CN110416560B - Calcium manganese oxide material and preparation method and application thereof - Google Patents
Calcium manganese oxide material and preparation method and application thereof Download PDFInfo
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- CN110416560B CN110416560B CN201810388389.XA CN201810388389A CN110416560B CN 110416560 B CN110416560 B CN 110416560B CN 201810388389 A CN201810388389 A CN 201810388389A CN 110416560 B CN110416560 B CN 110416560B
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/90—Selection of catalytic material
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a calcium manganese oxide material, a preparation method and application thereof, and MnO to be synthesized2Physically mixing the tube with calcium nitrate in different proportions by a rotary evaporator, and calcining at high temperature, wherein when the content of calcium ions is high, MnO is added2The tube is reduced to Mn after calcination3O4Rods, simultaneously adsorbing Mn3O4The calcium ion on the surface of the bar will react with Mn3O4The manganese atoms in the calcium manganese oxide particles are converted into calcium manganese oxide particles with uniform size in situ through solid phase reaction, and the calcium manganese oxide particles have excellent oxygen reduction performance due to variable valence states, large specific surface area and acceleration of electron transmission by a heterostructure.
Description
Technical Field
The invention relates to a preparation method of in-situ conversion calcium manganese oxide, in particular to calcium ion in trimanganese tetroxide (Mn)3O4) A preparation method and application of a material with surface converted into calcium manganese oxide.
Background
With the deepening of energy crisis and the increasing serious environmental pollution problem, the development and utilization of new clean energy sources are urgent. Among various types of novel clean energy, fuel cells are one of the most promising green energy sources because they can directly convert chemical energy into electric energy without going through a heat engine process, without being limited by carnot cycle, with high energy conversion efficiency, without noise and pollution.
The cathode reaction, i.e. Oxygen Reduction Reaction (ORR), of the fuel cell greatly limits the wide application of the fuel cell due to its slow kinetics, so improving the catalytic activity of the catalyst on the ORR has been a research hotspot of the fuel cell. The most used platinum-based catalyst in the commercial fuel cell has excellent catalytic performance, but the cost of the fuel cell catalyst is high due to the high price, the lack of resources and the poor stability of platinum, and the production cost of the fuel cell is greatly increased. Therefore, the development of non-metallic catalytic materials with high catalytic activity, high stability and low cost is currently an important challenge in this field.
In recent years, various transition metal oxides have been extensively studied in electrocatalytic oxygen reduction, among themManganese-based oxides are inexpensive, abundant and of variable valence (Mn)2+、Mn3+、Mn4+、Mn6+And Mn7+) The method can form oxides and composite oxides (perovskite and spinel) with various structures, has a simple synthesis method, shows good ORR activity and becomes a research hotspot. Compared with other manganese oxides (e.g. MnO)2、Mn2O3) Hausmannite Mn3O4Is the most stable oxide at high temperature, is an important chemical raw material, and has a mixed valence state (Mn)2+、Mn3+、Mn4+) The characteristics of (a) make it active in some catalytic processes, especially the electrocatalytic performance in oxygen reduction processes, has been a research hotspot.
Recent studies have shown that the incorporation of calcium (Ca) into oxides of manganese can improve their water oxidation activity to a greater extent, and that Ca also has an important role in the ORR electrocatalytic process of Ca-Mn-O oxides, which can affect the adsorption, activation and reduction of surface oxygen. Meanwhile, the combination of calcium ions and manganese improves the chemical and structural stability of the crystal. Reported calcium manganese oxides such as perovskite-structured CaMnO3Ca of a layered structure2MnO4、Ca2Mn3O8And CaMn of the rear spinel type2O4、Ca Mn3O6The composite metal oxides have the problems of large size and small specific surface area, so that the electrocatalytic performance of the calcium manganese oxide in the oxygen reduction process can be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a calcium manganese oxide material, a preparation method and application thereof, wherein MnO is synthesized2Physically mixing the tube with calcium nitrate in different proportions by a rotary evaporator, and calcining at high temperature, wherein when the content of calcium ions is high, MnO is added2The tube is reduced to Mn after calcination3O4Rods, simultaneously adsorbing Mn3O4The calcium ion on the surface of the bar will react with Mn3O4The manganese atom in the steel is converted into a ruler in situ through solid phase reactionThe uniform calcium manganese oxide particles show excellent oxygen reduction performance due to variable valence states, large specific surface area and acceleration of electron transport by a heterostructure.
The invention is realized by the following technical scheme:
the calcium-manganese oxide material comprises calcium-manganese oxide particles distributed in a cluster shape, wherein the particle size of the calcium-manganese oxide particles is 20-395 nm; the preparation method comprises the following steps:
step 1, slowly adding 37 wt% of concentrated hydrochloric acid into deionized water, then adding 0.45 g of potassium permanganate, wherein the volume ratio of the concentrated hydrochloric acid to the deionized water is 1:40, placing the mixture into a hydrothermal reaction kettle after ultrasonic stirring for half an hour, reacting for 10-12h at the temperature of 130-150 ℃, cooling to room temperature, washing the reaction product for 3-5 times by using the deionized water and ethanol in sequence, placing the reaction product into a vacuum drying box, and drying for 4-8h at room temperature to obtain a brownish black reaction product MnO2A nanotube;
In the above technical solution, the particle size of the calcium manganese oxide particles is preferably 25 to 125 nm.
In the above technical scheme, the reaction temperature in the hydrothermal reaction kettle in the step 1 is preferably 135-145 ℃, and the reaction time is preferably 11-12 h.
In the above technical scheme, in the step 2, the addition amount of the calcium nitrate is 0.2-0.6g, preferably 0.25-0.55 g.
In the above technical solution, the heating rate in step 3 is preferably 1.5-2.5 ℃/min, the constant temperature is preferably 800-.
The preparation method of the calcium manganese oxide material comprises the following steps:
step 1, slowly adding 37 wt% of concentrated hydrochloric acid into deionized water, then adding 0.45 g of potassium permanganate, wherein the volume ratio of the concentrated hydrochloric acid to the deionized water is 1:40, placing the mixture into a hydrothermal reaction kettle after ultrasonic stirring for half an hour, reacting for 10-12h at the temperature of 130-150 ℃, cooling to room temperature, washing the reaction product for 3-5 times by using the deionized water and ethanol in sequence, placing the reaction product into a vacuum drying box, and drying for 4-8h at room temperature to obtain a brownish black reaction product MnO2A nanotube;
in the step 1, the reaction temperature in the hydrothermal reaction kettle is preferably 135-145 ℃, and the reaction time is preferably 11-12 h;
in step 2, the addition amount of calcium nitrate is 0.2-0.6g, preferably 0.25-0.55 g;
in step 3, the heating rate is preferably 1.5-2.5 ℃/min, the constant temperature is preferably 800-.
An application of calcium-manganese oxide material in electrocatalytic oxygen reduction.
The invention has the advantages and beneficial effects that:
(1) the calcium manganese oxide material disclosed by the invention is prepared by adopting an in-situ conversion method, so that the oxygen reduction performance of a sample is optimized.
(2) The invention leads the electro-catalytic oxygen reduction performance of the sample to be closer to commercial platinum carbon through modification, and has the characteristics of low cost and strong stability.
(3) The invention can be applied to the fields of fuel cells and the like, and opens up a new idea for the design and synthesis of other novel supported heterostructure electrocatalysts.
Drawings
Fig. 1 is a scanning electron micrograph of a calcium manganese oxide material prepared according to a first embodiment of the present invention.
Fig. 2 is a scanning electron micrograph of a calcium manganese oxide material prepared according to example two of the present invention.
Fig. 3 is an XRD pattern of calcium manganese oxide material prepared by the first example of the present invention.
Fig. 4 is an XRD pattern of calcium manganese oxide material prepared by example two of the present invention.
Fig. 5 is a graph comparing the performance of the calcium manganese oxide material prepared in example one of the present invention and the calcium manganese oxide material prepared in example two.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to the accompanying drawings and specific embodiments. It should be noted that: the following examples are illustrative and not intended to be limiting, and are not intended to limit the scope of the invention. The starting materials required in the following examples are all commercially available, chemically pure reagents.
Example one
Raw materials: concentrated hydrochloric acid solution, potassium permanganate and calcium nitrate.
(1) While stirring, 1ml of 37 wt% concentrated hydrochloric acid was slowly added to 40ml of deionized water, followed by 0.45 g of permanganic acidStirring for half an hour, uniformly dispersing by using an ultrasonic machine, pouring into a 50 ml hydrothermal reaction kettle, and placing in an oven at 140 ℃ for reaction for 12 hours. Cooling the reaction kettle to room temperature, and adding MnO as a brownish black reaction product2Repeatedly washing the nano-tubes with deionized water and ethanol for 3 times, and then drying the nano-tubes in a vacuum drying oven at room temperature for 6 hours to obtain brownish black reaction product MnO2A nanotube;
(2) adding 0.1 g of MnO2The nanotubes were dissolved in 10 ml of ethanol and 0.27 g of calcium nitrate was added so that the molar ratio of manganese to calcium was 1: 1, uniformly mixing and dispersing the manganese dioxide and the calcium nitrate in a solvent through ultrasonic treatment, and evaporating the solvent by a rotary evaporator to dryness to obtain a mixed product of the manganese dioxide and the calcium nitrate;
(3) placing the sample obtained in the last step in a tubular furnace, heating to 850 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and keeping the temperature for 4 hours to obtain the final product CaMnO3。
Example two
Raw materials: concentrated hydrochloric acid solution, potassium permanganate and calcium nitrate.
(1) During stirring, 1ml of 37 wt% concentrated hydrochloric acid is slowly added into 40ml of deionized water, then 0.45 g of potassium permanganate is added, the mixture is stirred for half an hour, uniformly dispersed by an ultrasonic machine, poured into a 50 ml hydrothermal reaction kettle and placed in an oven at 140 ℃ for reaction for 12 hours. Cooling the reaction kettle to room temperature, and adding MnO as a brownish black reaction product2Repeatedly washing the nanotubes with deionized water and ethanol for 3 times, and drying in a vacuum drying oven at room temperature for 6 hours to obtain brownish black reaction product MnO2A nanotube;
(2) adding 0.1 g of MnO2The nanotubes were dissolved in 10 ml of ethanol and 0.54 g of calcium nitrate was added so that the molar ratio of manganese to calcium was 1: 2, uniformly mixing and dispersing the manganese dioxide and the calcium nitrate in a solvent through ultrasonic treatment, and evaporating the solvent by a rotary evaporator to dryness to obtain a mixed product of the manganese dioxide and the calcium nitrate;
(3) placing the sample obtained in the last step into a tubular furnace, heating to 850 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and keeping the temperature for 4 hours to obtain the final product Ca2MnO4。
From FIG. 1 calcium manganese oxide materials (CaMnO)3) Scanning electron micrograph of (1) and FIG. 2 calcium manganese oxide Material (Ca)2MnO4) The scanning electron microscope picture shows that the obtained calcium manganese oxide particles are gradually small and uniform along with the increase of the content of calcium ions.
As can be seen from fig. 3 and 4, when the molar ratio of manganese to calcium is 1: 1, the obtained calcium manganese oxide material is CaMnO3(ii) a When the molar ratio of manganese to calcium is 1: 2, the obtained calcium manganese oxide material is Ca2MnO4。
From FIG. 5 calcium manganese oxide material CaMnO3With Ca2MnO4The property comparison graph shows that the CaMnO of the perovskite structure3Ca of structure specific to Ruddlesden-Popper2MnO4The performance is more excellent.
The test adopts a three-electrode system, and the adopted test instruments are Shanghai Chenghua electrochemical workstation and American Pine rotary disk electrode, and the working electrodes are respectively CaMnO3With Ca2MnO4The counter electrode is a platinum column, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is a KOH solution with the concentration of 0.1M.
Although the present invention has been described in more detail in the examples and the drawings, the present invention is not limited to the above embodiments, and the preparation of the calcium manganese oxide material can be achieved by adjusting the process parameters according to the present disclosure, and the calcium manganese oxide material exhibits substantially the same properties as the above examples. It should be noted that any simple variations, modifications or changes in various forms which can be made without inventive work within the teaching of the present invention fall within the scope of protection of the present invention without departing from the core of the present invention.
Claims (5)
1. The calcium-manganese oxide material is characterized by comprising calcium-manganese oxide particles distributed in a cluster shape, wherein the particle size of the calcium-manganese oxide particles is 25-125 nm; the preparation method comprises the following steps:
step 1, slowly adding 1mL of 37 wt% concentrated hydrochloric acidAdding the mixture into 40mL of deionized water, adding 0.45 g of potassium permanganate, ultrasonically stirring for half an hour, placing the mixture into a hydrothermal reaction kettle, reacting for 12 hours at 140 ℃, cooling to room temperature, washing the reaction product for 3-5 times by using deionized water and ethanol in sequence, placing the reaction product into a vacuum drying oven, and drying for 4-8 hours at room temperature to obtain a brownish black reaction product MnO2A nanotube;
step 2, MnO obtained in the step 12Dissolving nanotube in ethanol solution, adding calcium nitrate, and ultrasonic treating to obtain MnO2Uniformly distributing the nano-tubes and calcium nitrate in an ethanol solution, and evaporating the solvent by a rotary evaporator to obtain MnO2A mixed product with calcium nitrate, wherein the molar ratio of manganese to calcium is 1 (1-2);
step 3, placing the sample obtained in the step 2 into a tubular furnace, heating to 850 ℃ from the room temperature of 20-25 ℃ at the heating rate of 2 ℃/min in the air atmosphere, keeping the temperature for 4h, naturally cooling to the room temperature of 20-25 ℃ along with the furnace, and adsorbing Mn3O4The calcium ion on the surface of the bar will react with Mn3O4The manganese atoms in the solution are converted into calcium manganese oxide particles with uniform size in situ through solid phase reaction to obtain a calcium manganese oxide material, and the calcium manganese oxide material is CaMnO3Or Ca2MnO4。
2. The calcium manganese oxide material according to claim 1, wherein: in the step 2, the addition amount of the calcium nitrate is 0.2-0.6 g.
3. A preparation method of a calcium manganese oxide material is characterized by comprising the following steps: the method comprises the following steps:
step 1, slowly adding 1mL of 37 wt% concentrated hydrochloric acid into 40mL of deionized water, then adding 0.45 g of potassium permanganate, ultrasonically stirring for half an hour, placing the mixture into a hydrothermal reaction kettle, reacting for 12 hours at 140 ℃, cooling to room temperature, washing the reaction product for 3-5 times by using deionized water and ethanol in sequence, placing the reaction product into a vacuum drying oven, and drying for 4-8 hours at room temperature to obtain a brownish black reaction product MnO2A nanotube;
step 2, the step 1Obtained MnO2Dissolving nanotube in ethanol solution, adding calcium nitrate, and ultrasonic treating to obtain MnO2Uniformly distributing the nano-tubes and calcium nitrate in an ethanol solution, and evaporating the solvent by a rotary evaporator to obtain MnO2A mixed product with calcium nitrate, wherein the molar ratio of manganese to calcium is 1 (1-2);
step 3, placing the sample obtained in the step 2 into a tube furnace, heating the sample to 850 ℃ from the room temperature of 20-25 ℃ at the heating rate of 2 ℃/min in the air atmosphere, keeping the temperature for 4h, naturally cooling the sample to the room temperature of 20-25 ℃ along with the furnace, and adsorbing Mn3O4The calcium ion on the surface of the bar will react with Mn3O4The manganese atoms in the solution are converted into calcium manganese oxide particles with uniform size in situ through solid phase reaction to obtain a calcium manganese oxide material, and the calcium manganese oxide material is CaMnO3Or Ca2MnO4。
4. The method for preparing calcium manganese oxide material according to claim 3, characterized in that: in the step 2, the addition amount of the calcium nitrate is 0.2-0.6 g.
5. Use of a calcium manganese oxide material according to claim 1 in electrocatalytic oxygen reduction.
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| CN111320211A (en) * | 2020-03-02 | 2020-06-23 | 吉林师范大学 | Perovskite type calcium manganate material, preparation method thereof and application thereof in wide-temperature-zone lithium ion battery |
| CN111871422A (en) * | 2020-07-21 | 2020-11-03 | 上海交通大学 | Application of calcium-manganese oxide catalyst in degradation of organic pollutants in wastewater and soil |
| CN112156766B (en) * | 2020-09-25 | 2022-08-19 | 天津大学 | Two-dimensional layered metal calcium/indium double hydroxide and preparation method and application thereof |
| CN114656243A (en) * | 2022-02-25 | 2022-06-24 | 纯钧新材料(深圳)有限公司 | Calcium-manganese-oxygen thermoelectric material and preparation method thereof |
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