CN110040783B - Manganous-manganic oxide nano material, preparation method and application thereof - Google Patents
Manganous-manganic oxide nano material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a trimanganese tetroxide nano material, a preparation method and application thereof, relating to the technical field of trimanganese tetroxide functional material synthesis. The preparation method of the manganous-manganic oxide nano material comprises the following steps: carrying out hydrothermal reaction on a mixed system formed by manganese acetate, thiophene dicarboxylic acid compounds, bipyridine compounds, strong base and water; preferably, the thiophenedicarboxylic compound is 2, 5-thiophenedicarboxylic acid; preferably, the bipyridine compound is 4, 4' -bipyridine. The manganous-manganic oxide nano material is prepared by the preparation method, has a one-dimensional nano rod structure, has good oxygen reduction (ORR) activity and stability, and can be used as an ORR catalyst to be applied to a fuel cell.
Description
Technical Field
The invention relates to the technical field of synthesis of manganomanganic oxide functional materials, and particularly relates to a manganomanganic oxide nano material, and a preparation method and application thereof.
Background
With the rapid development of economy and science and technology in China, the demand of traditional fossil energy such as coal, oil, natural gas and the like on which people live is increasing, and the shortage problem of the energy is becoming serious due to the limited reserves and the non-renewable property of the energy. Therefore, research and development of clean renewable energy sources to replace traditional fossil energy sources are of great significance to solve the two problems of energy crisis and environmental pollution.
Fuel cells (Fuel cells) are known as the fourth generation power generation technology following water power, firepower and nuclear energy, and are also the most environmentally-friendly and reliable power generation mode. Half the cost of the fuel cell stack is used in the cathode catalyst layer and will continue to increase as platinum is consumed and in short supply worldwide. And the fuel cell catalyst with low development cost and high activity and stability is the key of large-scale commercial development of the fuel cell. Transition metal oxides are expected to replace platinum-based catalysts due to their simple preparation and better oxygen reduction (ORR) activity and stability in low temperature alkaline fuel cells. Manganese oxide is popular because of its low price, abundant reserves, and good ORR activity and hydrogen peroxide decomposition activity. Oxides of manganese including MnO, Mn2O3，Mn3O4，MnO2，Mn5O8MnOOH, etc. In particular, Mn3O4The most stable crystalline phase at high temperatures. Mn by means of high specific capacitance, cost-effectiveness and environmental compatibility3O4Have exhibited significant catalytic properties.
At present, Mn3O4The preparation method mainly comprises a hydrothermal method, a solvent method, an oxidation method, a reduction method, a baking method and the like. Wherein, the oxidation method mostly adopts the oxidation method of metal manganese, the process is slow, and the industrialization is inconvenient; the baking method requires a high temperature, resulting in high energy consumption; preparation of Mn by thermal decomposition3O4Manganese oxide and manganese carbonate are mostly used as raw materials, the process is simple, equipment is few, but the manganese oxide and the manganese carbonate are required to be roasted at high temperature, the product has coarse granularity and low activity in the sintering process, and the raw materials are required to be higher and the preparation conditions are harsh, so the manganese oxide and the manganese carbonate are almost only limited to be carried out in a laboratory, and the experimental industrial production is difficult; mn with high specific surface area and high purity can be prepared by manganese salt hydrothermal oxidation method3O4Mn produced by hydrothermal oxidation system3O4In addition to the problem of high sulfur content, conventional preparation of Mn3O4The method of (3) also has a problem that ORR activity and stability are not satisfactory.
Disclosure of Invention
The invention aims to provide a preparation method of a mangano-manganic oxide nano material, aiming at fundamentally solving the problem of Mn prepared by a manganese salt method3O4High sulfur content, and increase of Mn3O4ORR activity and stability of (A).
The invention also aims to provide a manganous-manganic oxide nano material and application thereof, wherein the manganous-manganic oxide nano material is prepared by the preparation method, is in the form of a one-dimensional nanorod, has good ORR activity and stability, and can be used as a potential fuel cell oxygen reduction catalyst.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a manganous-manganic oxide nano material, which comprises the following steps:
carrying out hydrothermal reaction on a mixed system formed by manganese acetate, thiophene dicarboxylic acid compounds, bipyridine compounds, strong base and water;
preferably, the thiophenedicarboxylic compound is 2, 5-thiophenedicarboxylic acid;
preferably, the bipyridine compound is 4, 4' -bipyridine.
The invention also provides a manganous-manganic oxide nano material prepared by the preparation method;
preferably, the manganous-manganic oxide nano material structure is a one-dimensional nanorod.
The invention also provides application of the manganous-manganic oxide nano material in a fuel cell.
The embodiment of the invention provides a preparation method of a manganous-manganic oxide nano material, which has the beneficial effects that: the present inventors carried out hydrothermal reaction using a mixed system of manganese acetate, a thiophene dicarboxylic acid compound, a bipyridine compound, a strong base, and water to obtain trimanganese tetroxide. The method is simple and easy to implement, and fundamentally solves the problem of high sulfur content in the process of preparing the manganous-manganic oxide by a hydrothermal method.
The invention also provides a trimanganese tetroxide nano material prepared by the preparation method, the trimanganese tetroxide nano material has a one-dimensional nanorod structure, has good ORR activity and stability, and can be used as an ORR catalyst to be applied to fuel cells.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a scanning electron micrograph of trimanganese tetroxide prepared in example 4 of the present invention;
FIG. 2 is a transmission electron micrograph of trimanganese tetroxide prepared in example 4 of the present invention;
FIG. 3 is a scanning electron micrograph of trimanganese tetroxide prepared in example 5 of the present invention;
FIG. 4 is a diagram showing the X-ray powder diffraction detection result of trimanganese tetroxide prepared in example 4 of the present invention;
FIG. 5 is a diagram showing the result of X-ray photoelectron spectroscopy on the mangano-manganic oxide prepared in example 4 of the present invention;
FIG. 6 is a graph showing the results of the ORR activity assay of trimanganese tetroxide prepared in example 4 of the present invention;
FIG. 7 is a graph showing the results of ORR stability detection of trimanganese tetroxide prepared in example 4 of the present invention;
FIG. 8 is a field emission scanning electron micrograph of a product obtained in comparative example 1 of the present invention;
FIG. 9 is a field emission scanning electron micrograph of a product obtained in comparative example 2 of the present invention;
FIG. 10 is a field emission scanning electron micrograph of a product obtained in comparative example 3 of the present invention;
FIG. 11 is a field emission scanning electron micrograph of a product obtained in comparative example 4 of the present invention;
FIG. 12 is a field emission scanning electron micrograph of a product obtained in comparative example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The manganous-manganic oxide nano material provided by the embodiment of the invention, the preparation method and the application thereof are specifically explained below.
The preparation method of the manganous-manganic oxide nano material provided by the embodiment of the invention comprises the following steps:
s1 preparation of Mixed System
Manganese acetate, thiophene dicarboxylic acid compounds, bipyridine compounds, strong base and water are uniformly mixed to obtain a mixed system. Preferably, the thiophenedicarboxylic compound is 2, 5-thiophenedicarboxylic acid; the bipyridine compound is 4,4 '-bipyridine, and the manganous manganic oxide prepared by adopting 2, 5-thiophenedicarboxylic acid powder and 4, 4' -bipyridine as raw materials has good ORR activity and stability.
Carrying out ultrasonic treatment on a mixed system formed by manganese acetate, thiophene dicarboxylic acid compounds, bipyridine compounds, strong base and water for 15-25min, and dissolving the components in water after ultrasonic treatment.
Wherein, the strong base is selected from sodium hydroxide and/or potassium hydroxide, and is preferably sodium hydroxide. The inventor finds that the manganous-manganic oxide prepared by using sodium hydroxide as a raw material presents a relatively pure nanorod structure, but the manganous-manganic oxide prepared by using potassium hydroxide presents a mixed structure of relatively thick nanorods and small particles, which is probably because the existence of the potassium hydroxide can cause the crystal growth speed of the manganous-manganic oxide to be accelerated so as to facilitate agglomeration.
Further, the molar ratio of manganese acetate, thiophene dicarboxylic acid compounds, bipyridine compounds and strong base is 1:1-1.4:1.2-1.6: 2.4-2.8; preferably 1:1.1-1.3:1.3-1.5: 2.5-2.7. The thiophene dicarboxylic acid compound and the bipyridine compound are preferably slightly excessive relative to manganese acetate, so that the manganese acetate can be fully reacted, and the yield of the trimanganese tetroxide can be improved.
Further, in the mixing system, the concentration of manganese acetate is 2.3-3.5 mg/mL; preferably 2.5-3.2 mg/mL. Too high or too low concentration of manganese acetate is not favorable for the performance of the synthesized trimanganese tetroxide, for example, too high concentration of manganese acetate can affect the enrichment state of the final crystal, uniform nanorod-shaped crystals cannot be obtained, and the oxygen reduction performance can be further reduced.
S2 hydrothermal reaction
Carrying out hydrothermal reaction on the prepared mixed system liquid, wherein the hydrothermal reaction temperature is 100 ℃ and 160 ℃, and the reaction time is 48-72 h; preferably, the hydrothermal reaction temperature is 110-130 ℃, and the reaction time is 55-65 h. The hydrothermal reaction temperature and time can affect the form of the manganous-manganic oxide nano material, the reaction temperature and time are controlled within the range, the uniform and consistent nanorod-shaped crystal structure can be obtained, and the prepared crystal has good ORR activity and stability and is suitable for popularization and application.
It should be noted that, the specific reaction process in the reaction process may be: in the sodium hydroxide aqueous solution, 2, 5-thiophenedicarboxylic acid (Tdc) loses protons to form 2, 5-thiophenedicarboxylic acid dianions; 2, 5-thiophenedicarboxylic acid dianion and 4, 4' -bipyridine (Bpy) as a biligand, Mn2+As metal centers, the MOF precursor of manganese [ Mn (Tdc) (Bpy) is formed first]nAnd (4) nanorods. [ Mn (Tdc) first (Bpy)]nUnstable and continue to decompose into Mn3O4And (4) nanorods.
Specifically, the hydrothermal reaction is carried out in a stainless steel high-pressure hydrothermal kettle containing a polytetrafluoroethylene lining, and comprises the following steps: heating the mixed system at a heating rate of 0.8-1.2 ℃/min, then carrying out heat preservation for hydrothermal reaction, and then cooling at a cooling rate of 2.5-3.5 ℃/h; preferably, the temperature is reduced to 20-30 ℃. The oven with program temperature control is favorable for controlling the reaction temperature more accurately, and the heating rate and the cooling rate are controlled in a slower range.
S3, post-processing
After the hydrothermal reaction is completed, the solid precipitate is obtained by filtration, and preferably, the solid precipitate obtained by filtration is washed and dried. And filtering the solid-liquid mixed system after the hydrothermal reaction, separating the manganous-manganic oxide nano material, and washing to remove unreacted thiophene dicarboxylic acid compounds and bipyridine compounds to obtain the pure manganous-manganic oxide nano material. Specifically, the drying temperature is 40-60 ℃, the drying temperature is not too high, otherwise trimanganese tetroxide is easy to agglomerate, and the ORR activity and stability of the product are influenced.
The embodiment of the invention also provides a trimanganese tetroxide nano material prepared by the preparation method, the trimanganese tetroxide nano material has a one-dimensional nanorod structure, and particularly, a crystal structure prepared by using sodium hydroxide as a raw material presents a uniform and consistent one-dimensional nanorod structure.
The average diameter of the nano-rod prepared by the method is 28-31 nm; the limiting current density of the nano-rod is 6.1mA.cm-2(ii) a Rhe, after twenty thousand seconds of cycling at 0.75V vs. s, the ORR current density still maintained over 90% of the original current density. Therefore, the prepared mangano-manganic oxide has good ORR activity and stability, and can be used as an ORR catalyst to be applied to fuel cells.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a manganous-manganic oxide nano material, which comprises the following steps: 0.1176g of manganese acetate powder, 0.0747g of 2, 5-thiophenedicarboxylic acid powder, 0.0823g of 4, 4' -bipyridine powder and 0.0421g of sodium hydroxide solid were put into a 100mL beaker containing 50mL of secondary water and ultrasonically dispersed for 15 min.
And transferring the mixed system after the ultrasonic treatment to a 100mL stainless steel high-pressure hydrothermal kettle containing a polytetrafluoroethylene lining, heating to 100 ℃ at a heating rate of 0.8 ℃/min, then carrying out heat preservation for hydrothermal reaction for 72h, and cooling to 20 ℃ at a cooling rate of 2.5 ℃/h to obtain a solution containing the precipitate. And (4) carrying out suction filtration and washing on the mixed solution after reaction, and drying the obtained solid in an oven at 40 ℃.
Example 2
The embodiment provides a preparation method of a manganous-manganic oxide nano material, which comprises the following steps: 0.1176g of manganese acetate powder, 0.1046g of 2, 5-thiophenedicarboxylic acid powder, 0.1097g of 4, 4' -bipyridine powder and 0.0492g of sodium hydroxide solid were put into a 100mL beaker containing 35mL of secondary water and ultrasonically dispersed for 25 min.
And transferring the mixed system after the ultrasonic treatment to a 100mL stainless steel high-pressure hydrothermal kettle containing a polytetrafluoroethylene lining, heating to 140 ℃ at the heating rate of 1.2 ℃/min, then carrying out heat preservation for hydrothermal reaction for 48h, and cooling to 25 ℃ at the cooling rate of 3.5 ℃/h to obtain a solution containing the precipitate. And (4) carrying out suction filtration and washing on the mixed solution after reaction, and drying the obtained solid in an oven at 60 ℃.
Example 3
The embodiment provides a preparation method of a manganous-manganic oxide nano material, which comprises the following steps: 0.1176g of manganese acetate powder, 0.0822g of 2, 5-thiophenedicarboxylic acid powder, 0.0891g of 4, 4' -bipyridine powder and 0.0439g of sodium hydroxide solid were put into a 100mL beaker containing 47mL of secondary water and ultrasonically dispersed for 20 min.
And transferring the mixed system after the ultrasonic treatment to a 100mL stainless steel high-pressure hydrothermal kettle containing a polytetrafluoroethylene lining, heating to 110 ℃ at the heating rate of 1.0 ℃/min, then carrying out heat preservation for hydrothermal reaction for 65 hours, and cooling to 30 ℃ at the cooling rate of 3.0 ℃/h to obtain a solution containing the precipitate. And (4) carrying out suction filtration and washing on the mixed solution after reaction, and drying the obtained solid in an oven at 60 ℃.
Example 4
The embodiment provides a preparation method of a manganous-manganic oxide nano material, which comprises the following steps: 0.1176g of manganese acetate powder, 0.0971g of 2, 5-thiophenedicarboxylic acid powder, 0.1028g of 4, 4' -bipyridine powder and 0.0474g of sodium hydroxide solid were put into a 100mL beaker containing 37mL of secondary water and ultrasonically dispersed for 20 min.
And transferring the mixed system after the ultrasonic treatment to a 100mL stainless steel high-pressure hydrothermal kettle containing a polytetrafluoroethylene lining, heating to 130 ℃ at the heating rate of 1.0 ℃/min, then carrying out heat preservation for hydrothermal reaction for 55h, and cooling to 25 ℃ at the cooling rate of 3.0 ℃/h to obtain a solution containing the precipitate. And (4) carrying out suction filtration and washing on the mixed solution after reaction, and drying the obtained solid in an oven at 50 ℃.
Example 5
The embodiment provides a preparation method of a manganous-manganic oxide nano material, which has the same specific steps as the embodiment 4, and the difference is that: the sodium hydroxide was replaced by equimolar potassium hydroxide, i.e. 0.0474g of sodium hydroxide was replaced by 0.0699g of potassium hydroxide.
Comparative example 1
The comparative example provides a preparation method of a manganous-manganic oxide nano material, which has the same specific steps as the example 4, and is different from the following steps: the manganese acetate was replaced with equimolar manganese chloride.
Comparative example 2
The comparative example provides a preparation method of a manganous-manganic oxide nano material, which has the same specific steps as the example 4, and is different from the following steps: the manganese acetate was replaced by equimolar manganese nitrate.
Comparative example 3
The comparative example provides a preparation method of a manganous-manganic oxide nano material, which has the same specific steps as the example 4, and is different from the following steps: manganese acetate was replaced with equimolar manganese sulfate.
Comparative example 4
The comparative example provides a preparation method of a manganous-manganic oxide nano material, which has the same specific steps as the example 4, and is different from the following steps: the hydrothermal reaction temperature was 160 ℃.
Comparative example 5
The comparative example provides a preparation method of a manganous-manganic oxide nano material, which has the same specific steps as the example 4, and is different from the following steps: the hydrothermal reaction temperature was 80 ℃.
Test example 1
The manganous-manganic oxide nano material prepared in the example 4 is analyzed by a scanning electron microscope and a transmission electron microscope, and the results are shown in figures 1-2. The manganous-manganic oxide nano material prepared in the example 5 is analyzed by a scanning electron microscope, and the result is shown in figure 3.
From FIG. 1, it can be seen that the manganomanganic oxide exhibits a uniform one-dimensional nanorod structure, with the average diameter of the nanorods being about 29.8 nm. It can be seen from FIG. 2 that the lattice spacing of the nanorods is about 0.2 nm. As can be seen from FIG. 3, the manganous-manganic oxide nano-material prepared by using potassium hydroxide as a raw material is in a structure of mixing nano-rods and particles.
Test example 2
The manganous-manganic oxide nano material prepared in the example 4 is detected by X-ray diffraction, and the result is shown in figure 4. The X-ray diffraction result in FIG. 4 is compared with a standard manganomanganic oxide card, and the characteristic peak of the X-ray diffraction result is consistent with a standard manganomanganic oxide chart, so that the synthesis of the manganomanganic oxide nano material in the embodiment of the invention is proved.
The manganous-manganic oxide nano material prepared in the example 4 is subjected to X-ray photoelectron spectroscopy detection, and the result is shown in figure 5. From fig. 5, the main spin orbit lines of Mn 2p and O1 s peaks can be observed, which proves that the manganous-manganic oxide nano material is synthesized by the embodiment of the invention.
Test example 3
The ORR activity of the trimanganese tetroxide nanomaterial prepared in example 4 was mainly detected in a three-electrode system. Namely, a rotating disk electrode (glassy carbon electrode, diameter of 4mm) modified by a catalyst sample is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and a platinum sheet electrode (1 cm)2) Is a counter electrode. The temperature was 25. + -. 1 ℃ during the test. All measured potentials were converted to RHE.
The working electrode was prepared as follows: firstly, accurately weighing 4mg of catalyst sample, putting the catalyst sample into a 5mL reagent bottle, and adding 1mL of ethanol and 40 mu L of 5 wt% Nafion solution; performing ultrasonic dispersion for 20min to obtain black slurry-like dispersion liquid; 9 mu L of the dispersion liquid is transferred by a microsyringe, and is dripped on the surface of the cleaned glassy carbon electrode and is dried for standby application under an infrared lamp. The loading of the catalyst on the glassy carbon electrode is 275.6 mu g cm-2. Linear voltammetric scanning was performed in an oxygen-saturated 0.1M KOH solution at a scan rate of 5mV s-1The scanning range is 1.2V-0.0V vs. RHE, and the rotating speed is 1600 rpm.
Mn obtained in example 43O4The ORR polarization curves of the nanorods and Pt/C are shown in figure 6, and Mn can be seen3O4The limiting current density of (A) is higher than that of Pt/C, indicating better ORR activity.
Test example 4
The ORR stability of the trimanganese tetroxide nanomaterial prepared in example 4 was tested, and the results are shown in fig. 7. The test method comprises the following steps: chronoamperometric measurements were also carried out in 0.1M KOH solution saturated with oxygen, set at a potential of 0.75V vs. RHE and for a time of 20000 s. FIG. 7 shows a comparison of Mn obtained in example 43O4ORR stability of nanorods and Pt/C, Mn3O4The stability is better, and the current density still keeps more than 90 percent of the original current density after twenty thousand seconds of circulation.
Test example 5
By comparing the production methods of example 4 and comparative examples 1 to 5, the morphology of the obtained product and the properties of the product were observed. The field emission scanning electron micrographs of the products obtained in comparative examples 1-5 are shown in FIGS. 8-12, respectively.
The performance of the manganous-manganic oxide obtained in the comparative examples 1-5 is reduced compared with that of the manganous-manganic oxide obtained in the example 4, and the structures of the manganous-manganic oxide obtained in the comparative examples 1-5 are nanorods, nano particles and blocks, nanorods and small particles, and nanorods and blocks.
In summary, according to the preparation method of the trimanganese tetroxide nanomaterial provided by the invention, the inventors adopt a mixed system formed by manganese acetate, thiophene dicarboxylic acid compounds, bipyridine compounds, strong base and water to perform a hydrothermal reaction to obtain the trimanganese tetroxide. The method is simple and easy to implement, and fundamentally solves the problem of high sulfur content in the process of preparing the manganous-manganic oxide by a hydrothermal method.
The manganous-manganic oxide nano material provided by the invention has a one-dimensional nano rod structure, has good ORR activity and stability, can be used as an ORR catalyst, and can be applied to fuel cells.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (13)
1. The preparation method of the manganous-manganic oxide nano material is characterized by comprising the following steps of:
carrying out hydrothermal reaction on a mixed system formed by manganese acetate, thiophene dicarboxylic acid compounds, bipyridine compounds, strong base and water to obtain an MOF precursor [ Mn (Tdc) (Bpy)]nThe nano-rods are continuously decomposed into manganous manganic oxide nano-rods;
the thiophene dicarboxylic acid compound is 2, 5-thiophene dicarboxylic acid;
the bipyridine compound is 4, 4' -bipyridine; the strong base is sodium hydroxide;
the molar ratio of the manganese acetate to the thiophene dicarboxylic acid compound to the bipyridine compound to the strong base is 1:1-1.4:1.2-1.6: 2.4-2.8; the hydrothermal reaction temperature is 100-140 ℃, and the reaction time is 48-72 h;
in the mixed system, the concentration of the manganese acetate is 2.3-3.5 mg/mL;
the average diameter of the nano-rods is 28-31nm, and the lattice spacing of the nano-rods is 0.15-0.25 nm.
2. The method for preparing manganous-manganic oxide nano material according to claim 1, wherein the molar ratio of the manganese acetate to the thiophene dicarboxylic acid compound to the bipyridine compound to the strong base is 1:1.1-1.3:1.3-1.5: 2.5-2.7.
3. The method for preparing manganous-manganic oxide nano material according to claim 1, wherein the concentration of the manganese acetate in the mixed system is 2.5-3.2 mg/mL.
4. The method for preparing manganous-manganic oxide nano material as recited in claim 1, wherein the hydrothermal reaction temperature is 110-130 ℃ and the reaction time is 55-65 h.
5. The method for preparing manganous-manganic oxide nano material according to claim 1, wherein a mixed system formed by the manganese acetate, the thiophene dicarboxylic acid compound, the bipyridine compound, the strong base and water is subjected to ultrasonic treatment for 15-25min before hydrothermal reaction.
6. The method for preparing manganous-manganic oxide nano material according to claim 1, wherein the filtration is carried out after the hydrothermal reaction is finished to obtain solid precipitate.
7. The method of claim 6, wherein the filtered solid precipitate is washed and dried.
8. The method for preparing manganomanganic oxide nano material according to claim 7, wherein the drying temperature is 40-60 ℃.
9. The method for preparing manganous-manganic oxide nano material according to claim 1, wherein the hydrothermal reaction comprises the following steps: heating the mixed system at a heating rate of 0.8-1.2 ℃/min, then carrying out thermal insulation for hydrothermal reaction, and then cooling at a cooling rate of 2.5-3.5 ℃/h.
10. The method for preparing the manganous-manganic oxide nano material according to claim 9, wherein the temperature is reduced to 20-30 ℃.
11. A manganomanganic oxide nano material, which is prepared by the preparation method of any one of claims 1 to 10;
the manganous-manganic oxide nano material is a one-dimensional nano rod.
12. The trimanganese tetroxide nanomaterial of claim 11, wherein the nanorod has an ultimate current density of 5.9-6.3 mA cm-2(ii) a At 0.75Vvs.The reversible hydrogen electrode has the current density still kept over 90 percent of the original current density after twenty thousand seconds of circulation.
13. Use of the trimanganese tetroxide nanomaterial prepared by the preparation method of any one of claims 1-10 in a fuel cell.
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