CN112441620B - Alpha-type manganese dioxide with hydrogen ion filled pore canal and preparation method thereof - Google Patents
Alpha-type manganese dioxide with hydrogen ion filled pore canal and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of inorganic nano material synthesis, and discloses alpha manganese dioxide with a pore canal filled with hydrogen ions and a preparation method thereof. The preparation method comprises the following steps: completely dissolving manganese salt in pure water, then adding permanganate solution, standing at room temperature after ultrasonic oscillation, filtering, washing and drying to obtain amorphous manganese oxide; adding the obtained amorphous manganese oxide into an aqueous solution, dispersing, adding concentrated sulfuric acid, uniformly dispersing by ultrasonic vibration, standing for reaction, and then carrying out suction filtration, washing and drying to obtain the alpha-manganese dioxide with hydrogen ions filling the pore channels. The preparation method provided by the invention is simple, convenient to control, and capable of carrying out industrial large-scale production, and the prepared hydrogen ion filled alpha-MnO of the pore canal 2 Can effectively avoid the interference of other alkaline cations and has no side effect on alpha-MnO 2 The expansion significance of the application field is great.
Description
Technical Field
The invention belongs to the field of inorganic nano material synthesis, and in particular relates to alpha-manganese dioxide (alpha-MnO) with hydrogen ion filled pore canal 2 ) And a method for preparing the same.
Background
Among the many common oxides of manganese, manganese dioxide (MnO 2 ) Is one of the most complex structure and the most crystal form. MnO (MnO) 2 Is made of manganese oxide octahedron (MnO) 6 ]One Mn is positioned at the center of the octahedron, 6O are positioned at the vertex angles of the octahedron, octahedral chains are formed between the octahedrons in a co-prismatic mode, and the octahedral chains form different crystal structures in an edge/vertex combination mode. Manganese dioxide of different crystal forms, such as alpha-MnO, can be formed according to the difference of manganese oxide octahedral connection modes 2 ，β-MnO 2 ,γ-MnO 2 ,δ-MnO 2 Etc. Wherein, alpha-MnO 2 It generally shows better activity than other crystal forms of manganese dioxide in the fields of environmental catalysis (such as VOCs catalytic combustion and DeNOx), electrochemistry (such as ORR and OER) and the like.
α-MnO 2 Has a 2×2 pore structure with pore size of 0.46nm, and cation (K is required in the pore + 、Na + 、NH 4 + 、Ba 2+ Etc.) to maintain the tunnel structure. alpha-MnO 2 The preparation method can influence the type, distribution and the like of the pore cations, thereby influencing the activity of the material in different application fields. Common preparation methods, such as low-temperature liquid phase method, hydrothermal method, sol-gel method, reflux method, etc 2 Generally all have K + 、Na + 、NH 4 + The isoelectric cation fills the cells. These cations may mask the acidic sites of the material, allowing alpha-MnO to 2 The use of acid sites as reactive sites is limited. Whereas existing alpha-MnO regarding hydrogen ion filled channels 2 Are all based on NH 4 + alpha-MnO filling pore canal 2 Calcination was performed, but the NH could not be demonstrated in the prior experiments 4 + The ions are completely removed. Therefore, to avoid interference of other basic cations, a hydrogen ion filled alpha-MnO of the pore channel was studied 2 The preparation method has very important significance.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, a primary object of the present invention is to provide an alpha manganese dioxide (alpha-MnO) with hydrogen ion filled channels 2 ) Is prepared by the preparation method of (1). Preparing an amorphous manganese oxide precursor by a low-temperature liquid phase method, and then further converting the amorphous manganese oxide precursor into alpha-MnO of hydrogen ion filled pore channels under the condition of strong acid 2 The preparation method is simple and convenient to control.
Another object of the present invention is to provide an alpha-manganese dioxide (alpha-MnO) having hydrogen ion filled pore channels prepared by the above method 2 )。
The aim of the invention is achieved by the following technical scheme:
a preparation method of alpha-type manganese dioxide with hydrogen ion filling pore channels comprises the following steps:
s1, preparing amorphous manganese oxide: completely dissolving manganese salt in pure water, then adding permanganate solution, standing at room temperature after ultrasonic oscillation, filtering, washing and drying to obtain amorphous manganese oxide;
s2, preparing alpha-MnO of a hydrogen ion filling pore canal 2 : adding and dispersing the amorphous manganese oxide obtained in the step S1 into an aqueous solution, adding concentrated sulfuric acid, uniformly dispersing by ultrasonic vibration, standing for reaction, and then carrying out suction filtration, washing and drying to obtain the alpha-manganese dioxide with hydrogen ions filled in pore channels.
Preferably, the manganese salt in step S1 is manganese sulfate monohydrate; the mass ratio of the manganese salt to the pure water is 1:50-1:30.
Preferably, the permanganate solution in the step S1 is a 40wt.% sodium permanganate solution, and the mass ratio of the sodium permanganate solution to the pure water is 1:30-1:20.
Preferably, the molar ratio of manganese salt to permanganate in the permanganate solution described in step S1 is less than or equal to 3:2.
Preferably, the room temperature standing time described in step S1 is 12 to 24 hours.
Preferably, the mass ratio of the amorphous manganese oxide to the aqueous solution in the step S2 is 1:200-1:300.
Preferably, the volume ratio of the concentrated sulfuric acid to the aqueous solution in the step S2 is 1:10-1:5.
Preferably, the temperature of the standing reaction in the step S2 is 60-90 ℃ and the time is 8-24 h.
The alpha manganese dioxide with the pore canal filled with the hydrogen ions is prepared by the preparation method.
The principle of the invention is as follows:
common preparation methods, such as low-temperature liquid phase method, hydrothermal method, sol-gel method, reflux method, etc 2 Generally all have K + 、Na + 、NH 4 + The channels are filled with iso-basic cations that might mask the acidic sites of the material, such that alpha-MnO 2 The use of acid sites as reactive sites is limited. The invention provides an alpha-MnO of a hydrogen ion filling pore canal 2 The preparation method of the catalyst can effectively avoid other alkaline cationsInterference of the son with alpha-MnO 2 The expansion significance of the application field is great.
Compared with the prior art, the invention has the following advantages and effects:
the preparation method provided by the invention is simple, convenient to control, and capable of carrying out industrial large-scale production, and the prepared hydrogen ion filled alpha-MnO of the pore canal 2 Can effectively avoid the interference of other alkaline cations and has no side effect on alpha-MnO 2 The expansion significance of the application field is great.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalyst prepared in example 1 and comparative example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the catalyst prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
Example 1
alpha-MnO of hydrogen ion filling pore canal 2 The preparation method of (2) comprises the following steps:
s1, preparing amorphous manganese oxide: 3mmol of MnSO 4 Completely dissolving in 50mL of distilled water solution, then adding 2mmol of 40wt.% sodium permanganate water solution, carrying out ultrasonic oscillation for 5 minutes, standing for 24 hours at room temperature to obtain black precipitate, and then carrying out suction filtration and washing until the filtrate is transparent, and drying to obtain amorphous manganese oxide;
s2, preparing alpha-MnO of a hydrogen ion filling pore canal 2 : adding 0.5g of amorphous manganese oxide obtained in S1 into 50mL of distilled water solution, adding 6mL of concentrated sulfuric acid, carrying out ultrasonic oscillation for 5 minutes to uniformly disperse, and standing at 80 DEG CAfter 24 hours of reaction, carrying out suction filtration, washing and drying to obtain alpha-MnO of hydrogen ion filled pore canal 2 。
Subsequently we performed on the synthesized alpha-MnO in the step S2 2 A test characterization was performed and its XRD diffractogram is shown in figure 1. From the figure, it can be seen that the prepared manganese oxide and the alpha-MnO indicated by JCPDF standard card PDF#44-0141 2 Correspondingly, no other miscellaneous peaks exist, which indicates that the alpha-MnO with a pure phase 2x2 structure is synthesized 2 And no K is used in the present invention + 、Na + And NH 4 + And (3) an alkaline cation, which indicates that only hydronium ions can exist in the pore channel. And the diffraction peak position of the whole diffraction peak is shifted to a low angle by 0.9 degrees, which shows that the pore canal is enlarged when only hydronium ions exist. alpha-MnO prepared from this example 2 The alpha-MnO can be seen in the scanning electron microscope (FIG. 2) 2 Is a nanorod morphology with a diameter of 20nm and a length of about 200 nm.
Example 2
alpha-MnO of hydrogen ion filling pore canal 2 The preparation method of (2) comprises the following steps:
s1, preparing amorphous manganese oxide: 3mmol of MnSO 4 Completely dissolving in 50mL of distilled water solution, then adding 3 mmole of 40wt.% sodium permanganate water solution, carrying out ultrasonic oscillation for 5 minutes, standing for 24 hours at room temperature to obtain black precipitate, and then carrying out suction filtration and washing until the filtrate is transparent and drying to obtain amorphous manganese oxide;
s2, preparing alpha-MnO of a hydrogen ion filling pore canal 2 : adding 0.5g of amorphous manganese oxide obtained in the step S1 into 50mL of distilled water solution, adding 10mL of concentrated sulfuric acid, carrying out ultrasonic oscillation for 5 minutes to uniformly disperse, standing at 90 ℃ for reaction for 8 hours, and carrying out suction filtration, washing and drying to obtain alpha-MnO of hydrogen ion filled pore channels 2 。
Example 3
alpha-MnO of hydrogen ion filling pore canal 2 The preparation method of (2) comprises the following steps:
s1, preparing amorphous manganese oxide: 3mmol of MnSO 4 Completely dissolved in 50mL of distilled water, followed by the addition of 2mmol of 40wt.% aqueous sodium permanganate solutionStanding for 24 hours at room temperature after ultrasonic oscillation for 5 minutes to obtain black precipitate, and then carrying out suction filtration and washing until filtrate is transparent, and drying to obtain amorphous manganese oxide;
s2, preparing alpha-MnO of a hydrogen ion filling pore canal 2 : adding 0.5g of amorphous manganese oxide obtained in the step S1 into 50mL of distilled water solution, adding 8mL of concentrated sulfuric acid, carrying out ultrasonic oscillation for 5 minutes to uniformly disperse, standing at 65 ℃ for reaction for 18 hours, and carrying out suction filtration, washing and drying to obtain alpha-MnO of hydrogen ion filled pore channels 2 。
Comparative example 1
MnO (MnO) 2 The preparation method of (2) comprises the following steps:
s1, preparing amorphous manganese oxide: 3mmol of MnSO 4 Completely dissolving in 50mL of distilled water solution, then adding 2mmol of 40wt.% sodium permanganate water solution, carrying out ultrasonic oscillation for 5 minutes, standing for 24 hours at room temperature to obtain black precipitate, and then carrying out suction filtration and washing until the filtrate is transparent and drying to obtain amorphous manganese oxide;
s2, preparing alpha-MnO of a hydrogen ion filling pore canal 2 : adding 0.5g of amorphous manganese oxide obtained in the step S1 into 50mL of distilled water solution, adding 1mL of concentrated sulfuric acid, carrying out ultrasonic oscillation for 5 minutes to uniformly disperse, standing at 80 ℃ for reaction for 24 hours, and carrying out suction filtration, washing and drying to obtain MnO 2 。
As shown in the XRD diffraction pattern of the product of the comparative example in FIG. 1, it can be seen that the prepared manganese oxide and Gamma-MnO indicated by JCDF standard card PDF#14-0615 2 Correspondingly, the failure to produce alpha-MnO in the presence of a non-strong acid 2 。
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the alpha-type manganese dioxide with the hydrogen ion filling pore canal is characterized by comprising the following steps:
s1, preparing amorphous manganese oxide: completely dissolving manganese salt in pure water, then adding permanganate solution, standing at room temperature after ultrasonic oscillation, filtering, washing and drying to obtain amorphous manganese oxide;
s2, preparing alpha-MnO of a hydrogen ion filling pore canal 2 : adding and dispersing the amorphous manganese oxide obtained in the step S1 into an aqueous solution, adding concentrated sulfuric acid, uniformly dispersing by ultrasonic vibration, standing for reaction, and then carrying out suction filtration, washing and drying to obtain alpha-manganese dioxide with hydrogen ions filled in pore channels;
the mass ratio of the amorphous manganese oxide to the aqueous solution is 1:200-1:300; the volume ratio of the concentrated sulfuric acid to the aqueous solution in the step S2 is 1:10-1:5.
2. The method of manufacturing according to claim 1, characterized in that: the manganese salt in the step S1 is manganese sulfate monohydrate; the mass ratio of the manganese salt to the pure water is 1:50-1:30.
3. The method of manufacturing according to claim 1, characterized in that: the permanganate solution in the step S1 is 40wt.% sodium permanganate solution, and the mass ratio of the sodium permanganate solution to the pure water is 1:30-1:20.
4. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the manganese salt to the permanganate in the permanganate solution in the step S1 is less than or equal to 3:2.
5. The method of manufacturing according to claim 1, characterized in that: the standing time at room temperature in the step S1 is 12-24 hours.
6. The method of manufacturing according to claim 1, characterized in that: the temperature of the standing reaction in the step S2 is 60-90 ℃ and the time is 8-24 h.
7. An alpha manganese dioxide having hydrogen ion filled pores prepared by the preparation method of any one of claims 1 to 6.
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| CN102017997A (en) * | 2009-09-18 | 2011-04-20 | 唐幸福 | High-efficiency monatomic silver nanowire antibiotic material |
| CN102476831A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for synthesizing OMS-2 manganese oxide octahedral molecular sieve |
| CN107026026A (en) * | 2017-03-17 | 2017-08-08 | 东南大学 | A kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges |
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| CN102017997A (en) * | 2009-09-18 | 2011-04-20 | 唐幸福 | High-efficiency monatomic silver nanowire antibiotic material |
| CN102476831A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for synthesizing OMS-2 manganese oxide octahedral molecular sieve |
| CN107026026A (en) * | 2017-03-17 | 2017-08-08 | 东南大学 | A kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges |
Non-Patent Citations (2)
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| a-MnO2纳米棒水热法制备与表征;刘艳;《四川冶金》;20170630;第39卷;第14-17页 * |
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