CN118002119A - Preparation method and application of Pt-MnO2 catalyst - Google Patents
Preparation method and application of Pt-MnO2 catalyst Download PDFInfo
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- CN118002119A CN118002119A CN202311362421.4A CN202311362421A CN118002119A CN 118002119 A CN118002119 A CN 118002119A CN 202311362421 A CN202311362421 A CN 202311362421A CN 118002119 A CN118002119 A CN 118002119A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000376 reactant Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses a preparation method and application of a Pt-MnO2 catalyst, which belong to the technical field of catalyst preparation, and comprise the following steps of S1, dissolving Mn (CH 3COO)2·4H2 O) in glycol to form mixed salt solution, S2, preparing Na 2CO3 aqueous solution mixed with H 2PtCl6·6H2 O, S3, adding Na 2CO3 aqueous solution of step S2 into the mixed salt solution to obtain reaction solution, S4, heating the reaction solution to 140-180 ℃ and stirring for 1-3 hours to obtain reactant precipitate, S5, cleaning the reactant precipitate and drying the reactant precipitate at 50-70 ℃, and S6, calcining the reactant precipitate at 300-450 ℃ to obtain the Pt-MnO 2 catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a Pt-MnO2 catalyst.
Background
Volatile Organic Compounds (VOCs) are key intermediates for secondary organic aerosols and photochemical smog, which pose serious threats to the atmospheric environment and human health. At present, various methods for removing VOC in industrial waste gas are adopted, and noble metal supported catalyst catalytic combustion is generally adopted, so that the method has the advantages of high oxidation activity, low operation temperature, strong regeneration capacity and the like, and is also considered as a very promising method for removing VOC in industrial waste gas.
However, this method has problems in that the noble metal is expensive and scarce, and cannot be used on a large scale in industrial applications, and in order to improve the catalytic performance of the noble metal-supported catalyst, further reduction of the load is required to achieve cost-effectiveness and wider applicability, so that it is necessary to improve the catalytic performance of the noble metal-supported catalyst.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a Pt-MnO2 catalyst.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of Pt-MnO 2 catalyst comprises the following steps,
S1, dissolving Mn (CH 3COO)2·4H2 O in ethylene glycol to form mixed salt solution;
S2, preparing Na 2CO3 aqueous solution mixed with H 2PtCl6·6H2 O;
s3, adding the Na 2CO3 aqueous solution obtained in the step S2 into the mixed salt solution to obtain a reaction solution;
S4, heating the reaction solution to 140-180 ℃, stirring, and keeping for 1-3 hours to obtain reactant precipitate;
s5, cleaning the reaction precipitate, and drying at 50-70 ℃;
S6, precipitating the reactant, and calcining at 300-450 ℃ to obtain the Pt-MnO 2 catalyst
Further, in the step S1, mn (CH 3COO)2·4H2 O is dissolved in ethylene glycol at a temperature of 30 to 80 degrees celsius, and stirred under a protective atmosphere of nitrogen.
Further, in the step S3, the Na 2CO3 aqueous solution is added dropwise to the mixed salt solution.
Further, in the step S3, the pH of the reaction solution is maintained between 9 and 11.
In step S4, the reaction solution is heated in a protective atmosphere, and the protective atmosphere is nitrogen.
Further, in the step S5, the reactant precipitate is washed with water 3 times and then with alcohol 3 times.
Further, in the step S6, the calcination time for reactant precipitation is 3-5 hours, and the platinum loading of the Pt-MnO 2 catalyst is 0.09-0.34 wt%.
Further, a Pt-MnO 2 catalyst is used for catalytic oxidation of toluene.
The invention has the beneficial effects that:
1. The invention prepares the Pt supported MnO 2 catalyst by a one-step precipitation method, the method enhances the strong metal carrier interaction (SMSI) between Pt and MnO 2 carriers, can induce more Pt 0 and Mn +3 to be used for oxygen adsorption and activation, and enhances the capability of activating toluene by higher Mn +4/Mn+3 ratio. And the oxygen vacancies on the surface of MnO 2 can induce more active oxygen to be generated, the active oxygen can effectively migrate to the surface active site to replace the oxygen consumed by the surface, the catalytic activity is improved, the capability of desorbing CO 2 is enhanced, and the stability and the toluene catalytic activity are improved.
2. According to the preparation method disclosed by the invention, the consumption of the ethylene glycol used as the solvent is not limited, and the metal precursor in the solution can be fully dissolved.
3. The catalyst prepared by the invention has the advantages of uniform distribution, low load capacity, simple operation and easy preparation.
4. The preparation method has the advantages of simple process, mild condition, quick deposition, good controllability of the morphology and the size of the product, good dispersity of noble metal Pt, strong interaction between Pt and MnO 2 carriers, good repeatability and low cost, and is particularly suitable for catalyzing and oxidizing toluene.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
In order to make the objects, technical solutions and advantageous effects of the present invention clearer, the present invention provides the following drawings for explanation:
FIG. 1 is an XRD pattern for a 0.23wt% Pt-MnO 2 catalyst.
FIG. 2 is a Scanning Electron Microscope (SEM) image of 0.23wt% Pt-MnO 2 catalyst.
FIG. 3 shows toluene conversion at CO 2 mineralization for a 0.23wt% Pt-MnO 2 catalyst.
Detailed Description
Preparation method of Pt-MnO2 catalyst
S1, adding 2.8185gMn (CH 3COO)2·4H2 O and 50ml of ethylene glycol into a three-necked flask under the nitrogen atmosphere, and stirring for 10 minutes at 50 ℃ to completely dissolve the two to form mixed salt solution;
S2, preparing Na 2CO3 aqueous solution mixed with H 2PtCl6·6H2 O;
s3, dropwise adding 665uL of Na 2CO3 aqueous solution into the mixed salt solution to obtain a reaction solution with the pH value of 10;
S4, heating the reaction solution to 160 ℃, and continuously stirring for 2 hours in a nitrogen atmosphere to obtain reactant precipitation;
S5, washing the reactant precipitate with water for 3 times, washing with alcohol for 3 times, and placing the reactant precipitate in a vacuum drying oven to be dried at a constant temperature of 60 ℃ overnight;
And S6, placing the dried reactant precipitate in a muffle furnace, and calcining at 450 ℃ for 4 hours to obtain the Pt-MnO 2 catalyst.
Testing and analysis:
And carrying out noble metal loading test on the prepared Pt-MnO 2 catalyst: the test results showed that the loading of noble metal was 0.23wt%.
FIG. 1 is an XRD pattern for a 0.23wt% Pt supported MnO2 catalyst.
XRD pattern analysis thereof: the samples had distinct diffraction peaks at 12.8 °, 18.1 °, 28.8 °, 37.5 °, 41.9 ° and 49.8 °, which are related to the (110), (200), (310), (211), (301) and (411) crystal planes of spinel MnO 2 (JCPDS No. 44-0141). No diffraction peak corresponding to Pt or PtO X was observed in XRD, which means that Pt was highly dispersed and/or loaded on MnO 2 support at low levels.
FIG. 2 is an SEM image of a 0.23wt% Pt supported MnO2 catalyst.
SEM image analysis thereof: to understand the size of the catalyst, the catalyst was tested by Scanning Electron Microscopy (SEM), and it was clearly observed that the particle-like (100-200 nm) MnO 2 had a uniform morphology.
Toluene catalytic combustion performance test of Pt-MnO 2 metal oxide catalyst:
0.1g of Pt-MnO2 catalyst was mixed with 0.3g of quartz sand, and a toluene catalytic combustion test was performed in a continuous flow fixed bed quartz microreactor (tube diameter=6mm).
As shown in FIG. 3, the catalyst reached a temperature of 180℃for 90% conversion under 1000ppm and 20000mL/g h test conditions (T90), and a CO 2 mineralization rate of 182℃superior to the Pt-supported metal oxide catalysts reported so far.
The reason is that: 1. the preparation method of the application enhances the interaction (SMSI) of the strong metal carrier, can induce more Pt 0 and Mn +3 to be used for oxygen adsorption and activation, has higher Mn 4+/Mn+3 proportion, and improves the capability of activating toluene; 2. oxygen vacancies on the surface of the carrier can induce more active oxygen to be generated, active oxygen can effectively migrate to surface active sites to replace oxygen consumed by the surface, and desorption of CO 2 on the surface is enhanced, so that the stability and toluene degradation activity of the catalyst are improved.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that those skilled in the art will be understood that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a Pt-MnO 2 catalyst is characterized by comprising the following steps: comprises the steps of,
S1, dissolving Mn (CH 3COO)2·4H2 O in ethylene glycol to form mixed salt solution;
S2, preparing Na 2CO3 aqueous solution mixed with H 2PtCl6·6H2 O;
s3, adding the Na 2CO3 aqueous solution obtained in the step S2 into the mixed salt solution to obtain a reaction solution;
S4, heating the reaction solution to 140-180 ℃, stirring, and keeping for 1-3 hours to obtain reactant precipitate;
s5, cleaning the reaction precipitate, and drying at 50-70 ℃;
s6, precipitating the reactant, and calcining at 300-450 ℃ to obtain the Pt-MnO 2 catalyst.
2. The method for preparing the Pt-MnO 2 catalyst according to claim 1, wherein the method comprises the following steps: in the step S1, mn (CH 3COO)2·4H2 O is dissolved in glycol at 30-80 ℃, and is stirred under the protection atmosphere condition, wherein the protection atmosphere is nitrogen.
3. The method for preparing the Pt-MnO 2 catalyst according to claim 1, wherein the method comprises the following steps: in the step S3, the Na 2CO3 aqueous solution is added dropwise to the mixed salt solution.
4. A method for preparing a Pt-MnO 2 catalyst according to claim 1 or 3, characterized in that: in the step S3, the pH value of the reaction solution is kept between 9 and 11.
5. The method for preparing the Pt-MnO 2 catalyst according to claim 1, wherein the method comprises the following steps: in the step S4, the reaction solution is heated in a protective atmosphere, and the protective atmosphere is nitrogen.
6. The method for preparing the Pt-MnO 2 catalyst according to claim 1, wherein the method comprises the following steps: in the step S5, the reactant precipitate is washed with water for 3 times and then with alcohol for 3 times.
7. The method for preparing the Pt-MnO 2 catalyst according to claim 1, wherein the method comprises the following steps: in the step S6, the calcination time for reactant precipitation is 3-5 hours, and the platinum loading of the Pt-MnO 2 catalyst is 0.09-0.34 wt%.
8. A Pt-MnO 2 catalyst according to claim 7, for the catalytic oxidation of toluene.
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| CN202311362421.4A CN118002119A (en) | 2023-10-19 | 2023-10-19 | Preparation method and application of Pt-MnO2 catalyst |
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| CN202311362421.4A CN118002119A (en) | 2023-10-19 | 2023-10-19 | Preparation method and application of Pt-MnO2 catalyst |
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