CN114308031A - Perovskite type oxide material doped with noble metal and preparation method thereof - Google Patents
Perovskite type oxide material doped with noble metal and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 244000025254 Cannabis sativa Species 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 239000002086 nanomaterial Substances 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- 238000001354 calcination Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 11
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 230000010718 Oxidation Activity Effects 0.000 abstract description 3
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- 238000001179 sorption measurement Methods 0.000 abstract description 3
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- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- BIGXVYHHNTVTIZ-UHFFFAOYSA-N barium;oxoplatinum Chemical compound [Ba].[Pt]=O BIGXVYHHNTVTIZ-UHFFFAOYSA-N 0.000 description 2
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- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 241000380130 Ehrharta erecta Species 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 241001448530 Rohdea japonica Species 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- MEQJYARTTHUISP-UHFFFAOYSA-N barium(2+) oxygen(2-) platinum(2+) Chemical compound [Pt+2].[O-2].[Ba+2].[O-2] MEQJYARTTHUISP-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a perovskite type oxide material doped with noble metal and a preparation method thereof, the material is a metal oxide nano material with gold-vannamei grass shape and the surface exposed with the noble metal, the VOCs catalytic oxidation material applied by the invention is a perovskite type oxide material doped with the noble metal, and the chemical general formula of the material is Pt/LaMTiO3(M ═ Ca, Sr) due to perovskite ABO3In the configuration, AB site can replace the characteristic, Pt enters B site in S2) and Ba enters A site; the material has a flat surface and a pore channel, so that the specific surface area and potential VOCs adsorption sites are greatly improved; the material is subjected to hydrogen reduction, and a large number of Pt nanoclusters are exposed on the surface of the material, and the existence of the Pt nanoclusters enables the material to be used in the methodThe perovskite type oxide has extremely high catalytic oxidation activity, and has extremely high stability with six oxygen coordinated Pt, so that the problem of unstable activity of the noble metal catalyst at high temperature is solved.
Description
Technical Field
The invention relates to the field of preparation of environment and catalytic materials, in particular to a perovskite type oxide material doped with noble metal and a preparation method thereof.
Background
The atmospheric environment is closely related to happy life, and human activities include life and industrial emission of Volatile Organic Compounds (VOCs), Nitrogen Oxides (NO)x) Sulfur Oxide (SO)x) The current atmospheric environment is seriously influenced by greenhouse effect, haze, photochemical smog, ozone layer damage and the like caused by harmful gases. Volatile Organic Compounds (VOCs) are used as pollutants which are wide in range, various in variety and serious in pollution due to derivatives thereof, and the urban green sustainable development is seriously influenced. The current gaseous pollutant purification technology mainly comprises absorption adsorption, combustion, biological/membrane separation and catalytic oxidation, and the technology with the most development prospect and scale application under the large background of energy conservation and environmental protection belongs to the technology for purifying VOCs by the catalytic oxidation.
The catalyst design as a core problem in catalytic oxidation processes targets low complete conversion temperatures and high stability, and perovskite catalysts, noble metal catalysts, oxide catalysts and solid acid catalysts can be selected from a wide range of classifications.
The perovskite oxide is generally present in the form of ABO3Wherein A is rare earth metal with larger atomic radius and high-order alkaline earth metal, B is element with smaller atomic radius (usually transition metal with 3d and 4d orbitals) coordinated with six oxygen, and the whole body presents cubic or octahedral structure. Is widely favored by researchers because of its variable valence state, easy to adjust the redox properties of the material and naturally high structural stability, mainly having A according to different variable valence combinationsIBVO3、AIIBIVO3Or AIIIBIIIO3Configuration, and the substitutable property at position A, B allows it to be manipulated for corresponding dissociationThe oxidation-reduction performance is modulated by the valence state or oxygen vacancy.
In the modification and adjustment of perovskite type oxide, firstly attention is paid to the change of specific surface area, and LaFeO synthesized on the basis of SBA-15 by adopting a nano-casting method3The specific surface area can reach 158m2g-1(Journal of Materials Chemistry A,2014,2,17329) then supported perovskites such as 20 wt.% LaCoO have also been observed3/Ce0.9Zr0.1O2The activity is improved by utilizing the characteristics of the carrier through the interaction with the carrier (Applied Catalysis B: Environmental,2007,70(1-4): 400-405); how to maintain high stability while maintaining high activity remains a problem to be solved.
Disclosure of Invention
The present invention aims to overcome the drawbacks of the prior art by providing a noble metal-doped perovskite oxide material to solve the problems of the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a precious metal doped perovskite type oxide material is a metal oxide nano material with a gold wannian grass shape and with a surface exposed with precious metals, and the perovskite type is at least one of calcium titanate and strontium titanate; the noble metal is at least one of platinum, silver, palladium and gold.
Preferably, the metal compound in the material contains one of the metal elements of titanium, lanthanum and barium and calcium and strontium.
Preferably, the rohdea japonica shape is formed by adopting nano blades, the length of each nano blade is 50-200nm, and the width of each nano blade is 20-50 nm; the interior of the nano-leaf contains perovskite oxide and perovskite strontium oxide.
Preferably, the oxide substrate is a block having a diameter of 0.5 to 2 μm.
A preparation method of a perovskite type oxide material doped with noble metal comprises the following steps:
s1: mixing and grinding noble metal oxide and barium oxide to form uniform powder, and calcining at high temperature to form an oxide precursor for transferring noble metal;
s2: mixing the oxide precursor obtained in the step S1 with titanium oxide, calcium oxide/strontium oxide and lanthanum oxide, fully grinding, firstly calcining at high temperature in a muffle furnace, grinding and mixing again, and calcining in an oxygen atmosphere to obtain a noble metal B-site substituted perovskite oxide material;
s3: and (4) etching the perovskite oxide material obtained in the step (S2) for a period of time in an acid solution with a certain concentration and at a certain temperature, and washing and drying to obtain the precious metal doped perovskite oxide material.
Preferably, the barium oxide in S1 is barium carbonate with a purity of more than 99%.
Preferably, in the step S2, the mixing process is carried out by weighing according to a stoichiometric ratio, and grinding and mixing are carried out in an agate mortar; the muffle furnace calcination temperature is 1000 ℃; the oxygen atmosphere is pure oxygen environment; the oxygen atmosphere calcination was carried out at 1200 ℃.
Preferably, the etching process in S3 is performed in a nitric acid solution; the acid concentration is 1-10mol/L, the temperature is 10-90 ℃, and the time is 12-96 h.
Has the advantages that: the VOCs catalytic oxidation material is a perovskite type oxide material doped with noble metal, and the chemical general formula of the material is Pt/LaMTiO3(M ═ Ca, Sr) due to perovskite ABO3In the configuration, AB site can replace the characteristic, Pt enters B site in S2) and Ba enters A site; the material has a flat surface and a pore channel, so that the specific surface area and potential VOCs adsorption sites are greatly improved; the surface of the material is exposed with a large number of Pt nanoclusters after being reduced by hydrogen, the perovskite type oxide in the invention has extremely high catalytic oxidation activity due to the existence of the Pt nanoclusters, and meanwhile, the perovskite type oxide has extremely high stability with six oxygen coordinated Pt, so that the problem of unstable activity of a noble metal catalyst at high temperature is solved.
Drawings
The advantages and benefits of the described invention in the oxidation of VOCs will become apparent to those skilled in the art upon reading the following detailed description of the preferred embodiments. The drawings herein are for illustrative purposes only of the embodiments shown for ease of understanding and are not to be construed as limiting the invention.
In the drawings:
FIG. 1 is an X-ray crystal diffraction pattern of platinum barium oxide in an example of the present invention;
FIG. 2 is a field emission scanning electron micrograph of bulk Pt-doped perovskite oxide according to an embodiment of the present invention;
FIG. 3 is an X-ray crystal diffraction pattern of bulk Pt-doped perovskite oxide according to an embodiment of the present invention;
FIG. 4 is a field emission scanning electron micrograph of a Pt-exposed perovskite oxide according to an embodiment of the present invention;
FIG. 5 is an X-ray crystal diffraction pattern of a Pt-exposed perovskite oxide according to an embodiment of the present invention;
FIG. 6 is a graph of toluene oxidation activity curves for Pt-exposed perovskite oxides in test examples of the present invention.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly define the scope of the invention.
The invention provides a technical scheme that: a perovskite type oxide material doped with noble metals is a metal oxide nano material with gold-vannamei grass shape and with the surface exposed with the noble metals, and the perovskite type is at least one of calcium titanate and strontium titanate; the noble metal is at least one of platinum, silver, palladium and gold.
The metal compound in the material simultaneously contains titanium, lanthanum and barium metal elements and one metal element of calcium and strontium; the perennial grass shape is composed of nanometer leaves, the length of the nanometer leaves is 50-200nm, and the width of the nanometer leaves is 20-50 nm; the interior of the nano leaf contains perovskite lanthanum oxide and perovskite strontium oxide, and the interior of the nano leaf comprises at least one porous hollow nano prism of nickel-cobalt-based sulfide, nickel-cobalt-based phosphide or nickel-cobalt-based selenide, or a nickel/cobalt metal simple substance porous hollow nano prism, or a nickel-cobalt alloy porous hollow nano prism; the substrate of the oxide is a block with a diameter of 0.5-2 μm.
A preparation method of a perovskite type oxide material doped with noble metal comprises the following steps:
s1: mixing and grinding noble metal oxide and barium oxide to form uniform powder, and calcining at high temperature to form an oxide precursor for transferring noble metal;
s2: mixing the oxide precursor obtained in the step S1 with titanium oxide, calcium oxide/strontium oxide and lanthanum oxide, fully grinding, firstly calcining at high temperature in a muffle furnace, grinding and mixing again, and calcining in an oxygen atmosphere to obtain a noble metal B-site substituted perovskite oxide material;
s3: and (4) etching the perovskite oxide material obtained in the step (S2) for a period of time in an acid solution with a certain concentration and at a certain temperature, and washing and drying to obtain the precious metal doped perovskite oxide material.
For example: the material is a platinum-doped titanate material with a chemical general formula of Pt/LaMTiO3(M ═ Ca and Sr), the size of the titanate material is 300-1000nm, the titanate material has a pore structure, and the noble metal in the titanate is exposed on the surface of the perovskite.
A preparation method of a perovskite type oxide material doped with noble metal comprises the following steps:
s1: platinum oxide is used as a platinum source, and is fully ground and uniformly mixed with barium carbonate, and then solid-phase synthesis is adopted to prepare Ba by calcining at high temperature3Pt2O7(ii) a The material can be structurally decomposed into PtO2+Ba5Pt2O9The material carrying four non-equivalent Pt4+；
S2: lanthanum oxide, calcium carbonate/strontium carbonate, titanium oxide and Ba in S13Pt2O7The perovskite oxide Pt @ LaMTiO is prepared by the same solid phase synthesis method as the raw material3(M ═ Ca, Sr), obtaining a doped perovskite oxide of high crystallinity and high stability; the high-temperature calcination is carried out twice in the synthesis process, and grinding and mixing are carried out once in the synthesis process so as to improve the crystallinity and the surface flatness;
the perovskite type oxide is Pt @ LaCaTiO3、Pt@LaSrTiO3One of (1);
s3: with H2Reducing the material at high temperature under the atmosphere of hydrogen-argon mixture by using a reducing agent to obtain a noble metal doped perovskite type oxide material with noble metal exposed on the surface;
the noble metal doped perovskite type oxide material is Pt/LaCaTiO3、Pt/LaSrTiO3One kind of (1).
Example 1: with unequal coordination of Pt4+Preparation of barium platinum oxide
Anhydrous platinum oxide (molecular weight 227.08) and barium carbonate (molecular weight: 197.34, purity 99%) were mixed in a molar ratio of 2: 3, weighing, placing in a mortar, grinding for 1h under the condition of ethanol dispersion, and waiting for ethanol volatilization after no obvious color difference is observed. Placing the ground sample in a corundum crucible, calcining for 12h in a muffle furnace at 1000 ℃, and obtaining a product, namely platinum-bearing B3Pt2O7The width dimension of the barium platinum oxide precursor is about 1 μm, and the length dimension is about 3 μm; the XRD pattern is shown in figure 1.
Example 2: preparing a Pt-doped perovskite type oxide embedded at the B site;
lanthanum trioxide (molecular weight: 325.81, purity 99.99%), calcium carbonate (molecular weight: 100.09, purity 99%), strontium carbonate (molecular weight: 147.63, purity 99%), titanium dioxide (molecular weight: 79.9, purity 99%) were each baked at high temperature to completely remove moisture. Subsequently reacting the starting material with B3Pt2O7Weighing according to the stoichiometric ratio, placing the mixture in a mortar, grinding the mixture for 2 hours under the condition of acetone dispersion until the mixture is completely and uniformly mixed, and calcining the mixture for 12 hours in a muffle furnace at the temperature of 1000 ℃ after the acetone is completely volatilized. After the intermediate product is continuously ground once, 100ml/min pure oxygen is introduced into the tubular furnace as atmosphere, the temperature is raised to 1200 ℃, and the calcination is carried out for 12 hours. The product is the B-site embedded Pt doped perovskite oxide Pt @ LaMTiO3(M ═ Ca and Sr), as shown in FIG. 2, and as shown in FIG. 3, the XRD pattern showed a typical perovskite phase.
Example 3: preparing doped perovskite type oxide with Pt exposed on the surface;
a certain amount of the B-site embedded Pt doped perovskite oxide Pt @ LaMTiO synthesized in example 2 is taken3Weighing (M ═ Ca and Sr), placing in a beaker, dropwise adding a nitric acid solution with a certain concentration in a water bath environment at a certain temperature, standing for a period of time, washing and drying to obtain the perovskite oxide Pt/LaMTiO with the surface exposed with precious metals3(M ═ Ca and Sr), the scanning electron micrograph of which is shown in FIG. 4, and the X-ray crystal diffraction pattern thereof is shown in FIG. 5.
Test example 1: testing the toluene oxidation performance of the doped perovskite type oxide with Pt exposed on the surface;
the Pt-doped perovskite oxide material prepared in example 3 was subjected to tablet forming, particle size sieving and packing, respectively, and then tested for toluene catalytic oxidation performance in a mini fixed bed reactor. The test conditions were: 1000ppm toluene + 20% O2The balance gas is N2Mass airspeed of 30000mL g-1·L-1(ii) a The test results are shown in fig. 6.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (8)
1. A noble metal-doped perovskite-type oxide material, characterized in that: the material is a metal oxide nano material with the surface exposed with precious metal and in a gold wannian grass shape, and the perovskite type is at least one of calcium titanate and strontium titanate; the noble metal is at least one of platinum, silver, palladium and gold.
2. A noble metal-doped perovskite oxide material as claimed in claim 1, wherein: the metal compound in the material simultaneously contains titanium, lanthanum and barium metal elements and one metal element of calcium and strontium.
3. A noble metal-doped perovskite oxide material as claimed in claim 1, wherein: the Romannian grass shape is composed of nanometer blades, the length of each nanometer blade is 50-200nm, and the width of each nanometer blade is 20-50 nm; the interior of the nano-leaf contains perovskite oxide and perovskite strontium oxide.
4. A noble metal-doped perovskite oxide material as claimed in claim 1, wherein: the oxide has a bulk with a base diameter of 0.5-2 μm.
5. The method according to claim 1, wherein the perovskite oxide material is selected from the group consisting of: the method comprises the following steps:
s1: mixing and grinding noble metal oxide and barium oxide to form uniform powder, and calcining at high temperature to form an oxide precursor for transferring noble metal;
s2: mixing the oxide precursor obtained in the step S1 with titanium oxide, calcium oxide/strontium oxide and lanthanum oxide, fully grinding, firstly calcining at high temperature in a muffle furnace, grinding and mixing again, and calcining in an oxygen atmosphere to obtain a noble metal B-site substituted perovskite oxide material;
s3: and (4) etching the perovskite oxide material obtained in the step (S2) for a period of time in an acid solution with a certain concentration and at a certain temperature, and washing and drying to obtain the precious metal doped perovskite oxide material.
6. The method according to claim 5, wherein: the barium oxide in the S1 is barium carbonate with the purity higher than 99%.
7. The method according to claim 5, wherein: weighing in the mixing process of S2 according to the stoichiometric ratio, and grinding and mixing in an agate mortar; the muffle furnace calcination temperature is 1000 ℃; the oxygen atmosphere is pure oxygen environment; the oxygen atmosphere calcination was carried out at 1200 ℃.
8. The method according to claim 5, wherein: the etching process in the S3 is carried out in a nitric acid solution; the acid concentration is 1-10mol/L, the temperature is 10-90 ℃, and the time is 12-96 h.
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