CN109592715B - Method for controllably preparing manganese oxide with different structures by taking manganese terephthalate dihydrate as precursor - Google Patents
Method for controllably preparing manganese oxide with different structures by taking manganese terephthalate dihydrate as precursor Download PDFInfo
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Abstract
The invention discloses a method for controllably preparing manganese oxides with different structures by using manganese terephthalate dihydrate as a precursor, which adopts manganese terephthalate dihydrate as a precursor and potassium permanganate as an oxidant, adopts a thermal method, and adopts the following stepsAnd adjusting the pH value, the temperature and the molar ratio of the potassium permanganate to the precursor, thereby obtaining the manganese oxides with different structure types. The preparation method is simple, the reaction condition is mild, and the manganese oxide (such as the manganese potassium ore alpha-MnO) with various structures can be realized by utilizing the rich and stable pore channel structure of the complex2Pyrolusite beta-MnO2Hexagonal manganese ore gamma-MnO2Birnessite delta-MnO2Black manganese ore) is a very promising preparation method.
Description
Technical Field
The invention belongs to the technical field of manganese oxide preparation, and particularly relates to a method for preparing manganese oxides with different structures by using manganese terephthalate dihydrate as a precursor through a hydrothermal method.
Background
Manganese oxide is an amphoteric transition metal oxide and exists as a very stable black or brown powdery solid at ordinary temperature. The basic structural unit constituting the manganese oxide crystal is MnO6Octahedron, which is formed by 6 oxygen atoms at the top and 1 manganese atom at the center of the octahedron. Adjacent MnO6The octahedrons are connected in a mode of sharing edges or angles to form manganese oxide crystals with various structures. Although the basic structural units constituting the manganese oxide crystal are the same, due to MnO6Different octahedral connection modes, the manganese oxide crystal has various structures, such as: alpha-MnO of potassium manganese ore2(2 x 2 tunnel type), pyrolusite beta-MnO2(1 x 1 tunnel type), hexagonal manganese ore gamma-MnO2(1X 1+ 2X 1 tunnel type), birnessite delta-MnO2(layer-by-layer, with H between layers)2O), hausmannite (Mn)3O4) And the like. In recent years, although methods for producing manganese oxide materials mainly include a salt dissolution method, a solid-phase thermal decomposition method, a hydrothermal/solvothermal method, a sol-gel method, a microemulsion method, a chemical precipitation method, and a chemical vapor deposition method, a method for producing manganese oxide using a complex as a precursor by a hydrothermal/solvothermal method has not been reported.
The coordination polymer has high structural stability, unique space network structure and huge diameter distribution due to the strong interaction between metal ions or metal clusters and organic ligands. At present, many researches on carbon/oxide prepared by using a complex as a precursor are carried out, and the preparation method mainly adopts a calcination method, wherein the calcination method is used for calcining under the action of protective gas such as nitrogen, elements such as oxyhydrogen and the like leave the complex material in a gas form, and a carbon skeleton is reserved to form pores with the carbon as the skeleton. The calcining method requires higher temperature, can damage the original skeleton of the complex, and has single reaction condition and single product type.
Disclosure of Invention
The invention aims to provide a method for preparing manganese oxide with different structures by using manganese terephthalate dihydrate as a precursor through a hydrothermal method.
Aiming at the purposes, the technical scheme adopted by the invention is as follows: adding manganese terephthalate dihydrate and potassium permanganate into deionized water according to the molar ratio of 1: 0.25-2.00, adjusting the pH value to 1-13 with acid or alkali, reacting at 80-120 ℃ for 2-5 days under a sealed condition, cooling to normal temperature, centrifugally washing the obtained solid product with 0.1mol/L NaOH solution, and drying to obtain manganese oxide;
in the preparation method, manganese terephthalate dihydrate and potassium permanganate are added into deionized water according to the molar ratio of 1: 0.5-2.00, the pH value is adjusted to 3-11 by acid or alkali, the mixture reacts for 2-5 days at 80-120 ℃ under a closed condition, the mixture is cooled to normal temperature, and the obtained solid product is centrifugally washed by 0.1mol/L NaOH solution and then dried to obtain 2 x 2 tunnel type alpha-MnO2。
In the preparation method, manganese terephthalate dihydrate and potassium permanganate are added into deionized water according to the molar ratio of 1: 0.25-1.00, the pH value is adjusted to be 0.5-1 by acid or alkali, the mixture reacts for 2-5 days at 110-120 ℃ under a sealed condition, the mixture is cooled to normal temperature, the obtained solid product is centrifugally washed by 0.1mol/L NaOH solution and then dried to obtain 1 x 1 tunnel type beta-MnO2。
In the preparation method, manganese terephthalate dihydrate and potassium permanganate are added into deionized water according to the molar ratio of 1: 0.25-0.50, the pH value is adjusted to be 0.5-1 by acid or alkali, the mixture reacts for 2-5 days at 80-100 ℃ under a sealed condition, the mixture is cooled to normal temperature, the obtained solid product is centrifugally washed by 0.1mol/L NaOH solution and then dried to obtain 1 x 1+2 x 1 tunnel type gamma-MnO2。
In the preparation method, manganese terephthalate dihydrate and potassium permanganate are added into deionized water according to the molar ratio of 1: 0.50-2.00, the pH value is adjusted to 12-13 by acid or alkali, the reaction is carried out for 2-5 days at 80-120 ℃ under the sealed condition, the reaction is cooled to normal temperature, and the manganese terephthalate dihydrate and the potassium permanganate solution are obtainedThe solid product is centrifugally washed by 0.1mol/L NaOH solution and then dried to obtain layered delta-MnO2。
In the preparation method, manganese terephthalate dihydrate and potassium permanganate are added into deionized water according to the molar ratio of 1: 0.25-0.35, the pH value is adjusted to 3-11 by acid or alkali, the mixture reacts for 2-5 days at 85-120 ℃ under a sealed condition, the mixture is cooled to normal temperature, and the obtained solid product is centrifugally washed by 0.1mol/L NaOH solution and then dried to obtain Mn3O4。
The structural unit of the manganese terephthalate dihydrate is Mn (C)8H4O4)(H2O)2It is prepared according to the method disclosed in the literature "Terephthalate salts of synergistic locations, Acta Crystallographica. (2002). B58, 815-.
The acid is any one of sulfuric acid, phosphoric acid and acetic acid; the alkali is any one of sodium hydroxide, potassium hydroxide and ammonia water.
The invention has the following beneficial effects:
according to the invention, manganese oxide is prepared by taking manganese terephthalate dihydrate as a precursor through a hydrothermal method, and the structure variety of the product manganese oxide is more possible by utilizing the rich and stable pore structure of the precursor; the application of the hydrothermal method ensures that the reaction conditions are milder, and is favorable for oxidizing Mn in a precursor structure by potassium permanganate serving as an oxidant in situ2+And the reaction conditions (pH, temperature and the like) can be adjusted, so that the variety of the product is effectively improved, the performance of the product is regulated, and the preparation method is very promising.
Drawings
FIG. 1 shows the preparation of alpha-MnO of Melanese Potassium Ore prepared in examples 1 to 82Powder X-ray diffraction pattern of (1).
FIG. 2 shows the potassium manganate ore alpha-MnO prepared in example 72Field emission electron microscopy.
FIG. 3 is a pyrolusite beta-MnO prepared in examples 9 and 102Powder X-ray diffraction pattern of (1).
FIG. 4 is a pyrolusite beta-MnO prepared in example 102Field emission electron microscopy.
FIG. 5 is a block diagramThe gamma-MnO of the manganite prepared in examples 11 and 122Powder X-ray diffraction pattern of (1).
FIG. 6 shows birnessite delta-MnO prepared in examples 13 to 162Powder X-ray diffraction pattern of (1).
FIG. 7 shows hausmannite Mn prepared in examples 17 to 193O4Powder X-ray diffraction pattern of (1).
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
0.025g (0.157mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H with pH 3 were added2SO4Stirring and mixing the aqueous solution evenly, standing and reacting for 3.5 days at 85 ℃ under a closed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 2 x 2 tunnel type manganese potassium ore alpha-MnO2. As can be seen from FIG. 1, the powder X-ray diffraction curve of the obtained product was matched with that of a standard PDF card, indicating that the product was potassium manganate ore.
Example 2
Adding 0.025g (0.157mmol) of potassium permanganate, 0.080g (0.314mmol) of manganese terephthalate dihydrate and 10mL of deionized water into a glass bottle with a polytetrafluoroethylene cover, uniformly stirring and mixing, standing and reacting for 3.5 days at 85 ℃ under a sealed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 2 x 2 tunnel-type manganese potassium ore alpha-MnO2(see FIG. 1).
Example 3
Adding 0.050g (0.314mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with pH value of 9, stirring and mixing uniformly, standing and reacting for 3.5 days at 85 ℃ under a sealed condition, naturally cooling to normal temperature, and pouring out the supernatantWashing the bottom solid product with 0.1mol/L NaOH water solution, centrifuging, drying at 60 deg.C to constant weight to obtain 2 × 2 tunnel type manganese potassium ore alpha-MnO2(see FIG. 1).
Example 4
Adding 0.099g (0.628mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with the pH value of 11, stirring and mixing uniformly, standing and reacting at 85 ℃ under a sealed condition for 3.5 days, naturally cooling to normal temperature, pouring out a supernatant, washing a solid product at the bottom by using 0.1mol/L of NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain the 2X 2 tunnel-type manganese potassium ore alpha-MnO2(see FIG. 1).
Example 5
0.099g (0.628mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H with pH 3 were added2SO4Stirring and mixing the aqueous solution evenly, standing and reacting for 3.5 days at 120 ℃ under a closed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 2 x 2 tunnel type manganese potassium ore alpha-MnO2(see FIG. 1).
Example 6
0.025g (0.157mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H with pH 5 were added2SO4Stirring and mixing the aqueous solution evenly, standing and reacting for 3.5 days at 120 ℃ under a closed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 2 x 2 tunnel type manganese potassium ore alpha-MnO2(see FIG. 1).
Example 7
Adding 0.050g (0.314mmol) of potassium permanganate, 0.080g (0.314mmol) of manganese terephthalate dihydrate and 10mL of deionized water into a glass bottle with a polytetrafluoroethylene cover, stirring and mixing uniformly, and sealingStanding at 120 deg.C for 3.5 days, naturally cooling to normal temperature, pouring out supernatant, washing the bottom solid product with 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 deg.C to constant weight to obtain 2 × 2 tunnel type manganese potassium ore alpha-MnO2(see FIG. 1). The appearance of the field emission electron microscope image shown in FIG. 2 is an elongated rod shape.
Example 8
Adding 0.050g (0.314mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with the pH value of 11, stirring and mixing uniformly, standing and reacting for 3.5 days at 120 ℃ under a sealed condition, naturally cooling to normal temperature, pouring out a supernatant, washing a solid product at the bottom by using 0.1mol/L of NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain the 2 x 2 tunnel-type manganese potash ore alpha-MnO2(see FIG. 1).
Example 9
0.0125g (0.079mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H having a pH of 1 were added2SO4Stirring and mixing the aqueous solution evenly, standing and reacting for 3.5 days at 120 ℃ under a closed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 1 x 1 tunnel type pyrolusite beta-MnO2. As can be seen from FIG. 3, the powder X-ray diffraction curve of the obtained product was matched with that of a standard PDF card, indicating that the product was pyrolusite.
Example 10
0.050g (0.314mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H with pH 1 were added2SO4Stirring and mixing the aqueous solution evenly, standing and reacting for 3.5 days at 120 ℃ under a closed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 1 x 1 tunnel type pyrolusite beta-MnO2(see FIG. 3). From the field emission electron microscope shown in FIG. 4The figure shows that the appearance of the material is irregular and is approximate to a cuboid.
Example 11
0.0125g (0.079mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H having a pH of 1 were added2SO4Stirring and mixing the aqueous solution uniformly, standing and reacting for 3.5 days at 85 ℃ under a closed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 1 × 1+2 × 1 tunnel type hexagonal manganese ore gamma-MnO2. As can be seen from fig. 5, the powder X-ray diffraction curve of the obtained product was matched with a standard PDF card, indicating that the product was a manganite.
Example 12
0.025g (0.157mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H having a pH of 1 were added2SO4Stirring and mixing the aqueous solution uniformly, standing and reacting for 3.5 days at 85 ℃ under a closed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain 1 × 1+2 × 1 tunnel type hexagonal manganese ore gamma-MnO2(see FIG. 5).
Example 13
Adding 0.025g (0.157mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with pH value of 13, stirring and mixing uniformly, standing and reacting at 85 ℃ under a sealed condition for 3.5 days, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L of NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain layered birnessite delta-MnO2. As can be seen from fig. 6, the powder X-ray diffraction curve of the obtained product was matched with a standard PDF card, indicating that the product was birnessite.
Example 14
0.050g (0.314mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrateAdding into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with pH value of 13, stirring and mixing uniformly, standing and reacting for 3.5 days at 85 ℃ under a sealed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom with 0.1mol/L of NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain layered birnessite delta-MnO2(see FIG. 6).
Example 15
Adding 0.025g (0.157mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with pH value of 13, stirring and mixing uniformly, standing and reacting at 120 ℃ under a sealed condition for 3.5 days, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L of NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain layered birnessite delta-MnO2(see FIG. 6).
Example 16
Adding 0.099g (0.628mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with pH value of 13, stirring and mixing uniformly, standing and reacting at 120 ℃ under a sealed condition for 3.5 days, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L of NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain layered birnessite delta-MnO2(see FIG. 6).
Example 17
0.0125g (0.079mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate were placed in a glass bottle with a teflon cap, and 10mL of H having a pH of 3 were added2SO4Stirring and mixing the aqueous solution uniformly, standing and reacting for 3.5 days at 85 ℃ under a sealed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain the hausmannite Mn3O4. As can be seen from fig. 7, the powder X-ray diffraction curve of the obtained product was matched with a standard PDF card, indicating that the product was hausmannite.
Example 18
Adding 0.0125g (0.079mmol) of potassium permanganate, 0.080g (0.314mmol) of manganese terephthalate dihydrate and 10mL of deionized water into a glass bottle with a polytetrafluoroethylene cover, stirring and mixing uniformly, standing and reacting for 3.5 days at 85 ℃ under a sealed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain black manganese ore Mn3O4(see FIG. 7).
Example 19
Adding 0.0125g (0.079mmol) of potassium permanganate and 0.080g (0.314mmol) of manganese terephthalate dihydrate into a glass bottle with a polytetrafluoroethylene cover, adding 10mL of NaOH aqueous solution with the pH value of 11, stirring and mixing uniformly, standing and reacting for 3.5 days at 85 ℃ under a sealed condition, naturally cooling to normal temperature, pouring out supernatant, washing a solid product at the bottom by using 0.1mol/L of NaOH aqueous solution, centrifuging, and drying at 60 ℃ to constant weight to obtain black manganese ore Mn3O4(see FIG. 7).
Claims (3)
1. A method for controllably preparing oxides of manganese with different structures by taking manganese terephthalate dihydrate as a precursor is characterized by comprising the following steps:
adding manganese terephthalate dihydrate and potassium permanganate into deionized water according to the molar ratio of 1: 0.5-2.00, adjusting the pH value to be 3-11 by using acid or alkali, reacting for 2-5 days at 80-120 ℃ under a closed condition, cooling to normal temperature, centrifugally washing the obtained solid product by using 0.1mol/L NaOH solution, and drying to obtain 2 x 2 tunnel type alpha-MnO2；
Or adding manganese terephthalate dihydrate and potassium permanganate into deionized water according to the molar ratio of 1: 0.25-1.00, adjusting the pH value to be = 0.5-1 by acid or alkali, reacting for 2-5 days at 110-120 ℃ under a closed condition, cooling to normal temperature, centrifugally washing the obtained solid product by 0.1mol/L NaOH solution, and drying to obtain 1 x 1 tunnel type beta-MnO2；
Or adding manganese terephthalate dihydrate and potassium permanganate into deionized water according to the molar ratio of 1: 0.25-0.50, and adjusting the pH value with acid or alkali =0.5-1, reacting for 2-5 days at 80-100 ℃ under a closed condition, cooling to normal temperature, centrifugally washing the obtained solid product by using 0.1mol/L NaOH solution, and drying to obtain 1 × 1+2 × 1 tunnel type gamma-MnO2；
Or adding manganese terephthalate dihydrate and potassium permanganate into deionized water according to the molar ratio of 1: 0.50-2.00, adjusting the pH value to be 12-13 by using acid or alkali, reacting for 2-5 days at 80-120 ℃ under a closed condition, cooling to normal temperature, centrifugally washing the obtained solid product by using 0.1mol/L NaOH solution, and drying to obtain layered delta-MnO2；
Or adding manganese terephthalate dihydrate and potassium permanganate into deionized water according to the molar ratio of 1: 0.25-0.35, adjusting the pH value to be 3-11 by using acid or alkali, reacting for 2-5 days at 85-120 ℃ under a closed condition, cooling to normal temperature, centrifugally washing the obtained solid product by using 0.1mol/L NaOH solution, and drying to obtain Mn3O4；
The structural unit of the manganese terephthalate dihydrate is Mn (C)8H4O4)(H2O)2。
2. The method for controllably preparing the oxides of manganese with different structures by taking manganese terephthalate dihydrate as a precursor according to claim 1, characterized in that: the acid is any one of sulfuric acid, phosphoric acid and acetic acid.
3. The method for controllably preparing the oxides of manganese with different structures by taking manganese terephthalate dihydrate as a precursor according to claim 1, characterized in that: the alkali is any one of sodium hydroxide, potassium hydroxide and ammonia water.
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