasting are as follows: the process is carried out in nitrogen atmosphere, the temperature of secondary roasting is 200 ℃, and the time of secondary roasting is 2-3.5 h.
8. A high stable monatomic platinum-based catalytic material prepared by the method according to any one of claims 1 to 7, characterized in that the high stable monatomic platinum-based catalytic material has a specific surface area of 236.8 to 275.4m2Per g, the pore volume of the micropores is 0.14-0.29cm3/g。
9. Use of a highly stable monatomic platinum-based catalytic material prepared according to the method of any of claims 1 to 8 in the purification of volatile oxygen-containing hydrocarbons.
10. The use as claimed in claim 9, wherein the use as claimed in claim 13, is characterized in that the highly stable monatomic platinum-based catalytic material is used at a temperature of 100 ℃ and a space velocity of 36000 ℃ and 45000h-1And the volume concentration of the oxygen is 10-20%, and the purification of the methanol with the volume concentration of 0.08% is realized.
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| CN112958112B (en) * | 2021-02-07 | 2022-01-25 | 西安交通大学 | Monatomic platinum-based catalytic material under different atmospheres, and preparation method and application thereof |
| CN113262776A (en) * | 2021-04-20 | 2021-08-17 | 武汉理工大学 | W-TiO2Monatomic supported photocatalyst and preparation method thereof |
| CN113262776B (en) * | 2021-04-20 | 2023-09-22 | 武汉理工大学 | W-TiO 2 Monoatomic supported photocatalyst and preparation method thereof |
| CN116116442A (en) * | 2023-02-20 | 2023-05-16 | 常州大学 | Preparation method and application of low-load sub-nanometer noble metal catalyst |
| CN116116442B (en) * | 2023-02-20 | 2023-12-22 | 常州大学 | Preparation method and application of low-load sub-nanometer noble metal catalyst |
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