CN113996341A - Catalyst material, preparation method and application thereof - Google Patents
Catalyst material, preparation method and application thereof Download PDFInfo
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- CN113996341A CN113996341A CN202111436132.5A CN202111436132A CN113996341A CN 113996341 A CN113996341 A CN 113996341A CN 202111436132 A CN202111436132 A CN 202111436132A CN 113996341 A CN113996341 A CN 113996341A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 83
- 230000003197 catalytic effect Effects 0.000 claims abstract description 78
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000012855 volatile organic compound Substances 0.000 claims description 34
- 239000002131 composite material Substances 0.000 claims description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 28
- 150000004706 metal oxides Chemical class 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
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- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 5
- 150000002823 nitrates Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 5
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 230000002860 competitive effect Effects 0.000 abstract description 5
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- 230000002401 inhibitory effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 230000006872 improvement Effects 0.000 description 6
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- 230000001699 photocatalysis Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- -1 siloxanes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000005051 trimethylchlorosilane 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/83—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 rare earths or actinides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
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- B01D2257/708—Volatile organic compounds V.O.C.'s
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Abstract
The invention provides a catalyst material, a preparation method and application thereof. The catalyst material comprises a core containing a hydrophobic component and a shell layer coating the core, wherein the shell layer contains a perovskite catalytic material, and the chemical formula of the catalyst material is LaMyFe(1‑y)O3-R/Ce-M-Zr, wherein M comprises any one or a combination of two or more of Mn, Fe, Co, Ni, R is a hydrophobic component, y is 0-1; the hydrophobic component has a hydrophobic group, and the hydrophobic group is exposed on the surface of the catalyst material. The catalyst material provided by the invention has a special core-shell structure, the active component coats the hydrophobic component, and the low surface energy group is exposed by rearrangementOn the surface of the catalyst, the catalyst has good hydrophobicity, thereby inhibiting competitive adsorption of water vapor and reactants on the surface of the catalyst material and being beneficial to improving the catalytic efficiency of the catalyst material.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a catalyst material, and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) are a class of important pollutants discharged in the industrial production process, and seriously affect the natural environment and the human health. The method is one of important treatment means for catalytically decomposing VOCs into harmless components such as carbon dioxide, water and the like by using a catalyst and then discharging the harmless components, and the perovskite composite oxide is a typical VOCs decomposition catalyst. However, besides VOCs, the exhaust gas often contains moisture, and the catalytic decomposition of VOCs also generates moisture. The water vapor is easy to generate competitive adsorption with reactants on the surface of the catalyst, so that the number of active sites is reduced, and the catalytic reaction is not facilitated. In addition, the perovskite catalyst has small specific surface area, and the direct popularization and application of the perovskite catalyst in the field of practical engineering are limited.
The hydrophobic property of the catalyst is improved, so that the competitive adsorption of water vapor and reactants on the surface of the catalyst can be effectively inhibited. The study conditions of the hydrophobic catalyst in multiple fields are reviewed by the Husheng et al, the importance of development and application of the hydrophobic catalyst is explained, and the preparation process of the hydrophobic catalyst and the improvement of the catalytic performance of the catalyst on specific reactions are pointed out as main research directions. Lu Yi pavilion improves the hydrophobic property of the VOCs catalyst from the aspects of improving the silicon-aluminum ratio of the framework of the molecular sieve and improving the surface functional groups, but the process for improving the silicon-aluminum ratio of the framework of the molecular sieve is complicated, and the framework of the molecular sieve is easy to collapse, so that the specific surface area of the catalyst is reduced, and the pore structure is damaged; the improvement of the surface functional group is realized by introducing methyl through trimethylchlorosilane, although the initial hydrophobic effect is obtained, the methyl is used as a component in the VOCs catalyst, and because the catalyst has the performance of catalytically decomposing organic matters, the methyl with modified surface is easily oxidized and decomposed by the catalyst in actual operation, so that the hydrophobicity is lost. The case of the surface modification of a material surface from a superhydrophobic surface to a hydrophilic surface by photocatalytic decomposition of the surface-modified alkyl group is reported in hyacinolone et al. In addition, methyl is adsorbed on the surface of the catalyst and also occupies an adsorption site; low molecular siloxanes are also susceptible to volatilization at high temperatures resulting in loss of hydrophobicity. Therefore, the hydrophobic scheme design and the realization of the lasting hydrophobic effect aiming at specific reaction are also very important.
Perovskite catalysisThe preparation has the advantages of low price, flexible and changeable composition and the like, and becomes a research hotspot in the fields of thermal catalytic oxidation, battery materials, photocatalysis and the like. In the catalytic oxidation reaction of VOCs, the perovskite catalyst has better catalytic oxidation activity, but has a certain gap compared with the noble metal catalyst, and the improvement of the specific surface area of the catalyst is one of the main research directions of the application of the perovskite catalyst. The perovskite/oxide composite catalyst is prepared by modifying a perovskite catalyst by using an oxide. Chua super et al reported a supported combustion catalyst La0.8Ce0.2CoO3/Ce0.8Zr0.2O2LaCo is prepared from Chinese patent CN107983361A applied in Liuchangdong, etc(1-y)MnyO3/CeO2-ZrO2In the composite catalyst, the oxide and the perovskite component generate a certain synergistic effect, and the dispersity is improved, so that the improvement of the catalytic performance is promoted. However, in the above preparation method, the oxide and the perovskite component are difficult to be combined at a molecular level, and the improvement of the catalytic performance is limited. In the perovskite/oxide composite catalyst prepared by Chinese patent CN109364915A applied by Limon and the like and Chinese patent CN103182308A applied by Yunning and the like, the oxide is perovskite (ABO)3) The selective exposure of the corresponding oxide is realized through proper excess of the A-site or B-site element precursor of the oxide of the medium A-site or B-site element, the molecular-level combination of the oxide and the perovskite is realized, and the promotion of the catalytic performance is facilitated. It is generally believed that the B-site metal plays a major role in catalytic performance. However, this method cannot achieve improvement in the specific surface area of the perovskite catalyst, and the kind of the oxide bonded to the perovskite is limited.
In conclusion, the catalyst material prepared in the prior art has poor hydrophobicity durability and stability, the adsorption position occupied by the hydrophobic group influences the catalytic efficiency, and the dispersibility is poor and the specific surface area is small, so that the catalytic efficiency is further reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst material, a preparation method and application thereof.
In a first aspect, the present invention provides a catalyst materialThe catalyst material comprises a core containing a hydrophobic component and a shell layer coating the core, the shell layer contains a perovskite catalytic material, and the chemical formula of the catalyst material is LaMyFe(1-y)O3-R/Ce-M-Zr, wherein M comprises any one or a combination of two or more of Mn, Fe, Co, Ni, R is a hydrophobic component, y is 0-1; the hydrophobic component has a hydrophobic group, and the hydrophobic group is exposed on the surface of the catalyst material.
In some preferred embodiments, the hydrophobic component has a fluorine-containing group, and further, the hydrophobic component includes a fluorosilane and/or a fluorocarbon material.
In some preferred embodiments, the catalyst material further comprises a support, wherein a core-shell structure formed by the core and the shell layer is attached to the surface of the support; the catalyst material also comprises a multi-element metal oxide which is attached to the surface of the carrier together with the core-shell structure, and the multi-element metal oxide at least comprises a metal element M.
In a second aspect, the present invention provides a method for preparing a catalyst material, comprising:
providing a perovskite catalytic material; carrying out hydrophobic modification on the perovskite catalytic material by using a hydrophobic component to prepare a hydrophobic modified composite material of a perovskite coated hydrophobic component and a core-shell structure; providing a multi-metal oxide sol; and uniformly mixing the hydrophobic modified composite material with the multi-element metal oxide sol, applying the obtained slurry on a carrier, and sintering at high temperature to obtain the catalyst material.
In some preferred embodiments, the above method specifically comprises:
ultrasonically dispersing a perovskite catalytic material in a dispersion solvent to form a perovskite dispersion liquid; and dropwise adding the hydrophobic component into the perovskite dispersion liquid, stirring, and adding a catalytic substance to perform condensation reaction between the hydrophobic component and hydroxyl on the surface of the perovskite to obtain the hydrophobic modified composite material.
Furthermore, the mass ratio of the perovskite catalyst to the hydrophobic component is 1: 0.01-1: 0.3.
Further, the condensation reaction is carried out at the temperature of 30-70 ℃ for 0.5-10 h.
Further, the hydrophobic composition component comprises a fluorine-containing compound, and further comprises one or more of heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane and fluorine-containing polysilsesquioxane.
In a third aspect, the invention provides an application of the catalyst material in the field of catalytic decomposition of VOCs.
Further, the catalytic decomposition of VOCs comprises:
providing a VOCs decomposition catalyst comprising the above catalyst material;
and (3) fully contacting the gas to be treated possibly containing VOCs with the VOCs decomposition catalyst to realize the decomposition of the VOCs.
By adopting the technical scheme, the invention at least has the following beneficial effects
1. The invention provides a catalyst material, which is beneficial to the promotion of catalytic performance and the reduction of cost due to the special structural design: the catalyst has a special core-shell structure, the active component coats the hydrophobic component, and the low-surface-energy group is exposed on the surface of the catalyst through rearrangement, so that the catalyst has good hydrophobicity, the competitive adsorption of water vapor and reactants on the surface of the catalyst material is inhibited, and the catalytic efficiency of the catalyst material in an environment containing water is improved; hydrophobic substances are taken as cores, so that adsorption sites on the outer surface of the shell layer of the catalyst cannot be occupied, and hydrophobic groups have small steric hindrance, so that the diffusion, adsorption and desorption processes of reactants cannot be influenced, and the catalytic efficiency of the catalyst material is further improved; the catalyst is taken as a shell layer and is a typical porous hollow structure, so that the use amount of catalytic materials is saved, and the preparation cost of the catalyst materials is favorably reduced.
2. The catalyst material provided by the invention has lasting hydrophobicity: firstly, the hydrophobic substance is a core, and the structure of the shell part limits the thermal operation of molecules of the hydrophobic substance, inhibits the volatilization of the hydrophobic substance at high temperature and improves the thermal stability of the hydrophobic substance; secondly, the hydrophobic group is connected with the inner core part through chemical bonds, so that the bonding strength of the hydrophobic group is enhanced, and the durability of the hydrophobic ability is facilitated.
3. According to the catalyst material provided by the invention, the perovskite catalyst material and the multi-element metal oxide have synergistic effect, so that the catalytic performance is improved: the large specific surface area of the multi-element metal oxide improves the dispersion degree of the perovskite catalytic material and increases the catalytic active sites; the multi-element metal oxide and the perovskite catalytic material both contain the same metal elements, so that the multi-element metal oxide and the perovskite catalytic material achieve molecular-level chemical combination, and the doping effect causes lattice change, thereby being beneficial to improving the oxygen mobility and further improving the catalytic efficiency; and the perovskite catalytic material and the multi-element metal oxide are dispersed on the surface of the porous carrier, so that the specific surface area is large, and the catalytic efficiency is improved.
4. The preparation method of the catalyst material provided by the invention has the advantages that the used raw materials are easy to obtain, the preparation method is simple, and no pollutant is discharged in the preparation process.
In conclusion, the catalyst material, the preparation method and the application thereof provided by the invention solve the problems that the catalyst material prepared by the prior art is poor in hydrophobicity durability and stability, the hydrophobic groups occupy adsorption positions to influence the catalytic efficiency, and the catalytic efficiency is further reduced due to poor dispersibility and small specific surface area.
The above description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood and can be implemented according to the content of the description, the following detailed description is given with reference to the preferred embodiments of the present invention.
Drawings
FIG. 1 is a schematic diagram of the structure of a catalyst material in an exemplary embodiment of the present invention;
fig. 2 is an enlarged schematic view of a portion of the structure of a catalyst material in accordance with an exemplary embodiment of the present invention.
Wherein, 1, nucleus; 2. a shell layer; 3. a hydrophobic group; 4. a carrier; 5. an effective catalytic component.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the examples of the present invention, the raw materials and chemicals used are commercially available unless otherwise specified.
Referring to fig. 1, the present embodiment provides a catalyst material including a core 1 including a hydrophobic component and a shell layer 2 covering the core 1, the shell layer 2 including a perovskite catalytic material, and the catalyst material having a chemical formula represented by LaMyFe(1-y)O3-R/Ce-M-Zr, wherein M comprises any one or a combination of two or more of Mn, Fe, Co, Ni, R is a hydrophobic component, y is 0-1; the hydrophobic component has a hydrophobic group, and the hydrophobic group is exposed on the surface of the catalyst material.
In some embodiments, the hydrophobic component has a fluorine-containing group, preferably comprising fluorosilane and/or fluorocarbon materials.
Further, the shell layer 2 has a porous structure; further, the thickness of the shell layer 2 is 10-100 nm.
In some embodiments, the catalyst material further comprises a support 4, and the core-shell structure formed by the core 1 and the shell layer 2 is attached to the surface of the support 4.
Further, the carrier 4 comprises a porous material.
Further, the porous material includes cordierite, but is not limited thereto.
Further, the catalyst material also comprises a multi-element metal oxide which is attached to the surface of the carrier together with the core-shell structure, wherein the multi-element metal oxide at least comprises a metal element M;
further, the mass ratio of the perovskite catalytic material to the multi-element metal oxide is 1.5-2.5: 1.
The embodiment of the application also provides a preparation method of the catalyst material, which comprises the following steps: providing a perovskite catalytic material; carrying out hydrophobic modification on the perovskite catalytic material by using a hydrophobic component to prepare a hydrophobic modified composite material of a perovskite coated hydrophobic component and a core-shell structure; providing a multi-metal oxide sol; and uniformly mixing the hydrophobic modified composite material with the multi-element metal oxide sol, applying the obtained slurry on a carrier, and sintering at high temperature to obtain the catalyst material.
Fig. 2 is a schematic cross-sectional view showing a partial surface structure of the catalyst material, wherein the effective catalytic component 5 includes a core-shell structure and a multi-component metal oxide, and the effective catalytic component 5 is tightly bonded to the surface of the carrier 4 by sintering.
In some embodiments, the method may specifically comprise: ultrasonically dispersing a perovskite catalytic material in a dispersion solvent to form a perovskite dispersion liquid; and dropwise adding the hydrophobic component into the perovskite dispersion liquid at a dropwise adding rate of 25-35 drops/minute, stirring, and adding a catalytic substance to perform condensation reaction between the hydrophobic component and hydroxyl on the surface of the perovskite to obtain the hydrophobic modified composite material.
Furthermore, the mass ratio of the perovskite catalyst to the hydrophobic component is 1: 0.01-1: 0.3.
Further, the condensation reaction is carried out at the temperature of 30-70 ℃ for 0.5-10 h.
Further, the hydrophobic composition component comprises a fluorine-containing compound, and further, the fluorine-containing compound comprises one or more of heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane, fluorine-containing polysilsesquioxane and the like, but is not limited thereto.
Further, the dispersion solvent includes one or a combination of two or more of acetone, water, and ethanol, but is not limited thereto.
Further, the catalytic material includes an organic carboxylic acid, and is more preferably one or a combination of two or more of acetic acid, citric acid, and maleic acid, but is not limited thereto.
In some embodiments, the method may further comprise: providing a La-containing precursor, an M-containing precursor and an Fe-containing precursor, wherein M comprises any one or the combination of more than two of Mn, Fe, Co and Ni; and mixing the La precursor, the precursor containing M and the precursor containing Fe with water, adding a complexing agent for reaction, drying the obtained reaction product, and then performing high-temperature sintering treatment to obtain the perovskite catalytic material.
Further, the La-containing precursor, the M-containing precursor and the Fe-containing precursor include nitrates or acetates of corresponding metal elements.
Further, the complexing agent includes citric acid, but is not limited thereto.
Furthermore, the molar ratio of the sum of the M element and the Fe element to the La element is 1: 1.3-1: 1.
Further, the molar ratio of the M element to the Fe element is 1: 0-0: 1; the mol ratio of the complexing agent to the sum of La, M and Fe elements is 0.8-1.3.
Further, the reaction temperature is 40-80 ℃ and the reaction time is 0.5-10 h.
Furthermore, the temperature of the high-temperature sintering treatment is 500-1000 ℃, and the time is 0.5-10 h.
Further, the drying temperature is 100-150 ℃, and the drying time is 0.5-10 h.
In some embodiments, the method may further comprise: and mixing the Ce-containing precursor, the Zr-containing precursor and the M-containing precursor with water, and then adding a complexing agent for reaction to prepare the multi-element metal oxide sol.
Further, the Ce-containing precursor, the Zr-containing precursor, and the M-containing precursor include nitrates or acetates of corresponding metal elements.
Furthermore, the molar ratio of the total of Ce element and Zr element to M element is 1: 0.1-1: 0.6.
Furthermore, the molar ratio of the Ce element to the Zr element is 1: 2.5-3.5.
Furthermore, the addition amount of the complexing agent is 0.8-1.3 times of the total molar weight of the Ce, Zr and M elements.
Further, the reaction temperature is 40-80 ℃ and the reaction time is 0.5-10 h.
In some embodiments, the method may further comprise:
adding the hydrophobic modified composite material into the multi-element metal oxide sol, and uniformly stirring to obtain slurry; and soaking the carrier 4 in the slurry, blowing off the slurry remained in the pore channel of the carrier 4 by using compressed air, drying, and sintering at high temperature to obtain the catalyst material.
Further, the soaking time is 1-60 s.
Furthermore, the compressed air purging pressure is 0.2-0.8MPa, and the purging time is 1-10 s.
Further, the drying temperature is 100-150 ℃, and the drying time is 0.5-10 h.
Further, the temperature of the high-temperature sintering is 400-700 ℃, and the time is 0.5-10 h.
The embodiment of the application also provides application of the catalyst material in the field of VOCs catalytic decomposition.
Further, another aspect of the embodiments of the present invention provides a method for catalytic decomposition of VOCs, including: providing a VOCs decomposition catalyst comprising the above catalyst material; and (3) fully contacting the gas to be treated possibly containing VOCs with the VOCs decomposition catalyst to realize the decomposition of the VOCs.
The present invention is further illustrated by the following examples and figures, but it should not be construed that the scope of the subject matter set forth herein is limited to the examples set forth below. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1
Perovskite catalytic material (LaCo)yFe(1-y)O3) Preparation of
Is prepared by a citric acid complexation method. Weighing precursors of La, Co and Fe in proportion, adding the precursors into water, adding a certain amount of citric acid, uniformly stirring, keeping a certain temperature for reaction under stirring, drying a reaction product, and increasing the content of the dried reaction productThe catalytic material (LaCo) is obtained after the warm sinteringyFe(1-y)O3)。
Wherein, the precursors of La, Co and Fe are nitrates or acetates of corresponding metals; la element: the molar ratio of the (Co + Fe) elements is 1: 1.1; co element: the mol ratio of Fe element is 1: 0.2; the amount of citric acid is 1.1 times of the mole number of the metal elements, the reaction temperature is 50 ℃, and the reaction time is 2 hours; the drying temperature is 120 ℃, and the drying time is 3 hours; the sintering temperature is 800 ℃, and the sintering time is 3 h.
Example 2
Perovskite catalytic material (LaCo)yFe(1-y)O3) By hydrophobic modification of
The perovskite catalytic material provided in the embodiment 1 is placed in acetone, ultrasonically dispersed, a hydrophobic component is dropwise added into a perovskite dispersion liquid, the addition amount of the hydrophobic component is controlled, stirring is continued, acetic acid is added as a catalyst, so that the hydrophobic component and hydroxyl on the surface of the perovskite catalytic material are subjected to condensation reaction, and the hydrophobic modified composite material with the perovskite-coated hydrophobic modified component and the core-shell structure is obtained.
Wherein the hydrophobic component is a fluorine-containing compound, specifically one or more of heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane (PFOTES, the same below) and fluorine-containing polysilsesquioxane; the mass ratio of the perovskite catalyst to the hydrophobic component is 1: 0.05; the condensation reaction temperature is 50 ℃, and the condensation reaction time is 0.5 h.
Example 3
Preparation of a Multi-Metal oxide Sol
Is prepared by a citric acid complexation method. Weighing precursors of Ce, Zr and M according to a proportion, adding the precursors into water, adding a certain amount of citric acid, uniformly stirring, keeping a certain temperature under stirring for reaction to obtain a multi-element metal oxide sol, and cooling the sol for later use.
In this embodiment, the metal element M is Co.
Wherein, the precursors of Ce, Zr and M are nitrates or acetates of corresponding metals; the molar ratio of the (Ce + Zr) element to the M element is 1: 0.1; the molar ratio of Ce element to zr element is 1: 3; the amount of citric acid is 1.1 times of the mole number of the metal elements; the reaction temperature is 50 ℃ and the reaction time is 2 h.
Example 4
Preparation of catalyst materials
The hydrophobically modified catalyst material provided in example 2 was added to the multi-component oxide sol provided in example 3, and stirred uniformly to obtain a mixed slurry. And (3) putting the cordierite carrier 4 into the mixed slurry for dip-coating, blowing off redundant slurry in the pore channel of the cordierite carrier 4 by using compressed air, drying, and then sintering at high temperature to obtain a finished product of the catalyst material.
Those skilled in the art can appropriately select a suitable coating method according to the actual situation, and it is understood that the scope of the present invention is not limited by the preferred embodiments of the specific examples, which are subject to the claims.
Wherein, the dip-coating time is 5s, the compressed air purging pressure is 0.3MPa, and the purging time is 3 s; the drying temperature is 120 ℃, and the drying time is 3 hours; the sintering temperature is 500 ℃, and the sintering time is 3 h.
Example 5
Catalytic composite material: LaCo0.8Fe0.4O3-PFOTES/Ce0.2-Co0.2-Zr0.6Preparation of
The preferred catalytic composite described above was carried out using the preparation scheme provided in examples 1-4:
LaCo0.8Fe0.4O3-PFOTES/Ce0.2-Co0.2-Zr0.6the specific preparation process is not described herein again.
Wherein, when the hydrophobic modification is carried out, the hydrophobic compound is tridecafluorooctyltriethoxysilane (PFOTES).
Example 6
The preparation of the catalytic composite was substantially the same as the preparation procedure provided in examples 1-4, with the following differences:
perovskite catalytic material (LaCo)yFe(1-y)O3) In the preparation, the molar ratio of the La element to the (Co + Fe) element is 1: 1(ii) a The molar ratio of Co element to Fe element is 0.5: 1; the amount of citric acid is 0.8 times of the mole number of the metal elements, the reaction temperature is 80 ℃, and the reaction time is 10 hours; the drying temperature is 150 ℃, and the drying time is 10 hours; the sintering temperature is 500 ℃, and the sintering time is 10 hours;
when hydrophobic modification is carried out, the mass ratio of the perovskite catalyst to the hydrophobic component is 1: 0.25; the condensation reaction temperature is 70 ℃, and the condensation reaction time is 10 hours;
when the multi-element metal oxide sol is prepared, the molar ratio of (Ce + Zr) element to M element is 1: 0.6; the molar ratio of Ce element to Zr element is 1: 3.5; the amount of citric acid is 0.8 times of the mole number of the metal elements; the reaction temperature is 80 ℃, and the reaction time is 10 hours;
when the catalyst material is prepared, the dip-coating time is 60s, the compressed air purging pressure is 0.8MPa, and the purging time is 10 s; the drying temperature is 150 ℃, and the drying time is 0.5 h; the sintering temperature is 700 ℃, and the sintering time is 10 hours;
the catalytic composite material with similar catalytic effect can be successfully prepared.
Example 7
The preparation of the catalytic composite was essentially the same as in example 6, with the following differences:
perovskite catalytic material (LaCo)yFe(1-y)O3) When the preparation is carried out, the molar ratio of the La element to the (Co + Fe) element is 1: 1.3; the molar ratio of Co element to Fe element is 0.2: 1; the amount of citric acid is 1.3 times of the mole number of the metal elements, the reaction temperature is 40 ℃, and the reaction time is 0.5 h; the drying temperature is 100 ℃, and the drying time is 0.5 h; the sintering temperature is 1000 ℃, and the sintering time is 0.5 h;
when hydrophobic modification is carried out, the mass ratio of the perovskite catalyst to the hydrophobic component is 1: 0.01; the condensation reaction temperature is 30 ℃, and the condensation reaction time is 0.5 h;
when the multi-element metal oxide sol is prepared, the molar ratio of (Ce + Zr) element to M element is 1: 0.1; the mol ratio of Ce element to Zr element is 1: 2.5; the amount of citric acid is 1.3 times of the mole number of the metal elements; the reaction temperature is 40 ℃, and the reaction time is 0.5 h;
when the catalyst material is prepared, the dip-coating time is 1s, the compressed air purging pressure is 0.2MPa, and the purging time is 1 s; the drying temperature is 100 ℃, and the drying time is 10 hours; the sintering temperature is 400 ℃, and the sintering time is 0.5 h;
the catalytic composite material with similar catalytic effect can also be successfully prepared.
Example 8
Catalytic composite material: LaCo0.8Fe0.4O3-PFOTES/Ce0.2-Co0.2-Zr0.6Application of catalyzing VOCs oxidative decomposition
Using the catalytic composite described above as provided in example 5: LaCo0.8Fe0.4O3-PFOTES/Ce0.2-Co0.2-Zr0.6Catalyzing to carry out oxidative decomposition on VOCs, using toluene as probe molecules, and ensuring that the space velocity is 10000h-1The catalytic oxidation reaction was carried out under the conditions of an oxygen content of the gas of 21% and a relative humidity of the gas of 50% (wet state), and the reaction temperature corresponding to a conversion of toluene of 90%, i.e., T90, was monitored. Meanwhile, the performance (dry state) of the catalyst when no water was contained in the contaminated gas, T90, was tested for comparison.
The catalytic composite of this example had a wet T90 of 296 ℃ and a dry T90 of 274 ℃.
Comparative example 1
Application of catalytic composite material without hydrophobic modification in catalyzing oxidative decomposition of VOCs (volatile organic compounds)
Using catalytic composite material (LaCo) without hydrophobic modification0.8Fe0.4O3/Ce0.2-Co0.2-Zr0.6The same procedure as in example 5 except that hydrophobic modification was not performed) was used to catalyze oxidative decomposition of VOCs, and dry-wet T90 was tested using the same test method as in example 8.
The catalytic composite of this comparative example, which was not hydrophobically modified, had a wet T90 of 327 ℃ and a dry T90 of 269 ℃.
And (4) analyzing a comparison result:
it will be clear from the foregoing examples and comparative examples that the present invention provides catalytic composites, in particularPreferred catalytic composites: LaCo0.8Fe0.4O3-PFOTES/Ce0.2-Co0.2-Zr0.6When VOCs are catalyzed to be subjected to oxidative decomposition, dry T90 is close to dry T90 of a catalytic composite material which is not subjected to hydrophobic modification, which indicates that the steric hindrance effect of a hydrophobic group 3 is small, and the hydrophobic group hardly has negative influence on the catalytic efficiency; the wet T90 is obviously lower than the wet T90 of the catalytic composite material which is not subjected to hydrophobic modification, which shows that the hydrophobic groups can obviously reduce competitive adsorption of water and improve the catalytic efficiency in the wet state.
In addition, the catalyst material of the invention can be applied to the fields of hydrogen-water liquid phase catalytic exchange, hydrogen-oxygen recombination, selective catalytic reduction of nitrogen-containing oxides, treatment of ammonia-containing wastewater, treatment of VOCs-containing wastewater, photocatalysis or adsorption enrichment and the like through proper modification or processing.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A catalyst material comprising a core comprising a hydrophobic component and a shell layer surrounding the core, the shell layer comprising a perovskite catalytic material, the catalyst material having the formula LaMyFe(1-y)O3-R/Ce-M-Zr, wherein M comprises any one or a combination of two or more of Mn, Fe, Co, Ni, R is a hydrophobic component, y is 0-1;
the hydrophobic component has a hydrophobic group, and the hydrophobic group is exposed on the surface of the catalyst material.
2. The catalyst material of claim 1, wherein:
the hydrophobic component has fluorine-containing groups, preferably comprising fluorosilanes and/or fluorocarbon materials.
3. The catalyst material of claim 1, wherein: the shell layer has a porous structure; and/or the thickness of the shell layer is 10-100 nm.
4. A catalyst material according to claim 1, characterized in that: the catalyst material also comprises a carrier, and a core-shell structure formed by the core and the shell layer is attached to the surface of the carrier;
preferably, the carrier comprises cordierite;
and/or the catalyst material comprises a multi-element metal oxide which is attached to the surface of the carrier together with the core-shell structure, wherein the multi-element metal oxide at least comprises a metal element M;
preferably, the mass ratio of the perovskite catalytic material to the multi-element metal oxide is 1.5-2.5: 1.
5. The method of preparing the catalyst material of any one of claims 1 to 4, comprising:
providing a perovskite catalytic material;
carrying out hydrophobic modification on the perovskite catalytic material by using a hydrophobic component to prepare a hydrophobic modified composite material of a perovskite coated hydrophobic component and a core-shell structure;
providing a multi-metal oxide sol;
and uniformly mixing the hydrophobic modified composite material with the multi-element metal oxide sol, applying the obtained slurry on a carrier, and sintering at high temperature to obtain the catalyst material.
6. The preparation method according to claim 5, which specifically comprises:
ultrasonically dispersing a perovskite catalytic material in a dispersion solvent to form a perovskite dispersion liquid;
dripping the hydrophobic component into the perovskite dispersion liquid at a dripping rate of 25-35 drops/minute, stirring, and adding a catalytic substance to enable the hydrophobic component and hydroxyl on the surface of the perovskite to perform condensation reaction to prepare the hydrophobic modified composite material;
preferably, the mass ratio of the perovskite catalyst to the hydrophobic component is 1: 0.01-1: 0.3;
preferably, the condensation reaction is carried out at the temperature of 30-70 ℃ for 0.5-10 h;
and/or the hydrophobic component comprises a fluorine-containing compound, preferably, the fluorine-containing compound comprises one or more of heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane and fluorine-containing polysilsesquioxane;
and/or the dispersing solvent comprises one or the combination of more than two of acetone, water and ethanol;
and/or the catalytic substance comprises organic carboxylic acid, preferably one or the combination of more than two of acetic acid, citric acid and maleic acid.
7. The preparation method according to claim 5, which specifically comprises:
mixing a Ce-containing precursor, a Zr-containing precursor and an M-containing precursor with water, and then adding a complexing agent for reaction to prepare a multi-element metal oxide sol;
preferably, the Ce-containing precursor, the Zr-containing precursor and the M-containing precursor include nitrates or acetates of corresponding metal elements;
preferably, the molar ratio of the total of Ce element and Zr element to M element is 1: 0.1-1: 0.6,
preferably, the molar ratio of the Ce element to the Zr element is 1: 2.5-1: 3.5;
preferably, the addition amount of the complexing agent is 0.8-1.3 times of the total molar weight of Ce, Zr and M;
preferably, the reaction temperature is 40-80 ℃ and the reaction time is 0.5-10 h.
8. The preparation method according to claim 5, which specifically comprises:
adding the hydrophobic modified composite material into the multi-element metal oxide sol, and uniformly stirring to obtain slurry;
and soaking the carrier in the slurry, blowing off the slurry remained in the carrier pore channel by using compressed air, drying, and then sintering at high temperature to obtain the catalyst material.
9. The method of claim 8, wherein:
the soaking time is 1-60 s; and/or the compressed air purging pressure is 0.2-0.8MPa, and the purging time is 1-10 s; and/or the drying temperature is 100-150 ℃, and the drying time is 0.5-10 h; and/or the temperature of the high-temperature sintering is 400-700 ℃, and the time is 0.5-10 h.
10. Use of the catalyst material of any one of claims 1 to 9 in the field of catalytic decomposition of VOCs;
preferably, the catalytic decomposition of VOCs comprises:
providing a VOCs decomposition catalyst comprising the catalyst material of any one of claims 1-9;
and (3) fully contacting the gas to be treated possibly containing VOCs with the VOCs decomposition catalyst to realize the decomposition of the VOCs.
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