CN103896341A - Preparation method and catalytic application of alpha-MnO2 with three-dimensional structure - Google Patents
Preparation method and catalytic application of alpha-MnO2 with three-dimensional structure Download PDFInfo
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- CN103896341A CN103896341A CN201410070637.8A CN201410070637A CN103896341A CN 103896341 A CN103896341 A CN 103896341A CN 201410070637 A CN201410070637 A CN 201410070637A CN 103896341 A CN103896341 A CN 103896341A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
- 229910003144 α-MnO2 Inorganic materials 0.000 title abstract 3
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000004159 Potassium persulphate Substances 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention relates to the field of preparation and application of inorganic nano materials, and particularly relates to a preparation method and a catalytic application of alpha-MnO2 with a three-dimensional structure. The preparation method of alpha-MnO2 with the three-dimensional structure comprises the following steps: 1) dissolving soluble manganese salt, potassium persulfate and potassium sulfate in distilled water, and stirring to completely dissolve the components to form a solution A; 2) stirring the solution A, and meanwhile adding concentrated sulfuric acid to form a solution B; 3) reacting the solution B at 75-85 DEG C for 18-24 hours to obtain a product. The preparation method provided by the invention is cheap and easy in obtaining of raw materials, low in cost, low in synthesis temperature, simple in process, easy to implement, stable in product quality, good in process repeatability and easy for industrial production.
Description
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 its unique structure, the performance of excellence and cheap cost are all widely used at aspects such as secondary cell, magneticsubstance, catalyzer, sorbent material and ion-exchanges.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 of preparing at present manganese dioxide three-dimensional structure is generally hydrothermal method, catalysis method, masterplate method etc.Hard template method can by changing the pattern of template, to realize the size of the hollow structure to final product controlled, or control wall thickness and the wall composition of hollow structure by changing reaction conditions; But hard template method need to will be carried out aftertreatment to template after reaction finishes, need to pass through high-temperature calcination or soda acid etching, this not only consumes mass energy, and products therefrom is easily reunited, cause distribution of sizes inhomogeneous, and likely product pattern is destroyed or introduce other impurity.Hydrothermal method is to utilize encloses container at high temperature to produce high pressure, and reaction is carried out fast, still, due to the restriction of container volume and temperature of reaction, is generally difficult to large-scale production.Xie Yi group is with AgNO
3prepare at normal temperatures microballoon (the Chemical Communications of manganese dioxide three-dimensional structure with ammonium persulphate oxidation manganous sulfate as catalyzer, 918 pages of 7 phases in 2005), but long reaction time (2 days), and use precious metal Silver Nitrate as catalyzer.
But without any template, tensio-active agent or catalyzer in the situation that, be difficult at present prepare the α-MnO of three-dimensional structure under gentle condition
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 prepared α-MnO of 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 and dissolves the rear solution A that forms completely;
2) one side stirred solution A, adds the vitriol oil to form solution B on one side;
3) solution B is placed at 75 ~ 85 DEG C and reacts 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 that preparation method is prepared
2can be used as the application of catalyzer in catalysis.
Further, described in, be applied as the perfect combustion of catalysis toluene.
In the middle of the present invention, by adding the concentration of potassium sulfate control reactant potassium ion and sulfate radical, can induce and form 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 that forms three-dimensional structure
2.
The present invention has following beneficial effect:
(1) preparation method's provided by the invention raw material is cheap and 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, easily suitability for industrialized production.
(2) Manganse Dioxide that prepared by the present invention is three-dimensional structure, and size, pattern homogeneous, does not need to use any catalyzer, masterplate 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 catalytically, burning has good catalytic activity, its combustion initiation temperature T
10% (toluene conversion reaches 10% corresponding temperature of reaction) is 200 DEG C, perfect combustion temperature T
99% (toluene conversion reaches 99% corresponding temperature of reaction) is 230 DEG C.
Brief description of the drawings
Fig. 1 is the X x ray diffration pattern x of the prepared Manganse Dioxide of embodiments of the invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the prepared Manganse Dioxide of embodiments of the invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the prepared Manganse Dioxide of embodiments of the invention 2.
Fig. 4 is the toluene catalytically combustionproperty figure of the prepared Manganse Dioxide of embodiments of the invention 1 during as catalyzer.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in detail.
Material, reagent etc. used in following embodiment, 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 and dissolve the rear solution A that forms completely; Stir described solution A on one side, on one side 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; Described mixed liquid B is placed at 80 DEG C, to react after 24 hours obtains product, product is used respectively to 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 pattern obtains by scanning electron microscope result, as shown in Figure 2, and as figure can find out that material has three-dimensional structure, and size homogeneous.
embodiment 2
First 1.75mmol manganous sulfate, 2mmol Potassium Persulphate and 2mmol potassium sulfate are dissolved in 50mL distilled water, stir and dissolve the rear solution A that forms completely; Stir described solution A on one side, on one side 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; Described mixed liquid B is placed at 85 DEG C, to react after 20 hours obtains product, product is used respectively to 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 of preparing with embodiment 1 is similar); Material pattern obtains by scanning electron microscope result, as shown in Figure 3, and as figure can find out that material has three-dimensional structure, and size homogeneous.
embodiment 3
First 2mmol manganous sulfate, 2mmol Potassium Persulphate and 1.75mmol potassium sulfate are dissolved in 50mL distilled water, stir and dissolve the rear solution A that forms completely; Stir described solution A on one side, on one side 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; Described mixed liquid B is placed at 75 DEG C, to react after 22 hours obtains product, product is used respectively to 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 of preparing with embodiment 1 is similar), and known its material has three-dimensional structure, and size homogeneous.
embodiment 4
First manganese dioxide powder prepared embodiment 1 is pressed into sheet with tabletting machine, then uses mortar grind into powder, 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, taking toluene catalytically combustion reactions as 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, and after FID, detector detects online.Toluene combustion initiation temperature and approximate complete invert point are designated as respectively T
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 completely and transform at 230 DEG C.
The above embodiment has only expressed embodiments of the present invention; it describes comparatively concrete and detailed; but can not therefore be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme that adopts the form that is equal to replacement or equivalent transformation to obtain, within all should dropping on protection scope of the present invention.
Claims (7)
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 and dissolves the rear solution A that forms completely;
2) one side stirred solution A, adds the vitriol oil to form solution B on one side;
3) solution B is placed at 75 ~ 85 DEG C and reacts after 18 ~ 24 hours and obtain product.
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.
5. α-the MnO of a kind of three-dimensional structure according to claim 1
2preparation method, it is characterized in that, the volume ratio of the described vitriol oil and distilled water is 25:0.75 ~ 1.25.
6. α-the MnO of the three-dimensional structure as described in claim 1 ~ 5 any one
2α-MnO that preparation method is prepared
2can be used as the application of catalyzer in catalysis.
7. the application in catalysis according to claim 6, is characterized in that, described in be applied as the perfect combustion of catalysis toluene.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854871A (en) * | 2016-04-27 | 2016-08-17 | 广东工业大学 | Preparation method and application of catalyst for purification treatment of volatile organic compounds (VOCs) |
| 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 |
| 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 |
| CN112456561A (en) * | 2020-12-15 | 2021-03-09 | 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 |
| CN112607781A (en) * | 2020-12-16 | 2021-04-06 | 嘉应学院 | alpha-MnO of non-porous channel ion2Preparation method of (1) |
| CN112614607A (en) * | 2020-12-02 | 2021-04-06 | 中广核研究院有限公司 | Preparation method of radionuclide manganese-54 |
| CN112657529A (en) * | 2020-12-24 | 2021-04-16 | 广东工业大学 | Nitrogen-doped modified manganese dioxide catalyst and preparation method thereof |
| CN112875759A (en) * | 2021-01-28 | 2021-06-01 | 嘉应学院 | Three-dimensional echinoid Na-alpha-MnO2Hydrothermal synthesis method |
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|---|---|---|---|---|
| CN1824383A (en) * | 2005-02-21 | 2006-08-30 | 中国科学院大连化学物理研究所 | Manganese oxide catalyst used for toluene liquid phase catalytic oxidation, its preparation method and application |
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2014
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Patent Citations (1)
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| CN1824383A (en) * | 2005-02-21 | 2006-08-30 | 中国科学院大连化学物理研究所 | Manganese oxide catalyst used for toluene liquid phase catalytic oxidation, its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 陈冬梅等: "液相法制备纳米二氧化锰", 《贵州大学学报(自然科学版)》, vol. 26, no. 4, 31 August 2009 (2009-08-31), pages 20 - 23 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854871A (en) * | 2016-04-27 | 2016-08-17 | 广东工业大学 | Preparation method and application of catalyst for purification treatment of volatile organic compounds (VOCs) |
| 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 |
| CN112456561A (en) * | 2020-12-15 | 2021-03-09 | 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 |
| CN112607781A (en) * | 2020-12-16 | 2021-04-06 | 嘉应学院 | alpha-MnO of non-porous channel ion2Preparation method of (1) |
| 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 |
| CN112875759A (en) * | 2021-01-28 | 2021-06-01 | 嘉应学院 | Three-dimensional echinoid Na-alpha-MnO2Hydrothermal synthesis method |
| 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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