CN110482609B - High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method - Google Patents

High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method Download PDF

Info

Publication number
CN110482609B
CN110482609B CN201910716781.7A CN201910716781A CN110482609B CN 110482609 B CN110482609 B CN 110482609B CN 201910716781 A CN201910716781 A CN 201910716781A CN 110482609 B CN110482609 B CN 110482609B
Authority
CN
China
Prior art keywords
hydrothermal synthesis
mno
epsilon
hydrothermal
synthesis method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910716781.7A
Other languages
Chinese (zh)
Other versions
CN110482609A (en
Inventor
杨翠霞
代光剑
熊玉明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Midea Group Co Ltd
Guangdong Midea White Goods Technology Innovation Center Co Ltd
Original Assignee
Midea Group Co Ltd
Guangdong Midea White Goods Technology Innovation Center Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Midea Group Co Ltd, Guangdong Midea White Goods Technology Innovation Center Co Ltd filed Critical Midea Group Co Ltd
Priority to CN201910716781.7A priority Critical patent/CN110482609B/en
Publication of CN110482609A publication Critical patent/CN110482609A/en
Application granted granted Critical
Publication of CN110482609B publication Critical patent/CN110482609B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses epsilon-MnO2By controlling the temperature of the hydrothermal reaction and the concentration of potassium permanganate, epsilon-MnO having a very high specific surface area and crystal purity is unexpectedly prepared2Compared with other manganese dioxide on the market, the manganese dioxide can degrade formaldehyde with high efficiency.

Description

High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method
Technical Field
The invention relates to a preparation method of a material, in particular to epsilon-MnO2The hydrothermal synthesis method of (1).
Background
Formaldehyde is one of the most important indoor pollutants, and mainly comes from various artificial boards and indoor decorative materials. The peculiar smell in the existing air purification product is still adsorbed by an active carbon filter screen, the service life is short, and secondary pollution is often caused because the filter screen is not replaced in time. Therefore, the research and development of the catalyst can be used for catalytically oxidizing pollutants such as formaldehyde in the air into water and carbon dioxide, and meanwhile, the catalyst can be successfully applied to household appliances or fresh air systems, so that the purpose of purifying indoor air efficiently without consumables is achieved, and the method is of great significance.
Manganese dioxide is a known substance with a formaldehyde removing function at room temperature, and is widely used for preparing formaldehyde removing materials. It has been shown that manganese dioxide can catalytically oxidize formaldehyde, causing it to decompose into carbon dioxide and water. The crystal structure of manganese dioxide is complex, and researches show that the manganese dioxide has 5 main crystals of alpha, beta, gamma and the like and more than 30 secondary crystals, and manganese dioxide with different crystal forms has different characteristics.
The reported preparation methods of manganese dioxide include hydrothermal precipitation, hydrothermal decomposition, solid phase, coprecipitation, sol-gel, electrochemical, microemulsion, rheological phase, gamma-ray irradiation, ozone oxidation, and the like. The difference of the preparation method has different influences on the particle size distribution, the grain size and the crystal form transformation of the nano manganese dioxide, and the property, the structure and the appearance of the nano manganese dioxide have great relations with the preparation method and the preparation conditions. At present, the manganese dioxide with higher crystal form purity can be prepared by adopting a complex process, so that the development of a simple preparation method of the manganese dioxide with high crystal form purity has very practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of manganese dioxide, and the preparation method can simply, conveniently and efficiently prepare epsilon-MnO with high crystal form purity2。
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
Epsilon-MnO2The hydrothermal synthesis method comprises the following operations:
1) preparing a permanganate aqueous solution with the concentration of 2 g/(50-200 mL);
2) putting the permanganate aqueous solution into a hydrothermal kettle, and carrying out hydrothermal synthesis reaction at 150-250 ℃;
3) after the reaction is finished, solid-liquid separation is carried out to obtain epsilon-MnO2。
In some examples of the hydrothermal synthesis method, the concentration of the permanganate aqueous solution is 2 g/(100-200 mL).
In some examples of the hydrothermal synthesis method, the reaction temperature of the hydrothermal synthesis is 150-200 ℃.
In some examples of the hydrothermal synthesis method, the reaction time of the hydrothermal synthesis is 10-18 h.
In some examples of the hydrothermal synthesis method, the reaction temperature of the hydrothermal synthesis is 150-180 ℃, and the reaction time is 10-15 h.
In some examples of the hydrothermal synthesis method, MnO is further added into the hydrothermal kettle during the hydrothermal synthesis process2And (3) a carrier.
In some examples of hydrothermal synthesis methods, the support includes, but is not limited to, activated carbon, ceramic sheets, aluminum substrates, screens that are stable during hydrothermal reaction.
In some examples of hydrothermal synthesis methods, the permanganate is potassium permanganate, sodium permanganate.
In a second aspect of the present invention, there is provided:
an air purifying device comprises a carrier, wherein epsilon-MnO prepared by the hydrothermal synthesis method of the first aspect of the invention is loaded on the carrier2。
In some examples of air purification devices, the support includes, but is not limited to, activated carbon, ceramic sheets, aluminum substrates, screens.
The invention has the beneficial effects that:
in one aspect of the invention, the raw materials used are few, and the epsilon-MnO with high crystal purity can be simply, conveniently and efficiently prepared2。
In one aspect of the invention, the epsilon-MnO prepared2Has a large surface area.
In one aspect of the invention, the epsilon-MnO prepared2Has good formaldehyde degradation activity, and can prepare formaldehyde-removing materials with more excellent performance.
In one aspect of the invention, MnO is added during hydrothermal synthesis2Carrier, hydrothermal synthesizing to obtain supported MnO2The carrier of (3) simplifies subsequent processing.
The air purifying device has lasting formaldehyde removing capacity.
Drawings
FIG. 1 shows ε -MnO as synthesized in example 12An XRD pattern of (a);
FIG. 2 shows ε -MnO synthesized in various examples2The results of the comparison of formaldehyde removal performance of (1).
Detailed Description
In a first aspect of the present invention, there is provided:
Epsilon-MnO2The hydrothermal synthesis method comprises the following operations:
1) preparing a permanganate aqueous solution with the concentration of 2 g/(50-200 mL);
2) putting the permanganate aqueous solution into a hydrothermal kettle, and carrying out hydrothermal synthesis reaction at 150-250 ℃;
3) after the reaction is finished, solid-liquid separation is carried out to obtain epsilon-MnO2。
During the hydrothermal synthesis process, double decomposition reaction of permanganate occurs to generate-MnO2。
In some examples of the hydrothermal synthesis method, the concentration of the permanganate aqueous solution is 2 g/(100-200 mL). The concentration can obtain epsilon-MnO with higher purity2。
In some examples of the hydrothermal synthesis method, the reaction temperature of the hydrothermal synthesis is 150-200 ℃.
In some examples of the hydrothermal synthesis method, the reaction time of the hydrothermal synthesis is 10-18 h.
In some examples of the hydrothermal synthesis method, the reaction temperature of the hydrothermal synthesis is 150-180 ℃, and the reaction time is 10-15 h.
The specific reaction temperature and reaction time may be adjusted within the above ranges according to the reaction conditions.
In some examples of the hydrothermal synthesis method, MnO is further added into the hydrothermal kettle during the hydrothermal synthesis process2And (3) a carrier.
The carrier is used for loading epsilon-MnO2The particles themselves have no particular requirement. In some examples of hydrothermal synthesis methods, the support includes, but is not limited to, activated carbon, ceramic sheets, aluminum substrates, screens that are stable during hydrothermal reaction.
In some examples of hydrothermal synthesis methods, the permanganate is potassium permanganate, sodium permanganate.
In a second aspect of the present invention, there is provided:
an air purifying device comprises a carrier, wherein epsilon-MnO prepared by the hydrothermal synthesis method of the first aspect of the invention is loaded on the carrier2。
In some examples of air cleaning devices, the support includes, but is not limited to, commonly used support materials such as activated carbon, ceramic sheets, aluminum substrates, screens, and the like.
Example 1:
1) preparing a permanganate aqueous solution with the concentration of 2g/200 mL;
2) putting the permanganate aqueous solution into a hydrothermal kettle, and carrying out hydrothermal synthesis reaction for 12 hours at 150 ℃;
3) after the reaction is finished, solid-liquid separation is carried out to obtain epsilon-MnO2。
FIG. 1 shows ε -MnO as synthesized in example 12XRD pattern of (a). As can be seen from the figure, it is ε -MnO was prepared2。
Example 2:
1) preparing a permanganate aqueous solution with the concentration of 2g/100 mL;
2) putting the permanganate aqueous solution into a hydrothermal kettle, and carrying out hydrothermal synthesis reaction for 15h at 200 ℃;
3) after the reaction is finished, solid-liquid separation is carried out to obtain epsilon-MnO2。
Example 3:
1) preparing a permanganate aqueous solution with the concentration of 2g/50 mL;
2) putting the permanganate aqueous solution into a hydrothermal kettle, and carrying out hydrothermal synthesis reaction for 10 hours at 250 ℃;
3) after the reaction is finished, solid-liquid separation is carried out to obtain epsilon-MnO2。
Example 4:
1) preparing a permanganate aqueous solution with the concentration of 2g/120 mL;
2) putting the permanganate aqueous solution into a hydrothermal kettle, and carrying out hydrothermal synthesis reaction for 12 hours at 180 ℃;
3) after the reaction is finished, solid-liquid separation is carried out to obtain epsilon-MnO2。
Different entityExamples preparation of epsilon-MnO2Some of the physical properties are shown in table 1.
Table 1: MnO Synthesis in different examples2Table for comparing properties of
Figure BDA0002155703880000041
Setting the time of the hydrothermal reaction to 12h and the temperature to 180 ℃, comparing the concentrations of different potassium permanganate aqueous solutions to prepare epsilon-MnO by hydrothermal synthesis2The results are shown in Table 2.
Table 2: preparation of epsilon-MnO by hydrothermal synthesis based on concentration of potassium permanganate aqueous solution2Influence of (2)
Figure BDA0002155703880000042
The experimental result shows that when the concentration of the potassium permanganate aqueous solution is 2 g/(100-200) mL, epsilon-MnO2The purity of (2) is higher.
Setting the concentration of the potassium permanganate aqueous solution to be 2g/100ml, setting the time of the hydrothermal reaction to be 12h, and comparing different hydrothermal synthesis temperatures to prepare epsilon-MnO2The results are shown in Table 3.
Table 3: reaction temperature pair of hydrothermal synthesis for preparing epsilon-MnO2Influence of (2)
Figure BDA0002155703880000051
Experimental results show that when the hydrothermal reaction temperature is 150-250 ℃, epsilon-MnO with higher purity can be obtained2However, as the reaction temperature increases, ε -MnO2Relatively increases the particle size, resulting in a decrease in the specific surface area thereof.
Setting the concentration of the potassium permanganate aqueous solution to be 2g/100ml, setting the temperature of the hydrothermal reaction to be 150 ℃, and comparing different hydrothermal synthesis to prepare epsilon-MnO with time2The results are shown in Table 4.
Table 4: reaction time pair of hydrothermal synthesis for preparing epsilon-MnO2Influence of (2)
Figure BDA0002155703880000052
The experimental result shows that the epsilon-MnO is at the same reaction temperature2The particle size of (a) is basically the same, satisfactory results can be obtained when the reaction time is more than 6 hours, and when the reaction time is 10 hours or more, the content does not change significantly any more, preferably 10 to 18 hours.
And (3) performance testing:
ε -MnO prepared in different examples2Comparison of Formaldehyde removal Performance
1) Adding 10g of epsilon-MnO2Preparing slurry, loading the slurry on a paper honeycomb, and preparing a formaldehyde removal module with the size of 10mm by 15mm by 60 mm;
2) the module is placed in a 100L closed cabin, a circulating fan, a heater for formaldehyde volatilization and a support capable of placing a formaldehyde removal module are arranged in the cabin, and the support is provided with a fan;
3) adding a certain amount of formaldehyde solution on a heating volatilizer, heating and starting a circulating fan, closing the circulating fan and a heater in the cabin and starting a fan of a formaldehyde removal module device after a formaldehyde detection instrument displays that the concentration of formaldehyde is stable;
4) recording the initial formaldehyde concentration and the formaldehyde concentrations of 1min, 5min, 10min, 15min, 20min, 25min and 30min, and drawing a formaldehyde removal efficiency curve.
The experimental results are shown in FIG. 2, and the results show that the epsilon-MnO prepared in the embodiments 1-4 of the invention2Compared with the commercial manganese dioxide, the manganese dioxide has better methanol removal performance.
And (3) long-term formaldehyde removal performance test:
ε -MnO prepared by reference to the different examples above2The experimental design of the comparison of the formaldehyde removal performance tests the methanol removal capability of different manganese dioxide materials for multiple times respectively. The results show that the epsilon-MnO synthesized in the examples of the present invention2The formaldehyde removing effect is basically the same for multiple times, and the formaldehyde removing agent hasThe formaldehyde removing efficiency is stable.

Claims (8)

1. Epsilon-MnO2The hydrothermal synthesis method comprises the following operations:
1) preparing a permanganate aqueous solution with the concentration of 2 g/(50-200 mL);
2) putting the permanganate aqueous solution into a hydrothermal kettle, and carrying out hydrothermal synthesis reaction at 150-250 ℃;
3) after the reaction is finished, solid-liquid separation is carried out to obtain epsilon-MnO2；
In the hydrothermal synthesis process, MnO is also added into the hydrothermal kettle2A carrier;
the reaction time of the hydrothermal synthesis is 10-18 h.
2. The hydrothermal synthesis method according to claim 1, characterized in that: the concentration of the permanganate aqueous solution is 2 g/(100-200 mL).
3. The hydrothermal synthesis method according to claim 1 or 2, characterized in that: the reaction temperature of the hydrothermal synthesis is 150-200 ℃.
4. The hydrothermal synthesis method according to claim 1 or 2, characterized in that: the reaction temperature of the hydrothermal synthesis is 150-180 ℃, and the reaction time is 10-15 h.
5. The hydrothermal synthesis method according to claim 1, characterized in that: the carrier comprises at least one of active carbon, a ceramic chip, an aluminum substrate and a filter screen which are stable in the hydrothermal reaction process.
6. The hydrothermal synthesis method according to claim 1, characterized in that: the permanganate is at least one of potassium permanganate and sodium permanganate.
7. An air purification device, including the carrier, its characterized in that: the carrier having the structure of claim 1 to 6The epsilon-MnO prepared by the hydrothermal synthesis method2。
8. The air purification device of claim 7, wherein: the carrier comprises at least one of active carbon, a ceramic chip, an aluminum substrate and a filter screen.
CN201910716781.7A 2019-08-05 2019-08-05 High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method Active CN110482609B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910716781.7A CN110482609B (en) 2019-08-05 2019-08-05 High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910716781.7A CN110482609B (en) 2019-08-05 2019-08-05 High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method

Publications (2)

Publication Number Publication Date
CN110482609A CN110482609A (en) 2019-11-22
CN110482609B true CN110482609B (en) 2022-03-15

Family

ID=68547783

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910716781.7A Active CN110482609B (en) 2019-08-05 2019-08-05 High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method

Country Status (1)

Country Link
CN (1) CN110482609B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111389391A (en) * 2020-04-11 2020-07-10 广东中投环保股份有限公司 Ce doped-MnO2Preparation method and application of nanoparticles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101327959A (en) * 2008-08-01 2008-12-24 中国科学院电工研究所 Preparation of epsilon-MnO2 laminate structure nanosphere
CN102838168A (en) * 2011-06-24 2012-12-26 上海牛翼新能源科技有限公司 Mesoporous manganese oxide nanometer material capable of removing ozone and formaldehyde in air at room temperature simultaneously
CN103771524A (en) * 2014-02-25 2014-05-07 重庆大学 MnO2 nanometer composite material and preparation method thereof
CN107697952A (en) * 2017-10-27 2018-02-16 上海纳米技术及应用国家工程研究中心有限公司 For removing preparation method of manganese bioxide material of low concentration formaldehyde and products thereof and application in air

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101327959A (en) * 2008-08-01 2008-12-24 中国科学院电工研究所 Preparation of epsilon-MnO2 laminate structure nanosphere
CN102838168A (en) * 2011-06-24 2012-12-26 上海牛翼新能源科技有限公司 Mesoporous manganese oxide nanometer material capable of removing ozone and formaldehyde in air at room temperature simultaneously
CN103771524A (en) * 2014-02-25 2014-05-07 重庆大学 MnO2 nanometer composite material and preparation method thereof
CN107697952A (en) * 2017-10-27 2018-02-16 上海纳米技术及应用国家工程研究中心有限公司 For removing preparation method of manganese bioxide material of low concentration formaldehyde and products thereof and application in air

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Synthesis, Characterization and Optical Property of Shrimps-Like Nanostructures of MnO2 by Hydrothermal Route";Toufiq, Arbab Mohammad et al.;《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》;20131231;第13卷(第4期);第2948-2952页 *

Also Published As

Publication number Publication date
CN110482609A (en) 2019-11-22

Similar Documents

Publication Publication Date Title
CN110482610B (en) High-purity alpha-MnO with large surface area2Hydrothermal synthesis method
CN107876035B (en) Carbon quantum dot/titanium dioxide composite photocatalytic material and preparation method and application thereof
CN107555481B (en) Manganese oxide material and preparation method thereof
JP4787968B2 (en) High-efficiency manufacturing method of activated carbon supported with nanometal or metal oxide
CN110357172B (en) Method for preparing cobaltosic oxide nanosheets through MOF-Co and biological template double-confinement
EP2657191A1 (en) Preparation method and use of manganese dioxide nano-rod
CN102921416A (en) Nano composite photocatalytic material and method for preparing same
CN106622206B (en) A kind of mesoporous ceria hollow sphere or mesoporous ceria/carbon composite hollow sphere and preparation method thereof
CN107262133A (en) A kind of preparation method of the photochemical catalyst based on single dispersing bismuth with elementary and carbonitride
CN109762614B (en) Cobaltosic oxide catalyst for methane catalytic combustion, preparation and application thereof
CN114618589B (en) Preparation method and application of ozone degradation catalyst based on iron-based organic framework
CN110482609B (en) High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method
CN113262808A (en) Water-soluble graphite-phase carbon nitride nanosheet catalyst for efficiently removing formaldehyde at room temperature and preparation method thereof
Zhang et al. 3D flower-like NiZnAl multimetal oxide constructed by ultra-thin porous nanosheets: A long-term and stable sensing material for NOx at room temperature
CN103920459A (en) Method for preparing efficient adsorption composite material by taking silicate clay and rice husk as raw materials
CN114849729A (en) Ultraviolet light catalytic oxidation degradation pet peculiar smell composite material for air purification and preparation method thereof
JP2007090342A (en) Catalytic material for producing hydrogen gas from hydrocarbon gas and method of producing the same, and method of producing hydrogen gas using the catalytic material
CN107649145A (en) A kind of catalyst of ozone decomposition and preparation method thereof
CN115676896B (en) Amorphous manganese oxide composite material and preparation method and application thereof
CN111013528B (en) Material for absorbing and decomposing formaldehyde and preparation method thereof
CN115353189B (en) Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen
CN108187701B (en) Preparation method of AgCl/BiOCl photocatalyst with tubular AgCl structure
CN108097273B (en) AgCl/BiOCl photocatalyst with tubular AgCl structure
CN114602489A (en) High-stability non-noble metal-based formaldehyde catalyst and preparation method thereof
JP3047011B2 (en) Carbon-metal composite and method for producing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant