CN112456561B - 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 - Google Patents
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 Download PDFInfo
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- CN112456561B CN112456561B CN202011482507.7A CN202011482507A CN112456561B CN 112456561 B CN112456561 B CN 112456561B CN 202011482507 A CN202011482507 A CN 202011482507A CN 112456561 B CN112456561 B CN 112456561B
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Abstract
The invention belongs to the field of synthesis of inorganic nano materials, and discloses alpha-MnO filled with three-dimensional echinoid hydrogen ions 2 Low temperature liquid phase preparation method and prepared alpha-MnO 2 . TheThe preparation method comprises the following steps: completely dissolving manganese salt in an aqueous solution containing concentrated sulfuric acid, adding sodium persulfate, uniformly dispersing by ultrasonic oscillation, heating, standing, reacting, carrying out suction filtration, washing and drying to obtain the alpha-type manganese dioxide filled with three-dimensional sea urchin-shaped hydrogen ions. The preparation method provided by the invention is simple and convenient to control, and can complete the reaction at 100 ℃, so that industrial scale-up production can be carried out, and the prepared alpha-MnO of the hydrogen ion filled pore channel 2 In the shape of three-dimensional sea urchin, for alpha-MnO 2 The application field has great extension significance.
Description
Technical Field
The invention belongs to the field of inorganic nano material synthesis, and particularly relates to alpha-type manganese dioxide (alpha-MnO) filled with three-dimensional echinoid hydrogen ions 2 ) The low temperature liquid phase preparation method and the prepared alpha-type manganese dioxide.
Background
Among the many common manganese oxides, manganese dioxide (MnO) 2 ) The crystal form is the most complex structure and the most crystal form. MnO 2 Is manganese oxygen octahedron [ MnO ] 6 ]The structure unit is one of Mn in the center of octahedron and 6O in the vertex angle of the octahedron, and octahedron chains are formed between the octahedrons in a co-edge mode and 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 different manganese-oxygen octahedral connection modes 2 ，β-MnO 2 ，γ-MnO 2 ，δ-MnO 2 And the like. And alpha-MnO 2 The preparation method is various, and the controllable synthesis of the compound is usually based on the regulation of parameters such as a redox system, temperature, acidity, time and the like to control the morphology size, the specific surface area, the pore channel filling ions, the conductivity and the crystallinity of the product.
α-MnO 2 Has a 2 × 2 pore channel structure, pore channel size of 0.46nm, and pore channels with different pore diametersTo have a cation (K) + 、Na + 、NH 4 + 、Ba 2+ Etc.) to maintain the cell structure. alpha-MnO 2 The preparation method can influence the species and distribution of the cations in the pore channels, and further influence 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 and the like, for preparing alpha-MnO 2 Generally all have K + 、Na + 、NH 4 + Etc. basic cations fill the pores. These cations may mask the acid sites of the material, allowing alpha-MnO 2 The application of the method is limited in that the acid site is used as a reactive site. The existing alpha-MnO for filling the pore channel with hydrogen ions 2 All reports are based on the use of NH 4 + alpha-MnO for filling pore channel 2 Obtained by calcination, but the prior experiments can not prove NH 4 + The ions are completely removed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide three-dimensional echinoid hydrogen ion filled alpha-type manganese dioxide (alpha-MnO) 2 ) The low temperature liquid phase preparation method of (1). The method synthesizes the alpha-MnO filled with hydrogen ions in the three-dimensional sea urchin shape by one step through oxidation-reduction reaction under the conditions of strong acid and low temperature 2 The preparation method is simple and convenient to control.
The invention also aims to provide the preparation method
The purpose of the invention is realized by the following technical scheme:
a low-temperature liquid phase preparation method of three-dimensional sea urchin-shaped hydrogen ion filled alpha-type manganese dioxide comprises the following steps: completely dissolving manganese salt in an aqueous solution containing concentrated sulfuric acid, adding sodium persulfate, uniformly dispersing by ultrasonic oscillation, heating, standing, reacting, carrying out suction filtration, washing and drying to obtain the alpha-type manganese dioxide filled with three-dimensional sea urchin-shaped hydrogen ions.
Preferably, the manganese salt is manganese sulfate.
Preferably, the molar ratio of the manganese salt to the sodium persulfate is 1:1-2.
Preferably, the volume ratio of the concentrated sulfuric acid to the water in the aqueous solution containing the concentrated sulfuric acid is 1.
Preferably, the time for the heating and standing reaction is 6 to 24 hours.
Preferably, the temperature of the heating and standing reaction is 60-90 ℃.
An alpha-type manganese dioxide prepared by the above preparation method.
Compared with the prior art, the invention has the following advantages and effects:
the preparation method provided by the invention is simple and convenient to control, and can complete the reaction at 100 ℃, so that industrial scale-up production can be carried out, and the prepared alpha-MnO of the hydrogen ion filled pore channel 2 In the shape of three-dimensional sea urchin, for alpha-MnO 2 The application field has great extension significance.
Drawings
FIG. 1 is an X-ray diffraction pattern of catalysts prepared in example 1 of the present invention and comparative example 1.
FIG. 2 is a scanning electron micrograph of a catalyst prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes from the invention, including those variations and alterations made by those skilled in the art, are intended to be covered by the claims.
Example 1
Three-dimensional echinoid hydrogen ion filled alpha-MnO 2 The low-temperature liquid phase preparation method comprises the following steps:
adding 3mmol of MnSO 4 Completely dissolved in 50mL of distilled water, followed by addition of 8mL of concentrated sulfuric acid, followed by addition of 3mmol of Na 2 S 2 O 8 Standing for 12h at 80 ℃ after complete stirring and dissolution to obtain black precipitate, then performing suction filtration and washing until filtrate is transparent, and drying to obtain alpha-MnO filled with three-dimensional echinoid hydrogen ions 2 。
We subsequently investigated the alpha-MnO obtained above 2 The test characterization is carried out, and the XRD diffraction pattern of the test characterization is shown in figure 1. From the figure, the manganese oxide prepared and the alpha-MnO indicated by JCPDF Standard card PDF #44-0141 are known 2 Correspondingly, no other miscellaneous peak exists, which indicates that the alpha-MnO with the pure phase 2x2 structure is synthesized 2 And no K is used in the present invention + And NH 4 + And alkaline cations, which indicates that only hydronium ions may exist in the pore channels. And the diffraction peak position of the whole body is shifted to a low angle by 0.9 degrees, which shows that the pore channels are enlarged when the pore channels only contain hydronium ions. alpha-MnO prepared from this example 2 The alpha-MnO can be seen in the scanning electron micrograph (FIG. 2) 2 Is in a three-dimensional sea urchin-shaped appearance, and the sea urchin is composed of nano rods.
Example 2
Three-dimensional echinoid hydrogen ion filled alpha-MnO 2 The low-temperature liquid phase preparation method comprises the following steps:
adding 3mmol of MnSO 4 Completely dissolved in 50mL of distilled water, followed by addition of 5mL of concentrated sulfuric acid, followed by addition of 6mmol of Na 2 S 2 O 8 Standing for 6h at 90 ℃ after complete stirring and dissolution to obtain black precipitate, then performing suction filtration and washing until filtrate is transparent, and drying to obtain alpha-MnO filled with three-dimensional echinoid hydrogen ions 2 。
Example 3
alpha-MnO filled with three-dimensional echinoid hydrogen ions 2 The low-temperature liquid phase preparation method comprises the following steps:
adding 3mmol of MnSO 4 Completely dissolved in 50mL of distilled water, followed by addition of 10mL of concentrated sulfuric acid, followed by addition of 1.5mmol of Na 2 S 2 O 8 Standing at 60 ℃ for 24h after complete stirring and dissolution to obtain black precipitate, then performing suction filtration and washing until filtrate is transparent, and drying to obtain alpha-MnO filled with three-dimensional echinoid hydrogen ions 2 。
Comparative example 1
MnO (MnO) 2 The preparation method comprises the following steps:
adding 3mmol of MnSO 4 Completely dissolved in 50mL of distilled water, followed by addition of 1mL of concentrated sulfuric acid and subsequent addition of 1.5mmol of Na 2 S 2 O 8 Stirring and dissolving completely, standing at 80 deg.C for 24 hr to obtain black precipitate, filtering, washing until filtrate is transparent, and drying to obtain MnO 2 。
The XRD diffractogram of the comparative product is shown in FIG. 1, and it is known that the manganese oxide prepared is gamma-MnO indicated by JCPDF Standard card PDF #14-0644 2 Correspondingly, it is shown that alpha-MnO cannot be generated under the condition of non-strong acid 2 。
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 (3)
1. A low-temperature liquid phase preparation method of three-dimensional sea urchin-shaped hydrogen ion filled alpha-type manganese dioxide is characterized by comprising the following steps: completely dissolving manganese sulfate in an aqueous solution containing concentrated sulfuric acid, adding sodium persulfate, performing ultrasonic oscillation and uniform dispersion, heating and standing for reaction, and performing suction filtration, washing and drying to obtain alpha-type manganese dioxide filled with three-dimensional sea urchin-shaped hydrogen ions; the molar ratio of the manganese sulfate to the sodium persulfate is 1 to 1; the volume ratio of concentrated sulfuric acid to water in the aqueous solution containing concentrated sulfuric acid is 1 to 10 to 1; the temperature of the heating and standing reaction is 60 to 90 ℃.
2. The low-temperature liquid-phase preparation method of three-dimensional echinoid hydrogen ion filled alpha-type manganese dioxide as claimed in claim 1, which is characterized in that: the heating and standing reaction time is 6 to 24h.
3. An alpha manganese dioxide produced by the method of any one of claims 1~2.
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