CN114950572B - Supported catalyst for efficiently removing formaldehyde at room temperature and preparation method and application thereof - Google Patents
Supported catalyst for efficiently removing formaldehyde at room temperature and preparation method and application thereof Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims description 46
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 20
- 229960005070 ascorbic acid Drugs 0.000 claims description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims description 19
- 239000011668 ascorbic acid Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229940099596 manganese sulfate Drugs 0.000 claims description 14
- 239000011702 manganese sulphate Substances 0.000 claims description 14
- 235000007079 manganese sulphate Nutrition 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004809 Teflon Substances 0.000 claims description 5
- 229920006362 Teflon® Polymers 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 9
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- 230000015572 biosynthetic process Effects 0.000 abstract description 4
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- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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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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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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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- Health & Medical Sciences (AREA)
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Abstract
The invention belongs to the field of catalysts and environmental catalysis, and particularly relates to a supported catalyst for efficiently removing formaldehyde at room temperature, and a preparation method and application thereof. The invention firstly prepares delta-MnO 2 Then using anti-cyclohaemacid to treat delta-MnO 2 Pretreatment is carried out to lead the surface to carry out charge transfer process, and delta-MnO is carried out 2 Surface formation of sufficient amount of Mn 3+ Defective sites for anchoring platinum atoms, prepared in delta-MnO 2 The catalyst is a catalyst with platinum atoms supported on a carrier and is used as a material capable of efficiently catalyzing and decomposing formaldehyde at room temperature. Under the conditions of 25 ℃ and normal pressure, when the formaldehyde concentration is 20ppm, the degradation rate of formaldehyde reaches 95% after 1h of catalytic oxidation, and the catalytic activity of catalyzing and decomposing formaldehyde is excellent, so that the method has good practicability.
Description
Technical Field
The invention belongs to the field of catalysts and environmental catalysis, and particularly relates to a supported catalyst for efficiently removing formaldehyde at room temperature, and a preparation method and application thereof.
Background
Formaldehyde is an important economic chemical, but is also a colorless toxic gas accompanied by strong pungent odor, and is recognized as one of serious environmental pollutants by the world health organization, and is one of the culprits for causing serious diseases such as cancer and distortion of human beings. At present, 80% of the life of modern people spends indoors, and indoor air quality problems have attracted close attention. Therefore, indoor air pollution has become a major problem to be solved urgently, and how to eliminate formaldehyde in indoor air, meeting strict environmental standards and the needs of human health, has become a hot spot for people to study.
At present, various air purification technologies have appeared at home and abroad to eliminate formaldehyde pollution in indoor air, mainly including adsorption method, biodegradation method, photocatalytic oxidation method, plasma oxidation method, ozone oxidation method, thermal catalytic oxidation method and the like. The adsorption method is a traditional method, can remove formaldehyde, is limited by the problems of adsorption balance, inactivation, replacement and the like of the adsorbent, and is not a good method for removing formaldehyde; although photocatalytic, plasma and ozone oxidation methods can effectively eliminate formaldehyde in the room, they require a light source and additional equipment, and toxic byproducts are also easily produced in the catalytic formaldehyde oxidation process; the biodegradation method is an environment-friendly method, can effectively remove formaldehyde, but has low formaldehyde degradation rate, and the life cycle of microorganisms is a very limited condition. The thermal catalytic oxidation method can completely catalyze and oxidize formaldehyde gas in indoor air into carbon dioxide and water at room temperature, has no secondary pollution, has high responsiveness to low-concentration formaldehyde, is quick in reaction, saves energy sources in the reaction process, is simple to operate and is environment-friendly, and the efficient formaldehyde elimination capability of the thermal catalytic oxidation method becomes a research hot spot of great importance.
The method for catalyzing and decomposing formaldehyde at room temperature has the characteristics of high efficiency, safety, stability and economy, and is concerned by the academic community. delta-MnO 2 The layered structure is formed by sharing [ MnO ] 6 ]The octahedral edges form a 2D layered structure. The material can provide a larger specific surface area and has certain moisture resistance, thus having excellent ion exchange property and good oxidation-reduction property, and also having excellent pore canal effect and adsorption effect, so that the material is favorable for the formaldehyde adsorption and formaldehyde decomposition processes, has great environmental catalytic potential, can be used for catalyzing formaldehyde oxidation, and has good activity only at high temperature. The platinum noble metal has excellent activity and can catalyze formaldehyde oxidation at room temperature. Then the platinum noble metal is loaded on delta-MnO 2 Can be used for catalyzing formaldehyde oxidation at room temperature to lead the armorThe aldehyde is converted to carbon dioxide and water. However, the prior art does not support the platinum noble metal on delta-MnO 2 As a material for decomposing formaldehyde.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary aim of the invention is to provide a preparation method of a supported catalyst for efficiently removing formaldehyde at room temperature, which firstly prepares delta-MnO 2 Then using anti-cyclohaemacid to treat delta-MnO 2 Pretreatment is carried out to lead the surface to carry out charge transfer process, and delta-MnO is carried out 2 Surface formation of sufficient amount of Mn 3+ Defective sites for anchoring platinum atoms, prepared in delta-MnO 2 The catalyst is a catalyst with platinum atoms supported on a carrier and is used as a material capable of efficiently catalyzing and decomposing formaldehyde at room temperature.
The invention also aims to provide the supported catalyst for efficiently removing formaldehyde at room temperature.
The invention also aims to provide application of the supported catalyst for efficiently removing formaldehyde at room temperature.
The aim of the invention is achieved by the following scheme:
the preparation method of the supported catalyst for efficiently removing formaldehyde at room temperature comprises the following steps:
(1) Dissolving manganese sulfate monohydrate in water to prepare manganese sulfate solution, adding the manganese sulfate solution into a stirred potassium permanganate aqueous solution, stirring and mixing to form uniform solution, transferring the uniform solution into a stainless steel autoclave with a Teflon lining, placing the stainless steel autoclave into an oven for hydrothermal reaction, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain black solid;
(2) The black solid is put into a muffle furnace for heat treatment to obtain delta-MnO 2 ；
(3) The delta-MnO obtained is 2 Dispersing in water, adding ascorbic acid, stirring at room temperature for reaction, centrifuging the reaction solution, washing with water, and drying to obtain product named delta-MnO 2 -AA；
(4) delta-MnO 2 Dispersing AA into water, adding chloroplatinic acid solution, stirring and soaking, adding alkali to adjust the pH value to 7-11, aging, adding a reducing agent into the aged solution for reduction, centrifuging, washing and drying the obtained suspension, thus obtaining the supported catalyst for efficiently removing formaldehyde at room temperature.
The dosage of the manganese sulfate solution and the potassium permanganate aqueous solution in the step (1) is as follows: the molar ratio of the potassium permanganate to the manganese sulfate is 1-10.
The stirring and mixing in the step (1) to form a uniform solution is preferably stirring for 10-60min;
the hydrothermal reaction in the step (1) means that the reaction is carried out for 10 to 30 hours in an oven at the temperature of 100 to 300 ℃;
the washing in the step (1) refers to washing with water, and the drying refers to drying in an oven at 60-120 ℃ for 8-12h.
The heat treatment in the step (2) is to heat from room temperature to 100-500 ℃ at a heating rate of 1-10 ℃/min, and keep the temperature for 2-10h.
delta-MnO as described in step (3) 2 And the amount of ascorbic acid is as follows: delta-MnO 2 And ascorbic acid in a molar ratio of 1-5:1.
The stirring reaction at room temperature in the step (3) means stirring reaction at room temperature for 1 to 10 hours, and stirring is only for sufficient contact between the raw materials, so that the stirring speed may not be limited.
The centrifugation in the step (3) is preferably centrifugation at 6000 to 10000 r/min; the drying is performed at 60-120deg.C for 8-20h.
delta-MnO as described in step (4) 2 The amounts of AA and chloroplatinic acid solution are such that: mass of platinum element and delta-MnO in chloroplatinic acid solution 2 The mass ratio of the AA is 0.1 to 1 wt.%, preferably 0.8 wt.%.
The stirring and soaking time in the step (4) is 1-10h.
The aging in the step (4) means aging at 30-100 ℃ for 1-10 hours.
The reducing agent in the step (4) is NaBH 4 At least one of ascorbic acid and ethylene glycol, wherein NaBH 4 And resistance to damageThe blood acid is preferably NaBH 4 Adding in the form of aqueous solution and ascorbic acid aqueous solution; the reducing agent in the step (4) is used in an amount which satisfies the following conditions: the mol ratio of the reducing agent to the platinum element in the chloroplatinic acid is 10-50:1.
The reduction in the step (4) means reduction at 40-100 ℃ for 5-60min;
the drying in the step (4) refers to drying at 60-120 ℃ for 8-20h.
The supported catalyst for efficiently removing formaldehyde at room temperature prepared by the method.
The supported catalyst for efficiently removing formaldehyde at room temperature is applied to formaldehyde removal.
The invention provides a method for preparing delta-MnO by selecting manganese sulfate monohydrate, potassium permanganate and chloroplatinic acid as raw materials and adopting a hydrothermal method 2 Then modified by ascorbic acid, and then carried by the dipping method to carry chloroplatinic acid on delta-MnO 2 Finally, the platinum atoms are obtained by reduction with a direct reduction method.
Compared with the prior art, the invention has the following advantages: simple surface engineering methods for preparing highly stable noble metal catalysts with atomic dispersibility using molecular-surface charge transfer adducts. The key to this approach is the adsorption of the reducing ascorbic acid molecules and subsequent surface charge transfer processes at the porous MnO 2 Surface formation of sufficient amount of Mn 3+ Defective bits. Subsequently, the noble metal Pt atoms can be dispersedly anchored in the porous MnO 2 Mn of nanorods 3+ In the bit, the loading density is as high as 1.0wt%.
Drawings
FIG. 1 shows the catalyst Pt/delta-MnO prepared in example 1 2 Catalyst Pt/delta-MnO prepared by AA3 and comparative example 1 2 Is a XRD spectrum of (C).
FIG. 2 is a schematic diagram of a formaldehyde catalyst performance evaluation apparatus in examples.
FIG. 3 is a graph showing the effect of the catalysts prepared in examples 1-2 and comparative example 1 on catalyzing formaldehyde.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
Step one: 1.5g KMnO was added at room temperature 4 Placing in a beaker, adding 60ml of deionized water, stirring and uniformly mixing, and keeping stirring.
Step two: putting 0.275g of manganese sulfate monohydrate into a beaker, adding 20ml of deionized water to prepare a manganese sulfate solution, dropwise adding the solution into the solution obtained in the step one, and stirring the mixed solution for 30min after the dropwise adding of the manganese sulfate solution is completed to form a uniform solution. It was then transferred into a teflon lined stainless steel autoclave.
Step three: the autoclave was placed in an oven and heated to 240 ℃ for 24 hours. When it naturally cooled to room temperature, the product was collected.
Step four: and (3) filtering the product obtained in the step (III), washing the product with deionized water for 3 times, placing the product in an oven, and drying the product at 60 ℃ for 12 hours to obtain black solid.
Step five: the black solid obtained in the step four is placed in a muffle furnace for heat treatment, the temperature is increased from room temperature to 300 ℃ at the heating rate of 2 ℃/min, and the black solid is dried for 3 hours at the temperature and cooled to the room temperature, thus obtaining delta-MnO 2 。
Step six: 1g of delta-MnO was added at room temperature 2 Put into beaker, add 175ml deionized water, stir for 5min and add 0.674g ascorbic acid (delta-MnO) 2 Molar ratio to ascorbic acid = 3:1), followed by vigorous stirring for 3h. The resulting suspension was divided into six equal parts and the solid particles of each part were collected by centrifugation at 8000r/min, washed 4 times with 30ml of deionized water each time, and then placed in an oven and dried at 60℃for 12h. The product obtained in this step is denoted as delta-MnO 2 -AA3。
Step seven: 0.5g of delta-MnO was added at room temperature 2 Placing AA in a beaker, adding 30ml deionized water, stirring for 5min, and then adding 0.841ml H 2 PtCl 6 Solution (10 mg/ml) stirred impregnation 1h, followed by addition of a 0.1mol/L NaOH solution, pH adjustment to 10, and aging at 60℃for 2h. 3ml of NaBH ready to be prepared are then added at room temperature 4 (0.1 mol/L) was added to the mixed solution and stirred for 0.5 hours, and the resulting solution was centrifuged at 8000r/min to collect solid particles, which were washed 4 times with 30ml of deionized water each time, and then placed in an oven and dried at 60℃for 12 hours. To obtain the final catalyst, which is named Pt/delta-MnO 2 -AA3。
Example 2:
step one: 1.5g KMnO was added at room temperature 4 Placing in a beaker, adding 60ml of deionized water, stirring and uniformly mixing, and keeping stirring.
Step two: putting 0.275g of manganese sulfate monohydrate into a beaker, adding 20ml of deionized water to prepare a manganese sulfate solution, dropwise adding the solution into the solution obtained in the step one, and stirring the mixed solution for 30min after the dropwise adding of the manganese sulfate solution is completed to form a uniform solution. It was then transferred into a teflon lined stainless steel autoclave.
Step three: the autoclave was placed in an oven and heated to 240 ℃ for 24 hours. When it naturally cooled to room temperature, the product was collected.
Step four: and (3) filtering the product obtained in the step (III), washing the product with deionized water for 3 times, placing the product in an oven, and drying the product at 80 ℃ for 12 hours to obtain black solid.
Step five: the black solid obtained in the step four is placed in a muffle furnace for heat treatment, the temperature is increased from room temperature to 300 ℃ at the heating rate of 2 ℃/min, and the black solid is dried for 4 hours and cooled to room temperature, thus obtaining delta-MnO 2 。
Step six: 1g of delta-MnO was added at room temperature 2 Put into a beaker, 175ml of deionized water was added, stirred for 5 minutes and 0.506g of ascorbic acid (delta-MnO) 2 Molar ratio to ascorbic acid = 4:1), followed by vigorous stirring for 3h. The resulting suspension was divided into six equal parts and the solid particles of each part were collected by centrifugation at 8000r/min, washed 4 times with 30ml of deionized water each time, and then placed in an oven and dried at 60℃for 12h. The product obtained in this step is denoted as delta-MnO 2 -AA4。
Step seven: 0.5g of delta-MnO was added at room temperature 2 Placing AA in a beaker, adding 30ml deionized water, stirring for 5min, and then adding 0.841ml H 2 PtCl 6 The solution (10 mg/ml) was immersed for 1 hour with stirring, followed by addition of 0.1mol/L NaOH solution, pH was adjusted to 10, and then aged at 60℃for 2 hours. 3ml of NaBH ready to be prepared are then added at room temperature 4 (0.1 mol/L) was added to the mixed solution and stirred for 0.5 hours, and the resulting solution was centrifuged at 8000r/min to collect solid particles, which were washed 4 times with 30ml of deionized water each time, and then placed in an oven and dried at 60℃for 12 hours. To obtain the final catalyst, which is named Pt/delta-MnO 2 -AA4。
Comparative example 1:
step one: 1.5g KMnO was added at room temperature 4 Placing in a beaker, adding 60ml of deionized water, stirring and uniformly mixing, and keeping stirring.
Step two: putting 0.275g of manganese sulfate monohydrate into a beaker, adding 20ml of deionized water to prepare a manganese sulfate solution, dropwise adding the solution into the solution obtained in the step one, and stirring the mixed solution for 30min after the dropwise adding of the manganese sulfate solution is completed to form a uniform solution. It was then transferred into a teflon lined stainless steel autoclave.
Step three: the autoclave was placed in an oven and heated to 240 ℃ for 24 hours. When it naturally cooled to room temperature, the product was collected.
Step four: and (3) filtering the product obtained in the step (III), washing the product with deionized water for 3 times, placing the product in an oven, and drying the product at 80 ℃ for 12 hours to obtain black solid.
Step five: the black solid obtained in the step four is placed in a muffle furnace for heat treatment, the temperature is increased from room temperature to 300 ℃ at the heating rate of 2 ℃/min, and the black solid is dried for 4 hours and cooled to room temperature, thus obtaining delta-MnO 2 。
Step six: 0.5g of delta-MnO was added at room temperature 2 Put into a beaker, add 30ml deionized water, stir for 5min, then add 0.841ml H 2 PtCl 6 The solution (10 mg/ml) was immersed for 1 hour with stirring, followed by addition of 0.1mol/L NaOH solution to adjust the pH to 10, thenAnd then aged at 60℃for 2h. 3ml of NaBH ready to be prepared are then added at room temperature 4 (0.1 mol/L) was added to the mixed solution and stirred for 0.5 hours, and the resulting solution was centrifuged at 8000r/min to collect solid particles, which were washed 4 times with 30ml of deionized water each time, and then placed in an oven and dried at 60℃for 12 hours. To obtain the final catalyst, which is named Pt/delta-MnO 2 。
The catalyst prepared in example 1 Pt/delta-MnO 2 Catalyst Pt/delta-MnO prepared by AA3 and comparative example 1 2 As can be seen from FIG. 1, the XRD spectrum of (C) is shown in FIG. 1 2 In the XRD spectrum of (2), the diffraction angle 2 theta = 12.8 degrees, 18.1 degrees, 28.8 degrees, and the absorption peaks of 37.522 degrees respectively correspond to (110), (200), (310) and (211) crystal faces, the diffraction peaks are basically consistent with standard cards, and the load of Pt is not equal to delta-MnO 2 The crystalline phase is changed. And ascorbic acid is added to delta-MnO 2 Platinum is carried after pretreatment, and it can be seen from the figure that Pt/delta-MnO 2 In the XRD spectrum of AA, in addition to the above absorption peaks, new absorption peaks appear at diffraction angles 2θ=31.0 (200), 32.3 (103), 36.0 (211), 44.4 (220), 58.5 (321), the diffraction peaks are substantially identical to those of the standard card (PDF card 24-0734), and the corresponding substances are Mn 3 O 4 Illustrating the addition of ascorbic acid in porous MnO by adsorption of reducing ascorbic acid molecules followed by a surface charge transfer process 2 Surface formation of sufficient amount of Mn 3+ Defective sites, after which noble metal Pt atoms can be anchored in a dispersed manner to the porous MnO 2 Mn of nanorods 3+ On the bit.
The catalysts prepared in examples 1-2 and comparative example were used to catalyze formaldehyde at room temperature, and formaldehyde performance evaluation experiments were performed at room temperature and atmospheric pressure in a plexiglas box (60L) in which a 1-formaldehyde detector, a 2-fan and 3-sample stage, and a 4-incandescent lamp (not shown) were placed, as shown in FIG. 2. The sample placement table has placed thereon 1 culture dish and 1 length: width: high = 10cm: an arched heating plate of 8cm:6cm, in which the dish was placed with 0.2g of catalyst dispersed and covered with glass flakes, under which an incandescent lamp was placed. Directly above the culture dish and the heating plate areTwo small holes are respectively formed on the organic glass, one small hole is used for injecting 5 mu L of 37% HCHO solution, the organic glass container is sealed after injection, HCHO is volatilized under the assistance of an electric fan and an incandescent lamp, when a formaldehyde detector shows that the formaldehyde concentration is in a stable state (20 ppm), a hole right above a culture dish with a catalyst is opened, a glass sheet is removed through the hole, then the organic glass container is sealed again for reaction, and the formaldehyde concentration in the organic glass box is determined through the indication of the formaldehyde detector in different time periods, so that the formaldehyde removal capacity of the catalyst is determined. The results are shown in FIG. 3, and it can be seen from FIG. 3 that the Pt/delta-MnO prepared according to the present invention 2 -AA 3 And Pt/delta-MnO 2 -AA 4 Compared with Pt/delta-MnO which is not modified by ascorbic acid 2 Has more excellent performance of catalyzing and decomposing formaldehyde, in particular Pt/delta-MnO 2 -AA 3 The formaldehyde has a degradation rate of 95% after catalytic oxidation for 1h at 25 ℃ and normal pressure when the formaldehyde concentration is 20ppm, shows excellent catalytic activity of catalyzing and decomposing formaldehyde, and has good practicability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the supported catalyst for efficiently removing formaldehyde at room temperature is characterized by comprising the following steps of:
(1) Dissolving manganese sulfate monohydrate in water to prepare manganese sulfate solution, adding the manganese sulfate solution into a stirred potassium permanganate aqueous solution, stirring and mixing to form uniform solution, transferring the uniform solution into a stainless steel autoclave with a Teflon lining, placing the stainless steel autoclave into an oven for hydrothermal reaction, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain black solid;
(2) Placing the obtained black solid in a muffle furnace for heatingAnd obtaining delta-MnO 2 ；
(3) The delta-MnO obtained is 2 Dispersing in water, adding ascorbic acid, stirring at room temperature for reaction, centrifuging the reaction solution, washing with water, and drying to obtain product named delta-MnO 2 -AA；
(4) delta-MnO 2 Dispersing AA into water, adding chloroplatinic acid solution, stirring and soaking, adding alkali to adjust the pH value to 7-11, aging, adding a reducing agent into the aged solution for reduction, centrifuging, washing and drying the obtained suspension to obtain the supported catalyst for efficiently removing formaldehyde at room temperature;
delta-MnO as described in step (3) 2 And the amount of ascorbic acid is as follows: delta-MnO 2 And ascorbic acid in a molar ratio of 1-5:1;
the stirring reaction at room temperature in the step (3) means stirring reaction at room temperature for 1-10h.
2. The method for preparing the supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, which is characterized in that:
the dosage of the manganese sulfate solution and the potassium permanganate aqueous solution in the step (1) is as follows: the molar ratio of the potassium permanganate to the manganese sulfate is 1-10;
the hydrothermal reaction in the step (1) is carried out in an oven at 100-300 ℃ for 10-30 hours.
3. The method for preparing the supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, which is characterized in that:
the heat treatment in the step (2) is to heat from room temperature to 100-500 ℃ at a heating rate of 1-10 ℃/min, and keep the temperature for 2-10h.
4. The method for preparing the supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, which is characterized in that:
delta-MnO as described in step (4) 2 The dosage of the AA and chloroplatinic acid solution is fullFoot: mass of platinum element and delta-MnO in chloroplatinic acid solution 2 -AA in a mass ratio of 0.1-1wt%;
the stirring and soaking time in the step (4) is 1-10h;
the aging in the step (4) means aging at 30-100 ℃ for 1-10 hours.
5. The method for preparing the supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, which is characterized in that:
the reducing agent in the step (4) is NaBH 4 At least one of ascorbic acid and ethylene glycol; the reducing agent in the step (4) is used in an amount which satisfies the following conditions: the mol ratio of the reducing agent to the platinum element in the chloroplatinic acid is 10-50:1;
the reduction in the step (4) means reduction at 40-100 ℃ for 5-60min.
6. A supported catalyst for efficient removal of formaldehyde at room temperature prepared according to the method of any one of claims 1 to 5.
7. The use of the supported catalyst for efficiently removing formaldehyde at room temperature according to claim 6 for removing formaldehyde.
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| CN101497042A (en) * | 2009-03-11 | 2009-08-05 | 华东理工大学 | Catalyst for eliminating formaldehyde in air by low-temperature catalytic oxidation |
| CN105013322A (en) * | 2015-06-25 | 2015-11-04 | 中国科学院生态环境研究中心 | Use of manganite catalyst in catalytic oxidation of formaldehyde |
| CN106268799A (en) * | 2016-08-26 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | Manganese oxide nanometer sheet material of the crystallization of supporting Pt and its preparation method and application |
| CN108786805A (en) * | 2018-05-28 | 2018-11-13 | 江汉大学 | A kind of composite catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101497042A (en) * | 2009-03-11 | 2009-08-05 | 华东理工大学 | Catalyst for eliminating formaldehyde in air by low-temperature catalytic oxidation |
| CN105013322A (en) * | 2015-06-25 | 2015-11-04 | 中国科学院生态环境研究中心 | Use of manganite catalyst in catalytic oxidation of formaldehyde |
| CN106268799A (en) * | 2016-08-26 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | Manganese oxide nanometer sheet material of the crystallization of supporting Pt and its preparation method and application |
| CN108786805A (en) * | 2018-05-28 | 2018-11-13 | 江汉大学 | A kind of composite catalyst and its preparation method and application |
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