CN115283001A - High-temperature-resistant supported metal catalyst and preparation method thereof - Google Patents
High-temperature-resistant supported metal catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 14
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 11
- 229920001690 polydopamine Polymers 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- -1 carboxylic acid compound Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of supported catalysts, and discloses a high-temperature-resistant supported metal catalyst and a preparation method thereof; the preparation method comprises the following steps: sequentially adding metal oxide, alkali and dopamine hydrochloride into a solvent A by taking the metal oxide as a carrier, and then carrying out stirring reaction to coat a polydopamine layer on the surface of the metal oxide to obtain a precursor A; sequentially adding the precursor A and a metal source into a solvent B, uniformly mixing, then carrying out heating treatment to remove the solvent B, and drying to obtain a precursor A with a surface containing metal ions, namely a precursor B; and carrying out pyrolysis treatment on the precursor B at the temperature of 500-1200 ℃ in an inert atmosphere to obtain the high-temperature-resistant supported metal catalyst. The preparation method is mild in preparation conditions, simple, green and environment-friendly, strong in sustainability and suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of supported catalysts, in particular to a high-temperature-resistant supported metal catalyst and a preparation method thereof.
Background
At present, the supported metal catalyst is widely applied to various fields such as petrochemical industry, coal chemical industry, fine chemical industry and the like. However, in industrial applications, especially in some high-temperature reactions, such as propane dehydrogenation, ammonia synthesis, hydrogen production by steam reforming, etc., the metal nanoparticles in the supported catalyst are often sintered due to ostwald ripening or particle fusion, resulting in nanoparticle growth, reduced dispersion, reduced active sites, and finally severe deactivation of the catalyst. In addition, in some liquid phase reactions using high polar substances as solvents, such as aqueous phase reaction systems, due to poor hydrothermal stability of traditional oxide (alumina, silica, molecular sieve, etc.) carriers, the supported metal catalyst has the situation that the oxides are hydrolyzed or collapsed during the reaction process, so that active metals on the surface of the carrier are lost or sintered, and finally the activity of the catalyst is reduced. On the other hand, the updating and the recovery of the deactivated catalyst can greatly increase the time and the economic cost, and influence the production benefit of enterprises. Therefore, the development of sintering-resistant high-temperature-resistant supported metal catalysts is a problem which needs to be solved urgently in the chemical industry.
When the metal particles are semi-embedded in the carrier, the agglomeration and loss of the metal particles can be effectively inhibited, the metal particles can be exposed, the utilization efficiency of metal is ensured, and the problems that the high-temperature reaction supported catalyst metal nanoparticles in the industry are easy to sinter and the supported catalyst metal nanoparticles in a liquid phase reaction system are easy to lose or sinter are hopefully solved. However, at present, such catalysts are mainly prepared by hard template method, the preparation process is complicated and time-consuming, and highly corrosive HF or NaOH is used.
Therefore, the invention provides a high-temperature-resistant supported metal catalyst and a preparation method thereof.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a high-temperature-resistant supported metal catalyst and a preparation method thereof, so that a supported metal catalyst with a semi-mosaic structure is simply and efficiently synthesized through a novel preparation process. The invention takes metal oxide as a carrier and polydopamine as a limited space shell, thereby not only ensuring the contact of active metal and reactants in the reaction process, but also preventing the agglomeration of metal atoms, and further showing excellent activity and stability so as to meet the requirements of application and development of related fields.
The invention relates to a high-temperature resistant supported metal catalyst and a preparation method thereof, which are realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of a high-temperature-resistant supported metal catalyst, which comprises the following steps:
step 1, taking a metal oxide as a carrier, sequentially adding the metal oxide, alkali and dopamine hydrochloride into a solvent A, and then carrying out stirring reaction to coat a polydopamine layer on the surface of the metal oxide to obtain a precursor A;
and 3, carrying out pyrolysis treatment on the precursor B at the temperature of 500-1200 ℃ in a nitrogen atmosphere to obtain the high-temperature-resistant supported metal catalyst.
Further, the metal oxide is Al 2 O 3 、TiO 2 And SiO 2 One or two of them.
Further, the solvent A is one or two of methanol, ethanol and water;
the alkali is any one of ammonia water, tris (hydroxymethyl) aminomethane, diethylamine, sodium bicarbonate, sodium hydroxide, potassium bicarbonate and potassium hydroxide.
Further, the mass ratio of the metal oxide to the alkali to the dopamine hydrochloride is 10;
the dosage ratio of the solvent A to the metal oxide is 80-120mL.
Further, the solvent B is one or two of methanol, ethanol and water;
the metal source is any one of an Fe source, a Co source, an Ni source, a Cu source, a Ru source, a Pd source, a Pt source, an Rh source and an Ir source.
Further, the mass ratio of the precursor A to the metal source is 1.05-0.2;
the dosage ratio of the solvent B to the precursor A is 100-150mL.
Further, the treatment time of the pyrolysis treatment is 0.5-12 h; the heating rate of the pyrolysis treatment is 1-10 ℃/min.
Further, the temperature of the stirring reaction is room temperature, the stirring speed is 0.5-72 h.
Further, the temperature of the heating treatment is 30 to 80 ℃.
The second purpose of the invention is to provide a high-temperature resistant supported metal catalyst prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes metal oxide as a carrier and polydopamine as a porous shell; a layer of polydopamine with controllable thickness is constructed on the surface of the metal oxide to construct a limited space shell, so that the exposure of acid-base sites of the oxide can be ensured, the agglomeration of metal atoms in the preparation and high-temperature use processes of the catalyst can be obviously inhibited, and the dispersibility and stability of active metals are enhanced.
The polydopamine shell coated on the surface of the metal oxide can be converted into nitrogen-doped porous carbon in situ in the pyrolysis process, the hydrophilicity and hydrophobicity, acid-base properties and the like of the surface of the catalyst can be effectively regulated and controlled by regulating the thickness and porosity of the nitrogen-doped porous carbon, and meanwhile, gas molecules such as hydrogen, carbon monoxide and the like can be released in the process of converting the polydopamine into the nitrogen-doped porous carbon, so that the in-situ reduction of metal ions can be realized without subsequent reduction treatment by using hydrogen.
The preparation method disclosed by the invention is mild in preparation conditions, simple, green and environment-friendly, strong in sustainability and suitable for industrial large-scale production.
The high-temperature-resistant supported metal catalyst prepared by the preparation method has an oxide-metal-carbon three-phase interface structure, shows excellent high-temperature-resistant stability, and can be applied to liquid-phase reactions taking high-polarity substances as solvents, such as carboxylic acid compound water-phase hydrogenation, and gas-solid reactions carried out under high-temperature and high-pressure conditions, such as alkane dehydrogenation, biomass and derivatives thereof reforming hydrogen production, carbon dioxide and methane conversion, and the like.
Drawings
FIG. 1 shows Ru/Al prepared in example 1 2 O 3 Transmission electron micrographs of @ CN-700 catalyst;
FIG. 2 shows Ru/Al prepared in example 2 2 O 3 Transmission electron micrograph of @ CN-900 catalyst;
FIG. 3 is Pd/Al prepared in example 3 2 O 3 Transmission electron micrographs of @ CN-500 catalyst;
FIG. 4 is a Pt/Al alloy prepared in example 4 2 O 3 Transmission electron micrograph of @ CN-700 catalyst;
FIG. 5 shows Ru/TiO prepared in example 5 2 Transmission electron micrograph of @ CN-800 catalyst;
FIG. 6 shows Ru/SiO solid prepared in example 6 2 Transmission electron micrograph of @ CN-700 catalyst;
FIG. 7 shows Pd/Al prepared in example 3 2 O 3 The X-ray diffraction pattern of the @ CN-500 catalyst;
FIG. 8 shows Ru/SiO solid prepared in example 6 2 The X-ray diffraction pattern of the @ CN-700 catalyst;
FIG. 9 is the Co/TiO prepared in example 7 2 The X-ray diffraction pattern of the @ CN-700 catalyst.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
The embodiment provides a high-temperature resistant supported metal catalyst, and the preparation method thereof is as follows:
step 1, taking a metal oxide as a carrier, sequentially adding the metal oxide, alkali and dopamine hydrochloride into a solvent A, and then carrying out stirring reaction to coat a polydopamine layer on the surface of the metal oxide to obtain a precursor A;
it should be noted that the present invention is not limited to a specific type of metal oxide, as long as a porous polydopamine shell layer can be coated on the surface of the metal oxide or oxide. Optionally, in this embodiment, al is used 2 O 3 Is a carrier.
The present invention is not limited to a specific type of the solvent a as long as it can form a uniform solution or suspension with the metal oxide. Alternatively, in this embodiment, methanol is used as the solvent a.
The present invention is not limited to a specific type of alkali as long as the stirring reaction can be carried out under an alkaline condition (pH 8 to 10). Alternatively, in this example, tris was used as the base.
The invention does not limit the specific operation process parameters of the stirring reaction, and the method only needs to be capable of coating the dopamine hydrochloride on the surface of the metal oxide to form a poly-dopamine layer in an alkaline solvent environment. Alternatively, in this example, 1.0g of carrier Al 2 O 3 Adding the mixture into 100mL of methanol solution, uniformly mixing, then adding 0.6g of tris (hydroxymethyl) aminomethane and 0.5g of dopamine hydrochloride, stirring at room temperature at the speed of 300r/min for 12 hours, carrying out solid-liquid separation, washing a solid component obtained by the solid-liquid separation with methanol, washing until a filtrate is colorless and transparent, and drying to obtain a precursor A.
The present invention is not limited to the specific form of the solid-liquid separation described above, as long as a solid product of the stirred reaction can be obtained. Optionally, in this embodiment, solid-liquid separation is performed by using a suction filtration method.
The present invention is not limited to the specific manner of the above-mentioned drying as long as the excess solvent on the surface of the solid component can be removed. Optionally, in this example, drying is carried out in an oven at 60 ℃ for 12h.
it should be noted that the present invention does not limit the specific type of solvent B, as long as it can form a uniform solution or suspension with precursor a and facilitate the removal by evaporation by means of heating. Optionally, in this embodiment, ethanol is used as the solvent B.
The invention is not limited to specific types of metal sources and can be carried out according to the actual material requiredAs long as the desired metal ions can be provided. Optionally, in this embodiment, a Ru source is used as the metal source, and specifically, ruCl with a concentration of 10mg/mL is used 3 The aqueous solution served as the Ru source.
The invention does not limit the specific mixing mode of the precursor A and the metal source in the solvent B, as long as the precursor A and the metal source can be uniformly dispersed in the solvent B to perform sufficient contact reaction. Optionally, in this embodiment, mixing is performed by stirring, and 0.5g of precursor a obtained in step 1 is weighed at room temperature, added to 60mL of ethanol solution, and then added to 1.0mL of RuCl 3 The aqueous solution was stirred at a rate of 300r/min for 30min to obtain a mixed solution.
The invention does not limit the specific temperature and time of the heating treatment, and can flexibly select the solvent according to the actually selected volatility of the solvent B. Optionally, in this embodiment, because ethanol is used as the solvent B, heating treatment is performed at 60 ℃, specifically, after the obtained mixed solution is heated to 60 ℃, until the solvent is completely evaporated to dryness, so as to obtain the precursor B.
In order to improve the efficiency of the heat treatment, the present embodiment further performs stirring during the heat treatment, and the stirring speed is 500r/min.
Step 3, carrying out pyrolysis treatment on the precursor B in a nitrogen atmosphere to obtain a high-temperature-resistant supported metal catalyst;
it should be noted that, the invention does not limit the specific reaction time of the pyrolysis treatment, and the reaction time can be flexibly adjusted according to the specific reaction temperature. Optionally, in this embodiment, the precursor B obtained in step 2 is loaded into a tube furnace, heated to 700 ℃ at a rate of 5 ℃/min in a nitrogen flow, and kept for 2 hours, and the obtained black powder is the high-temperature resistant supported metal catalyst of this embodiment, and is named as Ru/Al 2 O 3 @CN-700。
Example 2
This example provides a high temperature resistant supported metal catalyst, and the preparation method thereof is different from that of example 1 only in that:
in step 3 of this embodiment, the temperature of the pyrolysis treatment is 900 ℃;
the high temperature resistant supported metal catalyst obtained in the example is named as Ru/Al 2 O 3 @CN-900。
Example 3
This example provides a high temperature resistant supported metal catalyst, and the preparation method differs from that of example 1 only in that:
in step 2 of this embodiment, a Pd source is used as a metal source, and specifically PdCl with a concentration of 10mg/mL 2 The aqueous solution is a Pd source;
in step 3 of this embodiment, the temperature of the pyrolysis treatment is 500 ℃;
the high temperature resistant supported metal catalyst obtained in this example was named Pd/Al 2 O 3 @CN-500。
Example 4
This example provides a high temperature resistant supported metal catalyst, and the preparation method differs from that of example 1 only in that:
in step 2 of this example, a Pt source is used as a metal source, and specifically, H is used at a concentration of 10mg/mL 2 PtCl 6 The water solution is a Pt source;
the high temperature resistant supported metal catalyst obtained in this example was named Pt/Al 2 O 3 @CN-700。
Example 5
This example provides a high temperature resistant supported metal catalyst, and the preparation method thereof is different from that of example 1 only in that:
in step 1 of this example, tiO is used 2 Is a metal oxide;
in step 3 of this embodiment, the pyrolysis temperature is 800 ℃;
the high temperature resistant supported metal catalyst obtained in the example is named as Ru/TiO 2 @CN-800。
Example 6
This example provides a high temperature resistant supported metal catalyst, and the preparation method thereof is different from that of example 1 only in that:
the procedure of this example1 in SiO 2 Is an oxide;
the high temperature resistant supported metal catalyst obtained in the example is named as Ru/SiO 2 @CN-700。
Example 7
This example provides a high temperature resistant supported metal catalyst, and the preparation method differs from that of example 1 only in that:
in step 1 of this example, tiO is used 2 Is a metal oxide;
in step 2 of this embodiment, a Co source is used as a metal source, and specifically 50mg of cobalt acetate is used as a Co source;
the high temperature resistant supported metal catalyst obtained in this example was named Co/TiO 2 @CN-700。
Example 8
This example provides a high temperature resistant supported metal catalyst, and the preparation method differs from that of example 1 only in that:
in step 1 of this embodiment:
with Al 2 O 3 With SiO 2 The mixture mixed by equal mass is metal oxide;
ethanol is used as a solvent A;
ammonia water is used as alkali;
in the embodiment, the mass ratio of the metal oxide to the alkali and the dopamine hydrochloride is 10;
the dosage ratio of the solvent A to the metal oxide is 80mL;
the stirring speed of the stirring reaction is 200r/min, and the stirring time is 72h.
In step 2 of this embodiment:
methanol is used as a solvent B;
the mass ratio of the precursor A to the metal source is 1;
the dosage ratio of the solvent B to the precursor A is 100mL;
the temperature of the heat treatment was 30 ℃.
In step 3 of this embodiment:
the treatment time of the pyrolysis treatment is 12h; the heating rate of the pyrolysis treatment is 10 ℃/min;
example 9
This example provides a high temperature resistant supported metal catalyst, and the preparation method differs from that of example 1 only in that:
in step 1 of this embodiment:
deionized water is used as a solvent A;
diethylamine is used as a base;
in the embodiment, the mass ratio of the metal oxide to the alkali and the dopamine hydrochloride is 10;
the dosage ratio of the solvent A to the metal oxide is 120mL;
the stirring speed of the stirring reaction is 500r/min, and the stirring time is 0.5h.
In step 2 of this embodiment:
deionized water is used as a solvent B;
the mass ratio of the precursor A to the metal source is 1;
the dosage ratio of the solvent B to the precursor A is 150mL;
the temperature of the heat treatment was 80 ℃.
In step 3 of this embodiment:
the treatment time of the pyrolysis treatment is 0.5h; the heating rate of the pyrolysis treatment is 1 ℃/min;
example 10
This example provides a high temperature resistant supported metal catalyst, and the preparation method differs from that of example 1 only in that:
in step 1 of this embodiment:
taking a mixed solvent of deionized water and methanol which are mixed in equal volume as a solvent A;
sodium hydroxide is used as alkali;
in the embodiment, the mass ratio of the metal oxide to the alkali and the dopamine hydrochloride is 10;
the dosage ratio of the solvent A to the metal oxide is 90mL;
the stirring speed of the stirring reaction is 400r/min, and the stirring time is 12h.
In step 2 of this embodiment:
taking a mixed solvent of deionized water and ethanol which are mixed in equal volume as a solvent B;
the mass ratio of the precursor A to the metal source is 1;
the dosage ratio of the solvent B to the precursor A is 120mL;
the temperature of the heat treatment was 50 ℃.
In step 3 of this embodiment:
the treatment time of the pyrolysis treatment is 12h; the heating rate of the pyrolysis treatment is 3 ℃/min;
test section
(I) Transmission Electron microscopy testing
The transmission electron microscope tests of the high temperature resistant supported metal catalysts prepared in examples 1 to 6 were respectively carried out, and the test results are respectively shown in fig. 1 to 6.
FIG. 1 shows Ru/Al prepared in example 1 2 O 3 In a transmission electron microscope image of the @ CN-700 catalyst, it can be seen that in the high temperature resistant supported metal catalyst prepared in example 1 under the pyrolysis condition of 700 ℃, ru particles are still in a highly dispersed state, and the average particle size is about 1.3nm.
FIG. 2 shows Ru/Al prepared in example 2 2 O 3 In a transmission electron microscope image of the @ CN-900 catalyst, it can be seen that the Ru particles in the catalyst prepared in example 2 (pyrolysis at 900 ℃) are still in a high-dispersion state, and the average particle size is 1.5nm, which indicates that the alumina-supported ruthenium catalyst prepared by the method has very high thermal stability.
FIG. 3 is Pd/Al prepared in example 3 2 O 3 Transmission electron micrograph of @ CN-500 catalyst, it can be seen that Pd particles in the catalyst prepared in example 3 (500 ℃) are still in highly dispersed state, with an average particle size of 3nm.
FIG. 4 is a Pt/Al alloy prepared in example 4 2 O 3 Transmission electron microscopy of the @ CN-700 catalyst, it can be seen that the Pt particles in the catalyst remain highly dispersed after 700 ℃ pyrolysis, with an average particle size of 2.0nm.
FIG. 5 shows Ru/TiO prepared in example 5 2 Transmission electron micrograph of @ CN-800 catalyst shows that in the catalyst after 800 ℃ pyrolysisThe Ru particles were still in a highly dispersed state and had an average particle size of about 1.3nm.
FIG. 6 shows Ru/SiO solid prepared in example 6 2 Transmission electron microscopy of the @ CN-700 catalyst, it can be seen that the Ru particles in the catalyst prepared in example 6 (after 700 ℃ pyrolysis) are still in a highly dispersed state with an average particle size of 1.5nm.
(II) X-ray diffraction test
The high temperature resistant supported metal catalysts prepared in example 3, example 6 and example 7 were subjected to X-ray diffraction analysis, and the test results are shown in fig. 7 to 9, respectively.
FIG. 7 shows Pd/Al prepared in example 3 2 O 3 The X-ray diffraction pattern of the catalyst @ CN-500 showed that the characteristic diffraction peak ascribed to Pd was not observed in the X-ray diffraction pattern of the catalyst prepared in example 3, indicating that Pd in the catalyst was in a highly dispersed state.
FIG. 8 shows Ru/SiO solid prepared in example 6 2 The X-ray diffraction pattern of the catalyst @ CN-700 showed that the catalyst prepared in example 6 had no characteristic diffraction peak ascribed to Ru, indicating that Pd was in a highly dispersed state.
FIG. 9 is the Co/TiO prepared in example 7 2 The X-ray diffraction pattern of the catalyst @ CN-700 showed that the X-ray diffraction pattern of the catalyst prepared in example 7 did not show a characteristic diffraction peak attributed to Co, indicating that Co in the catalyst was in a highly dispersed state.
It follows that the porous polymer shell strategy is equally applicable to different oxide supports and metal species.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-temperature-resistant supported metal catalyst is characterized by comprising the following steps of:
step 1, taking a metal oxide as a carrier, sequentially adding the metal oxide, alkali and dopamine hydrochloride into a solvent A, and then carrying out stirring reaction to coat a polydopamine layer on the surface of the metal oxide to obtain a precursor A;
step 2, sequentially adding the precursor A and a metal source into a solvent B, uniformly mixing, then, carrying out heating treatment to remove the solvent B, and drying to obtain a precursor A with a surface containing metal ions, namely a precursor B;
and 3, carrying out pyrolysis treatment on the precursor B at the temperature of 500-1200 ℃ in a nitrogen atmosphere to obtain the high-temperature-resistant supported metal catalyst.
2. The method of claim 1, wherein the metal oxide is Al 2 O 3 、TiO 2 And SiO 2 One or two of them.
3. The method according to claim 1, wherein the solvent a is one or two of methanol, ethanol and water;
the alkali is any one of ammonia water, tris (hydroxymethyl) aminomethane, diethylamine, sodium bicarbonate, sodium hydroxide, potassium bicarbonate and potassium hydroxide.
4. The preparation method according to claim 1, wherein the mass ratio of the metal oxide to the alkali and dopamine hydrochloride is 10;
the dosage ratio of the solvent A to the metal oxide is 80-120mL.
5. The method according to claim 1, wherein the solvent B is one or two of methanol, ethanol and water;
the metal source is any one of an Fe source, a Co source, an Ni source, a Cu source, a Ru source, a Pd source, a Pt source, an Rh source and an Ir source.
6. The production method according to claim 1, wherein the mass ratio of the precursor a to the metal source is 1;
the dosage ratio of the solvent B to the precursor A is 100-150mL.
7. The method according to claim 1, wherein the pyrolysis treatment is carried out for a treatment time of 0.5 to 12 hours; the heating rate of the pyrolysis treatment is 1-10 ℃/min.
8. The preparation method of claim 1, wherein the stirring reaction is carried out at room temperature, at a stirring rate of 200 to 500r/min and for a stirring time of 0.5 to 72 hours.
9. The method according to claim 1, wherein the temperature of the heat treatment is 30 to 80 ℃.
10. A high temperature resistant supported metal catalyst prepared by the method of any one of claims 1 to 9.
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