CN103896341B - A kind of α-MnO of three-dimensional structure 2preparation method and catalytic applications - Google Patents

A kind of α-MnO of three-dimensional structure 2preparation method and catalytic applications Download PDF

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CN103896341B
CN103896341B CN201410070637.8A CN201410070637A CN103896341B CN 103896341 B CN103896341 B CN 103896341B CN 201410070637 A CN201410070637 A CN 201410070637A CN 103896341 B CN103896341 B CN 103896341B
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dimensional structure
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CN103896341A (en
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励春亚
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Shanghai Mclean Biochemical Technology Co ltd
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Xiangshan Xingqi Electric Appliance Technology Co Ltd
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Abstract

The present invention relates to inorganic nano material preparation and Application Areas, be specifically related to a kind of α-MnO of three-dimensional structure 2preparation method and catalytic applications.A kind of α-MnO of three-dimensional structure 2preparation method, comprise the following steps: 1) by soluble manganese salt, Potassium Persulphate, potassium sulfate is dissolved in distilled water, stir completely dissolve after form solution A; 2) one side stirred solution A, adds the vitriol oil and forms solution B; 3) react at solution B being placed in 75 ~ 85 DEG C after 18 ~ 24 hours and obtain product.The cheaper starting materials of preparation method provided by the invention is easy to get, and cost is low, and synthesis temperature is low, and technique is simple and easy to realize, and constant product quality and process repeatability can be good, easy suitability for industrialized production.

Description

A kind of α-MnO of three-dimensional structure 2preparation method and catalytic applications
Technical field
The present invention relates to inorganic nano material preparation and Application Areas, be specifically related to a kind of α-MnO of three-dimensional structure 2preparation method and catalytic applications.
Background technology
Manganse Dioxide is a kind of oxide compound with essential industry purposes, because the structure of its uniqueness, excellent performance and cheap cost are all widely used in secondary cell, magneticsubstance, catalyzer, sorbent material and ion-exchange etc.And the nano material of three-dimensional structure has high-specific surface area, special appearance structure, often can produce some peculiar physicochemical property, make the nano material of three-dimensional structure have important application in many technical fields such as photonic crystal, biochemistry and chemical industry.As existing document " American Chemical Society " (Journal of the American Chemical Society, 2005 41 phase 14184 pages) report utilizes hydrothermal method can prepare the α-MnO of three-dimensional structure 2.
The method preparing manganese dioxide three-dimensional structure is at present generally hydrothermal method, catalysis method, masterplate method etc.Hard template method can realize the size of the hollow structure of final product controlled by the pattern changing template, or controls wall thickness and the wall composition of hollow structure by changing reaction conditions; But hard template method needs to carry out aftertreatment to template after the completion of reaction, need through high-temperature calcination or soda acid etching, this not only consumes mass energy, and products therefrom is easily reunited, cause distribution of sizes uneven, and likely product morphology destroyed or introduce other impurity.Hydrothermal method utilizes encloses container at high temperature to produce high pressure, and reaction is carried out fast, but due to the restriction of container volume and temperature of reaction, be generally difficult to large-scale production.Xie Yi group is with AgNO 3prepare microballoon (the Chemical Communications of manganese dioxide three-dimensional structure at normal temperatures with ammonium persulphate oxidation manganous sulfate as catalyzer, 7 phase in 2005 918 pages), but long reaction time (2 days), and employ precious metal Silver Nitrate as catalyzer.
But when without any template, tensio-active agent or catalyzer, be difficult to the α-MnO preparing three-dimensional structure under mild conditions at present 2.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of without template, tensio-active agent or catalyzer, the α-MnO of easy industrialized three-dimensional structure 2preparation method.
Another object of the present invention is to provide the α-MnO prepared by this preparation method 2can be used as the application of catalyzer in catalysis.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of α-MnO of three-dimensional structure 2preparation method, comprise the following steps:
1) by soluble manganese salt, Potassium Persulphate, potassium sulfate is dissolved in distilled water, stirs after dissolving completely and forms solution A;
2) one side stirred solution A, adds the vitriol oil and forms solution B;
3) react at solution B being placed in 75 ~ 85 DEG C after 18 ~ 24 hours and obtain product.
Further, described soluble manganese salt is manganous sulfate.
Further, described soluble manganese salt, Potassium Persulphate, the mol ratio of potassium sulfate is 0.75 ~ 1.25:0.75 ~ 1.25:0.75 ~ 1.25.
Further, described soluble manganese salt, Potassium Persulphate, the mol ratio of potassium sulfate is preferably 1:1:1.
Further, the volume ratio of the described vitriol oil and distilled water is 25:0.75 ~ 1.25.
α-the MnO of three-dimensional structure 2α-MnO prepared by preparation method 2can be used as the application of catalyzer in catalysis.
Further, the perfect combustion of catalysis toluene is applied as described in.
In the middle of the present invention, control the concentration of reactant potassium ion and sulfate radical by adding potassium sulfate, can induced synthesis α-MnO 2; And the consumption of sulfuric acid in control reaction solution, make the oxidisability of reaction system higher, at 75 ~ 85 DEG C, just can react the nanometer α-MnO forming three-dimensional structure 2.
The present invention has following beneficial effect:
(1) cheaper starting materials of preparation method provided by the invention is easy to get, and cost is low, and synthesis temperature is low, and technique is simple and easy to realize, and constant product quality and process repeatability can be good, easy suitability for industrialized production.
(2) Manganse Dioxide that prepared by the present invention is three-dimensional structure, and size, pattern are homogeneous, does not need to use any catalyzer, template agent or tensio-active agent etc. in building-up process.
(3), when the Manganse Dioxide with hollow structure that prepared by the present invention is used as catalyzer, to toluene catalytic combustion, there is good catalytic activity, its combustion initiation temperature T 10% (toluene conversion reaches the temperature of reaction corresponding to 10%) is 200 DEG C, perfect combustion temperature T 99% (toluene conversion reaches the temperature of reaction corresponding to 99%) is 230 DEG C.
Accompanying drawing explanation
The X x ray diffration pattern x of the Manganse Dioxide of Fig. 1 prepared by embodiments of the invention 1.
The scanning electron microscope (SEM) photograph of the Manganse Dioxide of Fig. 2 prepared by embodiments of the invention 1.
The scanning electron microscope (SEM) photograph of the Manganse Dioxide of Fig. 3 prepared by embodiments of the invention 2.
The Manganse Dioxide of Fig. 4 prepared by embodiments of the invention 1 is as toluene catalytic combustion performance map during catalyzer.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in detail.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
embodiment 1
First 2mmol manganous sulfate, 2mmol Potassium Persulphate and 2mmol potassium sulfate are dissolved in 50mL distilled water, stir after dissolving completely and form solution A; While stir described solution A, the vitriol oil is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and sulfuric acid is 25:1; React at described mixed liquid B is placed in 80 DEG C after 24 hours and obtain product, product is used respectively distilled water and absolute ethanol washing for several times, put into 60 DEG C of loft drier dry, obtain the α-MnO of described three-dimensional structure 2.Product is accredited as α-MnO through X ray powder diffraction 2; Powder x-ray diffraction result is as shown in Fig. 1; Material morphology is obtained by scanning electron microscope result, as shown in Figure 2, as figure can find out that material has three-dimensional structure, and size uniformity.
embodiment 2
First 1.75mmol manganous sulfate, 2mmol Potassium Persulphate and 2mmol potassium sulfate are dissolved in 50mL distilled water, stir after dissolving completely and form solution A; While stir described solution A, the vitriol oil is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and sulfuric acid is 25:1.1; React at described mixed liquid B is placed in 85 DEG C after 20 hours and obtain product, product is used respectively distilled water and absolute ethanol washing for several times, put into 60 DEG C of loft drier dry, obtain the α-MnO of described three-dimensional structure 2.Product is accredited as α-MnO through X ray powder diffraction 2(Manganse Dioxide of the hollow structure prepared with embodiment 1 is similar); Material morphology is obtained by scanning electron microscope result, as shown in Figure 3, as figure can find out that material has three-dimensional structure, and size uniformity.
embodiment 3
First 2mmol manganous sulfate, 2mmol Potassium Persulphate and 1.75mmol potassium sulfate are dissolved in 50mL distilled water, stir after dissolving completely and form solution A; While stir described solution A, the vitriol oil is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and sulfuric acid is 25:1; React at described mixed liquid B is placed in 75 DEG C after 22 hours and obtain product, product is used respectively distilled water and absolute ethanol washing for several times, put into 60 DEG C of loft drier dry, obtain the α-MnO of described three-dimensional structure 2.Products therefrom is through X-ray powder diffraction, scanning electron microscope qualification (Manganse Dioxide of the three-dimensional structure prepared with embodiment 1 is similar), and its material known has three-dimensional structure, and size uniformity.
embodiment 4
First the manganese dioxide powder tabletting machine prepared by embodiment 1 is pressed into sheet, then uses mortar grinder powdered, be finally screened into 40 ~ 60 orders (d=0.3mm-0.45mm) with standard sieve, obtain catalyst fines finished product.On micro fixed-bed reactor with toluene catalytic combustion reaction for probe reaction, measure the activity of catalyzer, wherein toluene concentration is 4.0g/m 3, air speed is 10000h -1, α-MnO 20.2 g+ quartz sand 0.2 g is catalyst levels, uses gas-chromatography, detector on-line checkingi after FID.Toluene combustion initiation temperature and approximate complete invert point are designated as T respectively 10%and T 99%.As shown in Figure 4, the Manganse Dioxide of three-dimensional structure makes toluene just take fire at 210 DEG C to catalytic performance, can be similar to transform completely at 230 DEG C.
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.

Claims (1)

1. α-the MnO of a three-dimensional structure 2preparation method, it is characterized in that, comprise the following steps:
1) by soluble manganese salt, Potassium Persulphate, potassium sulfate is dissolved in distilled water, stirs after dissolving completely and forms solution A;
2) one side stirred solution A, adds the vitriol oil and forms solution B;
3) react at solution B being placed in 75 ~ 85 DEG C after 18 ~ 24 hours and obtain product;
The volume ratio of the described vitriol oil and distilled water is 1 ~ 1.1:25.
2. α-the MnO of a kind of three-dimensional structure according to claim 1 2preparation method, it is characterized in that, described soluble manganese salt is manganous sulfate.
3. α-the MnO of a kind of three-dimensional structure according to claim 1 2preparation method, it is characterized in that, described soluble manganese salt, Potassium Persulphate, the mol ratio of potassium sulfate is 0.75 ~ 1.25:0.75 ~ 1.25:0.75 ~ 1.25.
4. α-the MnO of a kind of three-dimensional structure according to claim 3 2preparation method, it is characterized in that, described soluble manganese salt, Potassium Persulphate, the mol ratio of potassium sulfate is preferably 1:1:1.
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CN105854871B (en) * 2016-04-27 2019-03-29 广东工业大学 A kind of preparation method and application of VOCs purified treatment catalyst
CN108751335A (en) * 2018-05-04 2018-11-06 中山大学 A kind of method of antibiotic in light-Fenton-like system concerted catalysis oxidative degradation water environment
CN108695520A (en) * 2018-05-22 2018-10-23 厦门理工学院 α-MnO2Oxygen reduction catalyst and preparation method thereof and metal-air battery
CN112614607A (en) * 2020-12-02 2021-04-06 中广核研究院有限公司 Preparation method of radionuclide manganese-54
CN112456561B (en) * 2020-12-15 2022-10-04 广东工业大学 Low-temperature liquid phase preparation method of three-dimensional sea urchin-shaped hydrogen ion filled alpha-type manganese dioxide and prepared alpha-type manganese dioxide
CN112607781B (en) * 2020-12-16 2022-12-23 嘉应学院 alpha-MnO of non-porous channel ion 2 Preparation method of (1)
CN112657529A (en) * 2020-12-24 2021-04-16 广东工业大学 Nitrogen-doped modified manganese dioxide catalyst and preparation method thereof
CN112875759B (en) * 2021-01-28 2022-11-22 嘉应学院 Three-dimensional echinoid Na-alpha-MnO 2 Hydrothermal synthesis method

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