CN114950572A - 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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- 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
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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 ascorbic acid is used to react with delta-MnO 2 Pre-treating the surface of the substrate to perform a charge transfer process in delta-MnO 2 A sufficient amount of Mn is generated on the surface 3+ Defect sites for anchoring platinum atoms to produce delta-MnO 2 The catalyst with platinum atoms loaded on the carrier is used for a material which can efficiently catalyze and decompose formaldehyde at room temperature. The degradation rate of formaldehyde is 1h of catalytic oxidation at the temperature of 25 ℃ and normal pressure when the concentration of formaldehyde is 20ppmReaches 95 percent, shows excellent catalytic activity for catalyzing and decomposing formaldehyde and 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 with strong pungent odor, which is recognized as one of serious environmental pollutants by the world health organization, and is one of the chief causes of serious diseases such as cancer and distortion in human beings. At present, the modern people spend 80% of their lives indoors, and the indoor air quality problem has attracted close attention. Therefore, indoor air pollution has become a major problem to be solved urgently, and how to eliminate formaldehyde in indoor air and meet the requirements of strict environmental standards and human health becomes a hotspot of research.
At present, various air purification technologies have appeared at home and abroad to eliminate formaldehyde pollution in indoor air, and the technologies mainly include an adsorption method, a biodegradation method, a photocatalytic oxidation method, a plasma oxidation method, an ozone oxidation method, a thermal catalytic oxidation method and the like. The adsorption method is a traditional method, can remove formaldehyde, but is limited by the problems of adsorption balance, inactivation, replacement and the like of an adsorbent, and is not a good method for removing formaldehyde; although the photocatalysis method, the plasma method and the ozone oxidation method can effectively eliminate indoor formaldehyde, a light source and additional equipment are needed, and toxic byproducts are easily generated 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 great limitation condition. The thermal catalytic oxidation method can completely catalytically oxidize formaldehyde gas in indoor air into carbon dioxide and water at room temperature, has no secondary pollution, has high response to low-concentration formaldehyde, is quick in reaction, saves energy in the reaction process, is simple to operate, is environment-friendly, and has high formaldehyde elimination capability, thus becoming a research hotspot which is widely focused.
The method for catalytically decomposing formaldehyde at room temperature has the characteristics of high efficiency, safety, stability and economy, and is concerned by the academic world. Delta-MnO 2 The layered structure being 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, so that the material has excellent ion exchange performance and good oxidation-reduction performance, and also has excellent pore channel effect and adsorption effect, so that the material is beneficial to the processes of adsorbing formaldehyde and decomposing formaldehyde, has great environmental catalysis potential, can be used for catalyzing formaldehyde oxidation, and has good activity at high temperature. The platinum noble metal has excellent activity and can catalyze formaldehyde oxidation at room temperature. Then the noble metal of platinum is loaded in delta-MnO 2 Can be used for catalyzing formaldehyde oxidation at room temperature to convert formaldehyde into carbon dioxide and water. However, in the prior art, the noble metal of platinum is not loaded in delta-MnO 2 As a material for decomposing formaldehyde.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention firstly aims to provide a preparation method of a supported catalyst for efficiently removing formaldehyde at room temperature 2 Then ascorbic acid is used to react with delta-MnO 2 Pre-treating the surface of the substrate to perform a charge transfer process in delta-MnO 2 A sufficient amount of Mn is generated on the surface 3+ Defect sites for anchoring platinum atoms to produce delta-MnO 2 The catalyst with platinum atoms loaded on the carrier is used for a material which can efficiently catalyze and decompose formaldehyde at room temperature.
The invention also aims to provide the supported catalyst for efficiently removing formaldehyde at room temperature, which is prepared by the method.
The invention further aims to provide the application of the supported catalyst for efficiently removing formaldehyde at room temperature.
The purpose of the invention is realized by the following scheme:
a preparation method of a supported catalyst for efficiently removing formaldehyde at room temperature comprises the following steps:
(1) dissolving manganese sulfate monohydrate in water to prepare a manganese sulfate solution, adding the manganese sulfate solution into a potassium permanganate aqueous solution in stirring, stirring and mixing to form a uniform solution, then transferring the uniform solution into a Teflon-lined stainless steel autoclave, placing the stainless steel autoclave in an oven for hydrothermal reaction, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain a black solid;
(2) placing the obtained black solid in a muffle furnace for heat treatment to obtain delta-MnO 2 ；
(3) The obtained delta-MnO 2 Dispersing in water, adding ascorbic acid, stirring at room temperature, reacting, centrifuging, washing with water, and drying to obtain delta-MnO 2 -AA；
(4) To make delta-MnO 2 Dispersing AA into water, adding a chloroplatinic acid solution, stirring and dipping, adding alkali to adjust the pH to 7-11, aging, adding a reducing agent into the solution for reduction after aging, centrifuging the obtained suspension, washing and drying to obtain the supported catalyst for efficiently removing formaldehyde at room temperature.
The usage amount of the manganese sulfate solution and the potassium permanganate solution in the step (1) meets the following requirements: the molar ratio of potassium permanganate to manganese sulfate is 1-10.
Stirring and mixing to form a uniform solution in the step (1), preferably stirring for 10-60 min;
the hydrothermal reaction in the step (1) refers to a reaction in an oven at 100-300 ℃ for 10-30 h;
the washing in the step (1) refers to washing with water, and the drying refers to drying in an oven at 60-120 ℃ for 8-12 h.
The heat treatment in the step (2) is to heat the mixture from room temperature to 500 ℃ at a heating rate of 1-10 ℃/min, and to keep the temperature for 2-10 h.
delta-MnO described in step (3) 2 And the amount of ascorbic acid is such that: Delta-MnO 2 And an antibodyThe molar ratio of the ascorbic acid is 1-5: 1.
The stirring reaction at room temperature in the step (3) means a stirring reaction at room temperature for 1 to 10 hours, and the stirring is only performed for sufficient contact between the raw materials, so that the stirring speed is not limited.
The centrifugal separation in the step (3) is preferably carried out at 6000-10000 r/min; the drying refers to drying for 8-20h at 60-120 ℃.
delta-MnO described in step (4) 2 The amounts of AA and chloroplatinic acid solution are such that: mass and delta-MnO of platinum element in chloroplatinic acid solution 2 The mass ratio of-AA is 0.1-1 wt%, preferably 0.8 wt%.
The stirring and dipping time in the step (4) is 1-10 h.
The aging in the step (4) refers to aging for 1-10h at 30-100 ℃.
The reducing agent in the step (4) is NaBH 4 At least one of ascorbic acid and ethylene glycol, wherein NaBH 4 And ascorbic acid are each preferably NaBH 4 Adding water solution and ascorbic acid water solution; the dosage of the reducing agent in the step (4) meets the following requirements: the molar ratio of the reducing agent to the platinum element in the chloroplatinic acid is 10-50: 1.
The reduction in the step (4) is carried out for 5-60min at 40-100 ℃;
the drying in the step (4) refers to drying for 8-20h at 60-120 ℃.
The supported catalyst for efficiently removing formaldehyde at room temperature is prepared by the method.
The supported catalyst for efficiently removing formaldehyde at room temperature is applied to the removal of formaldehyde.
The invention provides a method for preparing delta-MnO by using manganese sulfate monohydrate, potassium permanganate and chloroplatinic acid as raw materials and adopting a hydrothermal method 2 Then the modified product is modified by ascorbic acid and the chloroplatinic acid is loaded in delta-MnO by an impregnation method 2 Finally, platinum atoms are obtained by direct reduction.
Compared with the prior art, the invention has the following advantages and beneficial effects: addition by molecule-surface charge transferA simple surface engineering method for preparing a high-stability noble metal catalyst with atomic dispersity. The key of the method is to adsorb the reducing ascorbic acid molecules and then carry out the surface charge transfer process on the porous MnO 2 Sufficient amount of Mn is generated on the surface 3+ A defective bit. 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 1.0 wt%.
Drawings
FIG. 1 shows Pt/delta-MnO catalyst prepared in example 1 2 -AA3 and Pt/delta-MnO catalyst prepared in comparative example 1 2 XRD spectrum of (1).
FIG. 2 is a schematic view of an apparatus for evaluating the performance of a formaldehyde catalyst in the example.
FIG. 3 is a graph showing the effect of catalysts prepared in examples 1-2 and comparative example 1 in catalyzing formaldehyde.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
The method comprises the following steps: under the condition of room temperature, 1.5g of KMnO 4 Placing the mixture into a beaker, adding 60ml of deionized water, stirring and mixing uniformly, and keeping stirring.
Step two: and (3) placing 0.275g of manganese sulfate monohydrate in a beaker, adding 20ml of deionized water to prepare a manganese sulfate solution, dropwise adding the manganese sulfate solution into the solution obtained in the step one, and stirring the mixed solution for 30min after the manganese sulfate solution is completely added 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 h. And collecting the product when the product is naturally cooled to room temperature.
Step four: and (3) filtering the product obtained in the third step, washing the product for 3 times by using deionized water, placing the product in an oven, and drying the product for 12 hours at the temperature of 60 ℃ to obtain a black solid.
Step five: putting the black solid obtained in the fourth step into a muffle furnace for heat treatment, heating from room temperature to 300 ℃ at the heating rate of 2 ℃/min, drying for 3h at the temperature, and cooling to room temperature to obtain delta-MnO 2 。
Step six: at room temperature, 1g of delta-MnO 2 Placing in a beaker, adding 175ml of deionized water, stirring for 5min, and adding 0.674g ascorbic acid (delta-MnO) 2 Molar ratio to ascorbic acid 3:1) and then stirred vigorously for 3 h. The resulting suspension was divided into six equal portions and each portion of solid particles was collected by centrifugation at 8000r/min, washed 4 times with 30ml each time of deionized water, and then placed in an oven and dried at 60 ℃ for 12 h. The product obtained in this step is denoted delta-MnO 2 -AA3。
Step seven: at room temperature, 0.5g of delta-MnO 2 -AA in a beaker, 30ml of deionized water was added and after 5min of stirring, 0.841ml of H was added 2 PtCl 6 The solution (10mg/ml) was immersed with stirring for 1h, followed by addition of 0.1mol/L NaOH solution to adjust the pH to 10 and then aged at 60 ℃ for 2 h. Then 3ml of NaBH now prepared is added at room temperature 4 (0.1mol/L) was added to the mixed solution and stirred for 0.5h, and the resulting solution was centrifuged at 8000r/min to collect solid particles, which were washed 4 times with 30ml portions of deionized water each time, and then placed in an oven and dried at 60 ℃ for 12 h. The final catalyst, recorded as Pt/delta-MnO, was obtained 2 -AA3。
Example 2:
the method comprises the following steps: under the condition of room temperature, 1.5g of KMnO 4 Placing the mixture into a beaker, adding 60ml of deionized water, stirring and mixing uniformly, and keeping stirring.
Step two: and (3) placing 0.275g of manganese sulfate monohydrate in a beaker, adding 20ml of deionized water to prepare a manganese sulfate solution, dropwise adding the manganese sulfate solution into the solution obtained in the step one, and stirring the mixed solution for 30min after the manganese sulfate solution is completely added 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 h. And collecting the product when the product is naturally cooled to room temperature.
Step four: and (3) filtering the product obtained in the third step, washing the product for 3 times by using deionized water, placing the product in an oven, and drying the product for 12 hours at the temperature of 80 ℃ to obtain a black solid.
Step five: putting the black solid obtained in the fourth step into a muffle furnace for heat treatment, heating from room temperature to 300 ℃ at the heating rate of 2 ℃/min, drying for 4h at the temperature, and cooling to room temperature to obtain delta-MnO 2 。
Step six: at room temperature, 1g of delta-MnO 2 Placing in a beaker, adding 175ml of deionized water, stirring for 5min, and adding 0.506g ascorbic acid (delta-MnO) 2 Molar ratio to ascorbic acid 4:1) and then stirred vigorously for 3 h. The resulting suspension was divided into six equal portions and each portion of solid particles was 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 12 h. The product obtained in this step is denoted delta-MnO 2 -AA4。
Step seven: at room temperature, 0.5g of delta-MnO 2 -AA in a beaker, 30ml of deionized water was added and after 5min of stirring, 0.841ml of H was added 2 PtCl 6 The solution (10mg/ml) was immersed with stirring for 1h, followed by addition of 0.1mol/L NaOH solution to adjust the pH to 10 and then aged at 60 ℃ for 2 h. Then 3ml of NaBH now prepared is added at room temperature 4 (0.1mol/L) is added into the mixed solution to be stirred for 0.5h, the obtained solution is centrifuged at the rotating speed of 8000r/min to collect solid particles, the solid particles are washed 4 times by 30ml of deionized water each time, and then the solid particles are placed in an oven and dried for 12h at the temperature of 60 ℃. The final catalyst, recorded as Pt/delta-MnO, was obtained 2 -AA4。
Comparative example 1:
the method comprises the following steps: under the condition of room temperature, 1.5g of KMnO 4 Placing the mixture into a beaker, adding 60ml of deionized water, stirring and mixing uniformly, and keeping stirring.
Step two: and (3) placing 0.275g of manganese sulfate monohydrate in a beaker, adding 20ml of deionized water to prepare a manganese sulfate solution, dropwise adding the manganese sulfate solution into the solution obtained in the step one, and stirring the mixed solution for 30min after the manganese sulfate solution is completely added 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 h. And collecting the product when the product is naturally cooled to room temperature.
Step four: and (3) filtering the product obtained in the third step, washing the product for 3 times by using deionized water, placing the product in an oven, and drying the product for 12 hours at the temperature of 80 ℃ to obtain a black solid.
Step five: putting the black solid obtained in the step four into a muffle furnace for heat treatment, heating the black solid from room temperature to 300 ℃ at the heating rate of 2 ℃/min, drying the black solid for 4 hours at the temperature, and cooling the dried black solid to the room temperature to obtain delta-MnO 2 。
Step six: at room temperature, 0.5g of delta-MnO 2 Placing in a beaker, adding 30ml deionized water, stirring for 5min, and adding 0.841ml H 2 PtCl 6 The solution (10mg/ml) was immersed with stirring for 1h, followed by addition of 0.1mol/L NaOH solution to adjust the pH to 10 and then aged at 60 ℃ for 2 h. Then 3ml of NaBH now prepared is added at room temperature 4 (0.1mol/L) is added into the mixed solution to be stirred for 0.5h, the obtained solution is centrifuged at the rotating speed of 8000r/min to collect solid particles, the solid particles are washed 4 times by 30ml of deionized water each time, and then the solid particles are placed in an oven and dried for 12h at the temperature of 60 ℃. The final catalyst, noted Pt/delta-MnO, was obtained 2 。
Catalyst Pt/delta-MnO prepared in example 1 2 -AA3 and Pt/delta-MnO catalyst prepared in comparative example 1 2 The XRD spectrum of the compound is shown in FIG. 1, and Pt/delta-MnO can be seen from FIG. 1 2 The XRD spectrum of (1) has absorption peaks corresponding to (110), (200), (310) and (211) crystal planes respectively at diffraction angles 2 theta of 12.8 degrees, 18.1 degrees, 28.8 degrees and 37.522 degrees, the diffraction peaks are basically consistent with standard cards, and the load of Pt is not applied to delta-MnO 2 The crystal phase is changed. While adding ascorbic acid to the delta-MnO 2 The pretreatment was carried out and then platinum was loaded, as can be seen from the figure, Pt/delta-MnO 2 In the XRD spectrum of AA, in addition to the retention of the above absorption peaks, new absorption peaks appear at diffraction angles 2 θ of 31.0(200), 32.3(103), 36.0(211), 44.4(220), 58.5(321), the diffraction peaks and standard cards: (a), (b), (c), (d) and d), (d) and (d) aPDF card 24-0734) is basically consistent, and the corresponding substance is Mn 3 O 4 Indicating the addition of ascorbic acid by adsorption of reducing ascorbic acid molecules and subsequent surface charge transfer process at the porous MnO 2 Sufficient amount of Mn is generated on the surface 3+ Defect sites, and subsequently, noble metal Pt atoms can be dispersedly anchored in 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 the formaldehyde performance evaluation experiment was conducted at room temperature under normal pressure in a plexiglass box (60L) in which a 1-formaldehyde detector, a 2-fan and 3-sample holder, and a 4-incandescent lamp (not shown) were placed, as shown in FIG. 2. The sample is put and is placed 1 culture dish and 1 long on the thing platform: width: height 10 cm: an 8cm:6cm arched hot plate with a dispersed 0.2g catalyst placed in a petri dish and covered with a glass slide, and an incandescent lamp placed under the hot plate. Two small holes are respectively arranged on the organic glass right above the culture dish and the heating plate, wherein one small hole is used for injecting 5 mu L of 37 percent HCHO solution, the organic glass container is sealed after injection, the 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 (20ppm), the hole right above the culture dish with the catalyst is opened, a glass sheet is removed through the hole, then the organic glass container is sealed again for reaction, and the concentration of the formaldehyde in the organic glass box is determined through the indication number of the formaldehyde detector in different time periods, so that the removal capacity of the catalyst to the formaldehyde is determined. The results are shown in FIG. 3, and it can be seen from FIG. 3 that 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 When the concentration of formaldehyde is 20ppm at 25 ℃ and normal pressure, the degradation rate of formaldehyde reaches 95% through 1h of catalytic oxidation, the catalytic activity of the formaldehyde for catalytic decomposition is excellent, and the catalyst has good practicability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a supported catalyst for efficiently removing formaldehyde at room temperature is characterized by comprising the following steps:
(1) dissolving manganese sulfate monohydrate in water to prepare a manganese sulfate solution, adding the manganese sulfate solution into a potassium permanganate aqueous solution in stirring, stirring and mixing to form a uniform solution, then transferring the uniform solution into a Teflon-lined stainless steel autoclave, placing the stainless steel autoclave in an oven for hydrothermal reaction, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain a black solid;
(2) placing the obtained black solid in a muffle furnace for heat treatment to obtain delta-MnO 2 ；
(3) The obtained delta-MnO 2 Dispersing in water, adding ascorbic acid, stirring at room temperature, reacting, centrifuging, washing with water, and drying to obtain delta-MnO 2 -AA；
(4) Will delta-MnO 2 Dispersing AA into water, adding a chloroplatinic acid solution, stirring and dipping, adding alkali to adjust the pH value to 7-11, aging, adding a reducing agent into the solution for reduction after aging, centrifuging the obtained suspension, washing and drying to obtain the supported catalyst for efficiently removing formaldehyde at room temperature.
2. The method for preparing a supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, wherein the method comprises the following steps:
the usage amount of the manganese sulfate solution and the potassium permanganate solution in the step (1) meets the following requirements: the molar ratio of potassium permanganate to manganese sulfate is 1-10;
the hydrothermal reaction in the step (1) refers to a reaction in an oven at 100-300 ℃ for 10-30 h.
3. The method for preparing a supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, wherein the method comprises the following steps:
the heat treatment in the step (2) is to heat the mixture from room temperature to 500 ℃ at a heating rate of 1-10 ℃/min, and to keep the temperature for 2-10 h.
4. The method for preparing the supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, wherein the method comprises the following steps:
delta-MnO described in step (3) 2 And the amount of ascorbic acid is such that: Delta-MnO 2 And ascorbic acid in a molar ratio of 1-5: 1.
5. The method for preparing a supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, wherein the method comprises the following steps:
the stirring reaction at room temperature in the step (3) refers to stirring reaction at room temperature for 1-10 h.
6. The method for preparing a supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, wherein the method comprises the following steps:
delta-MnO described in step (4) 2 The amounts of AA and chloroplatinic acid solution are such that: mass and delta-MnO of platinum element in chloroplatinic acid solution 2 -AA in a mass ratio of 0.1-1 wt%;
the stirring and dipping time in the step (4) is 1-10 h;
the aging in the step (4) refers to aging for 1-10h at 30-100 ℃.
7. The method for preparing a supported catalyst for efficiently removing formaldehyde at room temperature according to claim 1, wherein the method comprises the following steps:
the reducing agent in the step (4) is NaBH 4 At least one of ascorbic acid and ethylene glycol; the dosage of the reducing agent in the step (4) meets the following requirements: the molar ratio of the reducing agent to platinum element in chloroplatinic acid is 10-50:1；
the reduction in the step (4) refers to reduction at 40-100 ℃ for 5-60 min.
8. A supported catalyst prepared according to the method of any one of claims 1 to 7 for efficient removal of formaldehyde at room temperature.
9. Use of the supported catalyst for efficient removal of formaldehyde at room temperature according to claim 8 for the removal of 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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| 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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