CN114950475B - Low-temperature preparation method and application of high-entropy two-dimensional catalyst - Google Patents
Low-temperature preparation method and application of high-entropy two-dimensional catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- 239000012855 volatile organic compound Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 12
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000002135 nanosheet Substances 0.000 abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000002490 spark plasma sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000809 air pollutant Substances 0.000 description 2
- 231100001243 air pollutant Toxicity 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 239000012047 saturated solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
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Abstract
The invention provides a low-temperature preparation method and application of a high-entropy two-dimensional catalyst. The invention uses polyvinylpyrrolidone as a template and metal salt as a precursor, and forms uniform two-dimensional nano-sheets through a freeze drying technology and air annealing. Ce prepared in the examples of the present invention 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The high-entropy catalyst can catalyze toluene, formaldehyde, acetone and chlorobenzene to burn with high selectivity and high efficiency; indicating the advantage that the high entropy catalyst component diversity can promote various catalytic reactions. The synthesis method of the high-entropy two-dimensional catalyst provided by the invention has the advantages of low preparation temperature, universality, simplicity, easiness in implementation, simplicity in equipment, environmental friendliness and the like, and provides a new way and a new idea for the application of the high-entropy material in the fields of catalysis, energy conversion and the like.
Description
Technical Field
The invention relates to the technical field of nano materials and catalysis, in particular to a low-temperature preparation method and application of a high-entropy two-dimensional catalyst.
Background
A High-entropy material (HEA) is a solid solution formed of five or more elements (the molar amount of each element is 5% -35%) with a higher entropy value. The high-entropy alloy has the characteristics of high strength (fracture resistance), high toughness (deformation resistance), high temperature resistance, wear resistance, corrosion resistance, oxidation resistance and the like, and is widely researched and applied in the field of structural materials. The unique high entropy effect exhibited by the high entropy alloy causes the worldwide research of high entropy materials, and the research scope of the high entropy materials is expanded from the high entropy alloy to the fields of oxide, nitride, boride, carbide and the like. The preparation method of the high-entropy material comprises conventional solid phase sintering (Conventional Sintering, CS), spark plasma sintering (Spark Plasma Sintering, SPS), flash sintering (Flash Sintering FS) and the like. However, these preparation methods require a relatively high temperature, and the preparation temperature exceeds 1000 ℃, so that the equipment and process used for the preparation are required to be high.
Volatile Organic Compounds (VOCs) are air pollutants that have a boiling point between 50-260 ℃ at standard atmospheric pressure. VOCs not only have toxicity andcarcinogenesis, also causes environmental damage to ozone voids, and more seriously, by contamination with other air pollutants (NO x And SO x ) Chemical smog is formed after the reaction, the human health is threatened, and irreversible damage can be caused to the human body after the chemical smog is exposed to VOCs for a long time. The catalytic oxidation method can oxidize VOCs into carbon dioxide, water and other substances which have no pollution to the environment at a low temperature (200-500 ℃ or even lower) with high efficiency and high selectivity. Efforts have been made to develop effective VOCs catalytic oxidation catalysts, wherein metal oxides have been widely used as promising candidate catalysts. However, existing metal oxide catalysts are inefficient in treating contaminated gases containing a variety of VOCs. This is because a single metal oxide catalyst generally contains two to three metal components which have catalytic combustion activity only for a few VOCs, so that the existing metal oxide catalyst cannot have efficient processing ability for complex VOCs mixture. The high-entropy catalyst contains five or more metal elements, can provide more active sites, and is one of the most potential candidates for various catalysts.
Disclosure of Invention
The invention aims to provide a low-temperature preparation method and application of a high-entropy two-dimensional catalyst, so as to solve the problem of overhigh temperature required by the preparation of a high-entropy material by the existing process.
The invention is realized in the following way: a low-temperature preparation method of a high-entropy two-dimensional catalyst specifically uses PVP as a template, a precursor is obtained through a freeze drying technology, and then a two-dimensional high-specific-surface-area high-entropy oxide catalyst is obtained through low-temperature slow annealing of air.
Referring to fig. 1, the preparation of the universal high-entropy two-dimensional nano-sheet catalyst provided by the invention comprises the following steps:
1) A certain amount of PVP (polyvinylpyrrolidone) and a plurality of metal salts are dissolved in deionized water and stirred uniformly to form a mixed solution.
2) Pouring the mixed solution obtained in the step 1) into liquid nitrogen, and freeze-drying for 48 hours in a freeze dryer to obtain a catalyst precursor (the catalyst precursor becomes solid).
3) And (3) placing the precursor in the step (2) into a muffle furnace, heating to 100 ℃ for 6 hours at a heating rate of 1 ℃/min in an air environment, heating to 200 ℃ for 4 hours, and heating to 450 ℃ for 12 hours.
Further, the metal salt in the step 1) is a target metal ion, and is selected from five or more than five of Pt, pd, eu, gd, au, ir, ag, rh, ni, cr, zn, ga, mo, tb, dy, ru, in, sn, hf, ta, W, ce, cu, pm, sm, ho, er, tm, yb, lu, tl, pb, mg, al, mn, fe, co, zr, Y, ce, la metal ions, and the metal salt in the step 1) is nitrate, acetate, chloride or sulfate.
The invention discloses a method for preparing a two-dimensional nano sheet-shaped high-entropy catalyst, which has adjustable components, uniform element distribution and single-phase nano sheet-shaped morphology.
The invention further discloses a method for preparing six-membered MgAlFe (ZrY) by using the template method 2 Pt 0.5 O 12 High-entropy nano-sheet and six-element Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 High-entropy nano sheet and ten-membered MgAlCaCuMnCoZrYCeLaO 14 High entropy nanoplatelets. The invention further discloses MgAlFe (ZrY) 2 Pt 0.5 O 12 The high entropy nano-sheet is applied to methylcyclohexane dehydrogenation, specifically, methylcyclohexane solution is loaded into a reaction device through argon, and hydrogen production performance is tested through heating. The invention further discloses Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The high-entropy two-dimensional catalyst is applied to catalytic combustion of various VOCs gases, and specifically, in nitrogen-oxygen mixed gas, catalytic activity is tested through heating. The results show that Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The catalytic combustion of toluene, formaldehyde, acetone and chlorobenzene has better performance and selectivity.
The invention has the following advantages:
1) The highest temperature of the method for preparing the high-entropy two-dimensional catalyst is only 450 ℃, so that the preparation temperature of the high-entropy material is greatly reduced.
2) The equipment for preparing the high-entropy two-dimensional catalyst only needs a freeze dryer and a muffle furnace, and has the advantages of simple equipment and low cost compared with other high-temperature smelting equipment for preparing high-entropy materials.
3) The preparation process of the invention does not need water washing, can prepare pure high-entropy material, and is environment-friendly.
4) The template method provided by the invention has expansibility in combination with a freeze-drying technology, can synthesize binary or more two-dimensional nano sheets, can synthesize five-membered or more high-entropy two-dimensional catalysts, and provides a new thought for synthesizing the high-entropy catalysts.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention.
FIG. 2 shows MgAlFe (ZrY) obtained in example 1 2 Pt 0.5 O 12 And (5) structural characterization and morphological characterization.
FIG. 3 shows MgAlFe (ZrY) obtained in example 1 2 Pt 0.5 O 12 Morphology and elemental distribution map of (a).
FIG. 4 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 Is characterized by the structure and the appearance of the steel.
FIG. 5 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 Is a pattern of elements of the pattern.
FIG. 6 is MgAlCaCuMnCoZrYCeLaO obtained in example 3 14 Morphology characterization of (c).
FIG. 7 is MgAlCaCuMnCoZrYCeLaO obtained in example 3 14 Is a pattern of elements of the pattern.
FIG. 8 shows MgAlFe (ZrY) obtained in example 1 2 Pt 0.5 O 12 Is a graph of thermocatalytic methylcyclohexane dehydrogenation performance.
FIG. 9 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The thermal catalytic toluene catalytic combustion performance diagram of (2).
FIG. 10 is an implementationCe obtained in case 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The thermal catalytic formaldehyde catalytic combustion performance diagram.
FIG. 11 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 Is a graph of the thermal catalytic combustion performance of the thermocatalytic acetone.
FIG. 12 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The thermal catalytic chlorobenzene catalytic combustion performance graph.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to examples.
Example 1
High entropy MgAlFe (ZrY) 2 Pt 0.5 O 12 The synthesis of the vitamin nano-sheet catalyst comprises the following steps:
(1) 1g PVP was dissolved in 10mL water and stirred for 30min.
(2) To the PVP aqueous solution, 0.1mmol of Mg, 0.1mmol of Al, 0.1mmol of Fe nitrate, 0.2mmol of Zr, 0.2mmol of Y nitrate, 0.05mmol of hexachloroplatinic acid were added, and the mixture was stirred and dissolved for 30 minutes.
(3) The solution is frozen by liquid nitrogen and put into a freeze dryer for freeze drying for 48 hours.
(4) The dried powder is placed in a muffle furnace, and is heated to 100 ℃ for 6 hours at a heating rate of 1 ℃/min under the air environment, then heated to 200 ℃ for 4 hours, and then heated to 450 ℃ for 12 hours. Naturally cooling, and taking out the sample for characterization. FIG. 2a is MgAlFe (ZrY) 2 Pt 0.5 O 12 FIG. 2b is an X-ray diffraction pattern of MgAlFe (ZrY) 2 Pt 0.5 O 12 FIG. 3 is a topography of MgAlFe (ZrY) 2 Pt 0.5 O 12 Is a topography and elemental distribution map.
Example 2
High entropy Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The two-dimensional nano-sheet catalyst is synthesized by the following steps:
(1) 2g PVP was dissolved in 20mL water and stirred for 30min.
(2) To the PVP aqueous solution, 0.1mmol Cu, 0.1mmol Mn, 0.1mmol Co nitrate, 0.05mmol Zr, 0.05mmol La nitrate, 0.3mmol Ce nitrate were added and dissolved by stirring for 30min.
(3) The solution is frozen by liquid nitrogen and put into a freeze dryer for freeze drying for 48 hours.
(4) The dried powder was placed in a muffle furnace and heated to 100 c for 6 hours at a heating rate of 1 c/min in an air atmosphere, then heated to 200 c for 4 hours, then heated to 450 c for 12 hours. Naturally cooling, and taking out the sample for characterization. FIG. 4a is Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 FIG. 4b is a view showing the X-ray diffraction pattern of Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 FIG. 4c shows the adsorption and desorption graph of Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 FIG. 4d is a topographical view of Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 Is a high resolution image of (a). FIG. 5 is Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 Is a pattern of elements of the pattern.
Example 3
With reference to the method described in example 2, the metal salt in this example is Mg, al, ca, cu, mn, co, zr, Y, ce, la nitrate, and the other conditions are the same as in example 2, and MgAlCaCuMnCoZrYCeLaO is obtained 14 Ten-element high-entropy two-dimensional nano-sheets. FIG. 6 is MgAlCaCuMnCoZrYCeLaO 14 FIG. 7 is a morphology and high resolution of MgAlCaCuMnCoZrYCeLaO 14 Is a pattern of elements of the pattern.
Example 4
MgAlFe (ZrY) obtained in example 1 2 Pt 0.5 O 12 20mg of the catalyst was placed in a quartz tube and then placed in a tube furnace. Argon was passed through the methylcyclohexane solution at an argon flow rate of 50mL/min and then injected into the reaction system to start the reaction. After each temperature point was kept for 30 minutes, the gas composition was detected by a gas chromatograph. The properties tested are shown in FIG. 8, mgAlFe (ZrY) at 300 ℃ 2 Pt 0.5 O 12 Is 8.7 times that of Pt/C and 45.9 times that of Pt/C at 350 ℃.
Example 5
Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 200mg of the catalyst was placed in a quartz tube and then placed in a tube furnace. The raw material gas is dry clean air (21% O) 2 +79％N 2 ) 50mL/min of the feed gas was passed through a saturated solution of toluene, and then injected into the reaction system to start the reaction. After each temperature point was kept for 30 minutes, the gas composition was detected by a gas chromatograph. The performance of the test is shown in FIG. 9, and the handling performance of the catalytic combustion of p-toluene at 300℃reaches about 55mmol g -1 h -1 The selectivity to carbon dioxide was 100%.
Example 6
Referring to example 5, the solutions were changed to formaldehyde, acetone, chlorobenzene solutions, and the respective tests of thermocatalytic combustion were performed. The tested performance is shown in fig. 10, 11 and 12, and shows better performance and high selectivity.
In general, the invention discloses a universal method for preparing a high-entropy two-dimensional nano catalyst by using PVP as a template, which can be used for dehydrogenating methylcyclohexane and also can be applied to catalytic combustion of various VOCs gases, and provides a new idea for preparing a multifunctional catalyst.
While specific embodiments of the invention have been described in detail in connection with the examples, it should not be construed as limiting the scope of protection of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (5)
1. The low-temperature preparation method of the high-entropy two-dimensional catalyst is characterized by comprising the following steps of:
a. PVP and at least five metal salts are dissolved in deionized water and stirred uniformly to form a mixed solution;
b. c, freezing the mixed solution in the step a by liquid nitrogen, and putting the mixed solution into a freeze dryer for freeze drying to obtain a catalyst precursor;
c. c, putting the catalyst precursor obtained in the step b into a muffle furnace, and annealing in an air environment to obtain a high-entropy two-dimensional catalyst;
in the step c, the specific annealing process is as follows: heating to 100 ℃ at a heating rate of 1 ℃/min to keep 6h, then heating to 200 ℃ to keep 4h, and then heating to 450 ℃ to keep 12 h;
the high-entropy two-dimensional catalyst obtained in the step c is of a single-phase structure;
the metal ions in the metal salt in step a are selected from Pt, pd, au, ir, ag, ni, ru, ce, cu, mg, al, mn, fe, co, zr, Y, la.
2. The method for preparing a high-entropy two-dimensional catalyst at low temperature according to claim 1, wherein in the step b, the freeze-drying time is 48 hours.
3. The method for preparing the high-entropy two-dimensional catalyst according to claim 1, wherein the metal salt is one or more of nitrate, acetate, chloride and sulfate.
4. The low-temperature preparation method of the high-entropy two-dimensional catalyst according to claim 1, wherein the specific surface area of the high-entropy two-dimensional catalyst obtained in the step c is 30-300 m 2 g -1 。
5. The application of the high-entropy two-dimensional catalyst prepared by the method of any one of claims 1-4 as a catalyst for dehydrogenation of methylcyclohexane and catalytic combustion of volatile organic compounds, wherein the volatile organic compounds are one or more of formaldehyde, toluene, chlorobenzene and acetone.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017011893A1 (en) * | 2017-12-21 | 2019-06-27 | Forschungszentrum Jülich GmbH | Particle-reinforced high-temperature material |
| CN110234431A (en) * | 2017-01-31 | 2019-09-13 | 科莱恩产品（德国）有限公司 | Specific surface area and the higher synthesis by the active MoVNbTe catalyst that oxidative dehydrogenation of ethane is ethylene with increase |
| WO2021128282A1 (en) * | 2019-12-27 | 2021-07-01 | 江南大学 | Iron-cobalt-nickel-copper-based high-entropy alloy water electrolysis catalytic material and preparation method therefor |
| CN113244907A (en) * | 2021-04-19 | 2021-08-13 | 润和催化材料(浙江)有限公司 | Rare earth metal modification-based low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN113649022A (en) * | 2021-10-20 | 2021-11-16 | 天津环科环境咨询有限公司 | Catalyst for catalytic combustion of organic volatile waste gas and preparation method thereof |
-
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- 2022-06-06 CN CN202210631332.4A patent/CN114950475B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110234431A (en) * | 2017-01-31 | 2019-09-13 | 科莱恩产品（德国）有限公司 | Specific surface area and the higher synthesis by the active MoVNbTe catalyst that oxidative dehydrogenation of ethane is ethylene with increase |
| DE102017011893A1 (en) * | 2017-12-21 | 2019-06-27 | Forschungszentrum Jülich GmbH | Particle-reinforced high-temperature material |
| WO2021128282A1 (en) * | 2019-12-27 | 2021-07-01 | 江南大学 | Iron-cobalt-nickel-copper-based high-entropy alloy water electrolysis catalytic material and preparation method therefor |
| CN113244907A (en) * | 2021-04-19 | 2021-08-13 | 润和催化材料(浙江)有限公司 | Rare earth metal modification-based low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN113649022A (en) * | 2021-10-20 | 2021-11-16 | 天津环科环境咨询有限公司 | Catalyst for catalytic combustion of organic volatile waste gas and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Sewage-free preparation of 2D metal oxides by a rapid freezing soft template method for extraordinarily activating solar-driven humidity VOC combustion";Dachao Yuan et al.;《Catal. Sci. Technol》;第11卷;第2456页 * |
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