CN114950475A - 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 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 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
- 238000010438 heat treatment Methods 0.000 claims description 18
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 12
- 239000012855 volatile organic compound Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
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- 238000003756 stirring Methods 0.000 claims description 3
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- 229910052775 Thulium Inorganic materials 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 10
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
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- 238000001308 synthesis method Methods 0.000 abstract 1
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- 239000000243 solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
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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 4
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract
The invention provides a low-temperature preparation method and application of a high-entropy two-dimensional catalyst. The invention utilizes polyvinylpyrrolidone as a template, metal salt as a precursor, and forms uniform two-dimensional nanosheets by freeze drying technology and air annealing. Utilizing Ce prepared in the examples of the invention 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The high-entropy catalyst can catalyze toluene, formaldehyde, acetone and chlorobenzene to be combusted in a high-selectivity and high-efficiency manner; the advantage that the diversity of the components of the high-entropy catalyst can promote various catalytic reactions is shown. The high-entropy two-dimensional method provided by the inventionThe synthesis method of the catalyst has the advantages of low preparation temperature, universality, simplicity, feasibility, simple equipment, environmental friendliness and the like, and provides a new way and a new idea for applying the high-entropy material to 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
High-entropy materials (HEA) are solid solutions with higher entropy formed from five or more elements (5% -35% molar amounts of each element). 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 shown by the high-entropy alloy causes the worldwide research hot trend of the high-entropy material, and the research range of the high-entropy material 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 Sintering (CS) of a solid phase, Spark Plasma Sintering (SPS), Flash Sintering (FS), and the like. However, these preparation methods require high temperature, and the preparation temperature exceeds 1000 ℃, so the requirements on the equipment and process used for preparation are high.
Volatile Organic Compounds (VOCs) are a class of air pollutants that have a boiling point between 50-260 c at normal atmospheric pressure. VOCs not only have toxic and carcinogenic effects, but also cause environmental damage through ozone cavitation, and more seriously, through interaction with other airborne pollutants (NO) x And SO x ) Chemical smog is formed after the reaction, the health of human beings is threatened, and irreversible damage can be caused to the human bodies after long-time exposure in VOCs gas. The catalytic oxidation method can oxidize VOCs into substances which are free from environmental pollution, such as carbon dioxide, water and the like, with high efficiency and high selectivity at lower temperature (200-500 ℃ or even lower). Efforts have been directed to the development of effective catalytic oxidation catalysts for VOCs, wherein metal oxides have been widely used as promising candidate catalysts. However, existing metal oxide catalysts are inefficient at treating contaminated gases containing a variety of VOCs. This is because a single metal oxide catalyst generally contains two to three metal components that are catalytically active for combustion of only a few VOCs, and thus, the existing metal oxide catalysts cannot effectively treat complex mixtures of VOCs. The high-entropy catalyst contains five or more metal elements, can provide more active sites, and is one of the most potential candidates of 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 that the temperature required by the existing process for preparing a high-entropy material is too high.
The invention is realized by the following steps: a low-temperature preparation method of a high-entropy two-dimensional catalyst specifically comprises the steps of using PVP as a template, obtaining a precursor through a freeze-drying technology, and then obtaining the two-dimensional high-entropy oxide catalyst with a large specific surface area through low-temperature and slow-speed annealing of air.
With reference to fig. 1, the preparation of a universal high-entropy two-dimensional nanosheet catalyst provided by the present invention comprises the following steps:
1) dissolving a certain amount of PVP (polyvinylpyrrolidone) and various metal salts in deionized water, and uniformly stirring to form a mixed solution.
2) Pouring the mixed solution obtained in the step 1) into liquid nitrogen, and putting the liquid nitrogen into a freeze dryer for freeze drying for 48 hours to obtain a catalyst precursor (the catalyst precursor becomes a solid).
3) Putting the precursor in the step 2) into a muffle furnace, heating to 100 ℃ at a heating rate of 1 ℃/min in the air environment, keeping the temperature for 6h, then heating to 200 ℃ and keeping the temperature for 4h, and heating to 450 ℃ and keeping the temperature for 12 h.
Further, the metal salt In step 1) is a target metal ion, and is selected from five or more 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 step 1) is a nitrate, acetate, chloride, sulfate, or the like.
The invention discloses a method for preparing a two-dimensional nano flaky high-entropy catalyst, which has the characteristics of adjustable components, uniform element distribution, single phase and nano flaky morphology.
The invention further discloses a method for preparing hexahydric MgAlFe (ZrY) by utilizing a template method 2 Pt 0.5 O 12 High-entropy nanosheet and hexahydric Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 High entropy nano-sheet and ten-element MgAlCaCuMnCoZrYCeLaO 14 High entropy nano-sheet. The invention further discloses MgAlFe (ZrY) 2 Pt 0.5 O 12 The high-entropy nanosheet is applied to methyl cyclohexane dehydrogenation, specifically, a methyl cyclohexane solution is loaded into a reaction device through argon, and the 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, catalytic activity is tested by heating in a nitrogen-oxygen mixed gas. The results show that Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The catalytic combustion of the toluene, formaldehyde, acetone and chlorobenzene has better performance and selectivity.
The invention has the following advantages:
1) the method for preparing the high-entropy two-dimensional catalyst has the highest temperature of only 450 ℃, and greatly reduces the preparation temperature of the high-entropy material.
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 materials, and is environment-friendly.
4) The template method provided by the invention has expansibility by combining with a freeze drying technology, can synthesize binary or more two-dimensional nanosheets, can synthesize more than five-membered high-entropy two-dimensional catalysts, and provides a new idea for the synthesis of 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 structural characterization and morphology characterization.
FIG. 3 shows MgAlFe (ZrY) obtained in example 1 2 Pt 0.5 O 12 The morphology and the elemental distribution map.
FIG. 4 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 And (4) characterizing the structure and the appearance.
FIG. 5 is an embodimentCe obtained in case 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 Element distribution map of (c).
FIG. 6 shows MgAlCaCuMnCoZrYCeLaO obtained in example 3 14 The morphology of (2) is characterized.
FIG. 7 shows MgAlCaCuMnCoZrYCeLaO obtained in example 3 14 Element distribution map of (c).
FIG. 8 shows MgAlFe (ZrY) obtained in example 1 2 Pt 0.5 O 12 Thermal catalytic methylcyclohexane dehydrogenation performance diagram.
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.
FIG. 10 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The thermal catalysis formaldehyde catalytic combustion performance diagram.
FIG. 11 shows Ce obtained in example 2 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The thermal catalysis acetone catalytic combustion performance diagram.
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 diagram.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
Example 1
High entropy MgAlFe (ZrY) 2 Pt 0.5 O 12 The synthesis of the nano-sheet catalyst comprises the following steps:
(1) 1g PVP was dissolved in 10mL water and stirred for 30 min.
(2) 0.1mmol of Mg, 0.1mmol of Al, 0.1mmol of Fe nitrate, 0.2mmol of Zr, 0.2mmol of Y nitrate and 0.05mmol of chloroplatinic acid hexahydrate are added into PVP aqueous solution, and stirred and dissolved for 30 min.
(3) Freezing the solution with liquid nitrogen, and freeze-drying in a freeze-dryer for 48 h.
(4) The dried powder was placed in a muffle furnace,heating to 100 deg.C at a heating rate of 1 deg.C/min in air environment for 6h, heating to 200 deg.C for 4h, and heating to 450 deg.C for 12 h. And naturally cooling, and taking out a sample for characterization. FIG. 2a is MgAlFe (ZrY) 2 Pt 0.5 O 12 FIG. 2b is MgAlFe (ZrY) 2 Pt 0.5 O 12 FIG. 3 is MgAlFe (ZrY) 2 Pt 0.5 O 12 The topographic map and the elemental distribution map.
Example 2
High entropy of Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 The synthesis of the two-dimensional nanosheet catalyst comprises the following steps:
(1) 2g PVP was dissolved in 20mL water and stirred for 30 min.
(2) 0.1mmol of Cu, 0.1mmol of Mn, 0.1mmol of Co nitrate, 0.05mmol of Zr, 0.05mmol of La nitrate and 0.3mmol of Ce nitrate were added to the PVP aqueous solution, and the mixture was dissolved by stirring for 30 min.
(3) Freezing the solution with liquid nitrogen, and freeze-drying in a freeze dryer for 48 h.
(4) And putting the dried powder into a muffle furnace, heating to 100 ℃ at a heating rate of 1 ℃/min in the air environment for 6 hours, then heating to 200 ℃ for 4 hours, and then heating to 450 ℃ for 12 hours. And naturally cooling, and taking out a sample for characterization. FIG. 4a is Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 X-ray diffraction pattern of (5), FIG. 4b is Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 FIG. 4c is a graph showing the adsorption and desorption of Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 FIG. 4d is a graph of Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 High resolution of (2). FIG. 5 is Ce 3 CuMnCoLa 0.5 Zr 0.5 O 12.25 Element distribution map of (c).
Example 3
Referring to the method of example 2, the metal salts in this example are nitrates of Mg, Al, Ca, Cu, Mn, Co, Zr, Y, Ce, La, and under the same conditions as in example 2, MgAlCaMnCoZrYCeLaO is obtained 14 The ten-element high-entropy two-dimensional nanosheet. FIG. 6 is MgAlCaCuMnCoZrYCeLaO 14 The morphology and high resolution of (1), FIG. 7 is MgAlCaCuMnCoZrYCeLaO 14 Element distribution map of (c).
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, and an argon flow rate of 50mL/min was then injected into the reaction system to start the reaction. And (3) preserving the heat of each temperature point for 30min, and detecting gas components by a gas chromatograph. The measured properties are shown in FIG. 8, MgAlFe (ZrY) at 300 ℃ 2 Pt 0.5 O 12 The performance of (2) 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 raw material gas was passed through a saturated solution of toluene and then injected into the reaction system to start the reaction. And (3) preserving the heat of each temperature point for 30min, and detecting gas components by a gas chromatograph. The tested properties are shown in FIG. 9, and the treatment performance of catalytic combustion of toluene at 300 ℃ reaches about 55mmol g -1 h -1 The selectivity to carbon dioxide was 100%.
Example 6
Referring to example 5, the solution was changed to formaldehyde, acetone, chlorobenzene solution, and the thermal catalytic combustion test was performed. The tested performances are shown in fig. 10, fig. 11 and fig. 12, and show better performance and high selectivity.
Generally speaking, 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 methyl cyclohexane dehydrogenation and catalytic combustion of various VOCs gases, and provides a new idea for preparation of multifunctional catalysts.
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (8)
1. A low-temperature preparation method of a high-entropy two-dimensional catalyst is characterized by comprising the following steps:
a. dissolving PVP and at least five metal salts in deionized water, and uniformly stirring to form a mixed solution;
b. b, pouring the mixed solution obtained in the step a into liquid nitrogen, and putting the mixed solution into a freeze dryer for freeze drying to obtain a catalyst precursor;
c. and c, putting the catalyst precursor obtained in the step b into a muffle furnace, and annealing in the air environment to obtain the high-entropy two-dimensional catalyst.
2. The low-temperature preparation method of the high-entropy two-dimensional catalyst according to claim 1, wherein in the step c, the annealing specifically comprises the following steps: heating to 100 deg.C at a heating rate of 1 deg.C/min for 6h, heating to 200 deg.C for 4h, and heating to 450 deg.C for 12 h.
3. The method for preparing the high-entropy two-dimensional catalyst at low temperature according to claim 1, wherein in the step b, the freeze-drying time is 48 hours.
4. The method for preparing the high-entropy two-dimensional catalyst at low temperature according to claim 1, wherein the metal ions In the metal salt are selected from 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 and La.
5. The low-temperature preparation method of the high-entropy two-dimensional catalyst according to claim 1, wherein the metal salt is one or more of nitrate, acetate, chloride and sulfate.
6. The low-temperature preparation method of the high-entropy two-dimensional catalyst according to claim 1, wherein the high-entropy two-dimensional catalyst obtained in the step c has a single-phase structure.
7. 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 。
8. Use of the high-entropy two-dimensional catalyst prepared by the method of any one of claims 1 to 7 as a catalyst for dehydrogenation of methylcyclohexane and catalytic combustion of volatile organic compounds.
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