CN105396599A - Porous MnCo2O4 and preparation method and application - Google Patents
Porous MnCo2O4 and preparation method and application Download PDFInfo
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- CN105396599A CN105396599A CN201510887941.6A CN201510887941A CN105396599A CN 105396599 A CN105396599 A CN 105396599A CN 201510887941 A CN201510887941 A CN 201510887941A CN 105396599 A CN105396599 A CN 105396599A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses porous MnCo2O4 and a preparation method and application. The preparation method comprises the steps that 1, metal salt, a surfactant, ethanol and water are mixed to prepare a mixed solution; 2, thermal decomposition is carried out on the mixed solution, and a product is collected; 3, the product is washed through water and ethanol in sequence, and then calcined in air to obtain the porous MnCo2O4. The metal salt contains soluble manganous salt and soluble cobalt salt. The porous MnCo2O4 has the excellent catalysis performance for ORR and OER, meanwhile, the preparation method is simple, and the raw materials are easy to obtain.
Description
Technical field
The present invention relates to nano-metal-oxide, particularly, relate to a kind of porous MnCo
2o
4and its preparation method and application.
Background technology
At present, the development of society still be unable to do without fossil fuel.The problems such as the finiteness of fossil fuel and the environmental pollution that causes, stimulate people to remove to develop power conversion and the energy-storage system of clean, sustainable development.O
2electrochemical research plays an important role promoting the development of this system, how to improve oxygen reduction (ORR) and oxygen evolution reaction (OER) and seems and be even more important.As long as have the following several reduction of mode catalytic oxygen (ORR) and oxygen evolution reaction (OER) at present: 1) utilize metal platinum: although Pt class catalyst has efficient catalytic to ORR, OER catalytic performance is barely satisfactory.2) utilize ruthenium-oxide, yttrium oxide: ruthenium-oxide, yttrium oxide are best OER catalyst, but their ORR performance is not as Pt.3) Pt/Ru/Ir alloy is utilized: although have people Pt, Ru, Ir to be combined prepared alloy, difunctional better performances, less stable.In addition, the amount of noble metal catalyst less, the reason such as expensive, can not extensively be applied.
Recently, carbide material is extensively studied in oxygen reduction (ORR) and oxygen evolution reaction (OER), although the difunctional character of this type of material is better, and synthesis temperature higher (at least 800 DEG C).
Summary of the invention
The object of this invention is to provide a kind of porous MnCo
2o
4and its preparation method and application, this porous MnCo
2o
4all have excellent catalytic performance to ORR and OER, preparation method is simple simultaneously, and raw material is easy to get.
To achieve these goals, the invention provides a kind of porous MnCo
2o
4, this porous MnCo
2o
4particle diameter be 30-50nm, specific area is 20-32m
2/ g.
Present invention also offers a kind of above-mentioned porous MnCo
2o
4preparation method, comprising:
1) slaine, surfactant, ethanol, water are carried out mixing with obtained mixed solution;
2) mixed solution carried out thermal decomposition and collect product;
3) product is washed through water and ethanol successively, then the obtained porous MnCo of calcining in air
2o
4;
Wherein, slaine contains soluble manganese salt and soluble cobalt; Preferred cobalt nitrate and manganese nitrate.
Invention further provides a kind of porous MnCo described above
2o
4application in oxygen reduction and oxygen evolution reaction.
Pass through technique scheme, the present invention, by soluble manganese salt, soluble cobalt are carried out thermal decomposition in the system of surfactant, second alcohol and water composition, then washs and calcines the bifunctional catalyst that just can obtain and can have catalytic performance simultaneously to ORR and OER.This preparation method's step is easy, and raw material is easy to get and then makes this porous MnCo
2o
4can be widely applied in ORR and OER.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is MnCo obtained in embodiment 1
2o
4scanning electron microscope (SEM) photograph;
Fig. 2 is MnCo obtained in embodiment 1
2o
4xRD figure;
Fig. 3 is MnCo obtained in embodiment 1
2o
4oER linear potential sweep figure;
Fig. 4 is MnCo obtained in embodiment 1
2o
4oRR linear potential sweep figure.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of porous MnCo
2o
4, this porous MnCo
2o
4particle diameter be 30-50nm, specific area is 20-32m
2/ g.
Present invention also offers a kind of above-mentioned porous MnCo
2o
4preparation method, comprising:
1) slaine, surfactant, ethanol, water are carried out mixing with obtained mixed solution;
2) mixed solution carried out thermal decomposition and collect product;
3) product is washed through water and ethanol successively, then the obtained porous MnCo of calcining in air
2o
4;
Wherein, slaine contains soluble manganese salt and soluble cobalt, and wherein the kind of soluble manganese salt and soluble cobalt to select in wide scope, but from cost and obtained porous MnCo
2o
4catalytic effect on consider, preferred cobalt nitrate and manganese nitrate.
Step 1 at said method) in, the consumption of each raw material can be selection in wide scope, but in order to make the porous MnCo obtained
2o
4there is more excellent ORR and OER catalytic performance, preferably, in step 1) in, relative to the slaine of 3-6mmol, the consumption of surfactant activity agent is 1-3mmol, and the consumption of ethanol is 15-60ml, and the consumption of water is 15-60ml.
Step 1 at said method) in, in slaine, the consumption of each component can be selection in wide scope, but in order to make the porous MnCo obtained
2o
4have more excellent ORR and OER catalytic performance, preferably, in slaine, the mol ratio of soluble manganese salt and soluble cobalt is 1:2.
Step 1 at said method) in, the kind of surfactant activity agent can be selection in wide scope, but in order to make the porous MnCo obtained
2o
4there is more excellent ORR and OER catalytic performance, preferably, surfactant activity agent be selected from the surfactant of dodecyl sodium sulfate, neopelex and trade mark P123 one or more.
Step 1 at said method) in, the condition of thermal decomposition can be selection in wide scope, but in order to make the porous MnCo obtained
2o
4there is more excellent ORR and OER catalytic performance, preferably, in step 2) in, thermal decomposition at least meets the following conditions: heat decomposition temperature is 480-700 DEG C.
Step 1 at said method) in, the condition of calcining can be selection in wide scope, but in order to make the porous MnCo obtained
2o
4there is more excellent ORR and OER catalytic performance, preferably, in step 3) in, calcining at least meets the following conditions: calcining heat is 500-700 DEG C, and calcination time is 2-6h.
And in step 1 of the present invention) in, in order to make each material to mix fully, preferably, carry out under being blended in ultrasonic condition.
And in step 3 of the present invention) in, the moisture remained to prevent the surface of solids is on the impact of calcining, and preferably, before being calcined, method also comprises: by the system drying and processing 1-6h at 60-80 DEG C after washing.
Invention further provides a kind of porous MnCo described above
2o
4application in oxygen reduction and oxygen evolution reaction.
Below will be described the present invention by embodiment.
Embodiment 1
1) by the Co (NO of 2mmol
3)
2, 1mmol Mn (NO
3)
2, the SDS (dodecyl sodium sulfate) of 2mmol, 15ml deionized water and 15ml EtOH Sonicate be mixed to form mixed liquor;
2) by the thermal decomposition at 480 DEG C of above-mentioned mixed liquor;
3) product of decomposition is washed 3 times with deionized water, ethanol respectively, then put into 80 DEG C of baking ovens and dry 2h, in the air of 600 DEG C, then calcine 4h with obtained porous MnCo
2o
4.
Embodiment 2
Carry out according to the method for embodiment 1, unlike, by step 3) in calcining heat change 500 DEG C into.
Embodiment 3
Carry out according to the method for embodiment 1, unlike, by step 3) in calcining heat change 700 DEG C into.
Embodiment 4
Carry out according to the method for embodiment 1, unlike, by step 3) in calcination time change 6h into.
Embodiment 5
Carry out according to the method for embodiment 1, unlike, change the consumption of SDS into 1mmol, step 3) in calcining heat change 500 DEG C into.
Embodiment 6
Carry out according to the method for embodiment 1, unlike, change the consumption of SDS into 1mmol.
Embodiment 7
Carry out according to the method for embodiment 1, unlike, change the consumption of SDS into 1mmol, step 3) in calcining heat change 700 DEG C into.
Embodiment 8
Carry out according to the method for embodiment 1, unlike, change the consumption of cobalt nitrate into 4mmol, the consumption of manganese nitrate changes 2mmol into, step 3) in calcining heat change 500 DEG C into.
Embodiment 9
Carry out according to the method for embodiment 1, unlike, change the consumption of cobalt nitrate into 4mmol, the consumption of manganese nitrate changes 2mmol into.
Embodiment 10
Carry out according to the method for embodiment 1, unlike, change the consumption of cobalt nitrate into 4mmol, the consumption of manganese nitrate changes 2mmol into, step 3) in calcining heat change 700 DEG C into.
Embodiment 11
Carry out according to the method for embodiment 1, unlike, by step 2) in heat decomposition temperature change 600 DEG C into.
Test example 1
By FDAC HitachS-4800SEM to the porous MnCo in embodiment 1
2o
4carry out ESEM detection, the results are shown in Figure 1, as seen from the figure, porous MnCo
2o
4particle diameter be 30-50nm, specific area is 24.2334m
2/ g.Porous MnCo obtained in embodiment 2-11
2o
4eSEM testing result and embodiment 1 in porous MnCo
2o
4be consistent.
Test example 2
By the XRD-6000 of Japanese Shimadzu Corporation to the porous MnCo in embodiment 1
2o
4carry out XRD detection, the results are shown in Figure 2, as seen from the figure, by contrasting known by XRD figure with standard card JCPDFCardNO.77-0471, the product in embodiment 1 is MnCo
2o
4.XRD testing result and Fig. 2 of product obtained in embodiment 2-11 are consistent.
Test example 3
First, by the MnCo of 2mg
2o
4(embodiment 1 obtains), the carbon (VulcanXC-72) of 1mg, the water of 665 μ L, the N of 335 μ L, dinethylformamide (DMF), 10 μ L 5 % by weight Nafion solution mixing system obtain electrode ink, then getting 20 μ L electrode ink drops on the glass-carbon electrode of 5mm, naturally dries with obtained working electrode.
Then, the KOH solution of itself OER and ORR linear potential sweep curve at the saturated 0.1M of oxygen is surveyed with electrochemical workstation (Shanghai occasion China 760e), the results are shown in Figure 3 and Fig. 4, wherein, the ORR linear potential sweep figure of Fig. 3 to be the OER linear potential sweep figure of the saturated 0.1MKOH of oxygen at 1600 rpm, Fig. 4 be saturated 0.1MKOH of oxygen at 1600 rpm.From Fig. 3 and 4, obtain in embodiment 1 and obtain MnCo
2o
4to OER and ORR, all there is excellent catalytic action.
Similarly, Electrochemical Detection result and Fig. 3-4 of obtained in embodiment 2-11 product are consistent.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a porous MnCo
2o
4, it is characterized in that, described porous MnCo
2o
4particle diameter be 30-50nm, specific area is 20-32m
2/ g.
2. a porous MnCo as claimed in claim 1
2o
4preparation method, it is characterized in that, comprising:
1) slaine, surfactant, ethanol, water are carried out mixing with obtained mixed solution;
2) described mixed solution carried out thermal decomposition and collect product;
3) described product is washed through water and ethanol successively, then the obtained described porous MnCo of calcining in air
2o
4;
Wherein, described slaine contains soluble manganese salt and soluble cobalt; Preferred cobalt nitrate and manganese nitrate.
3. preparation method according to claim 2, wherein, in step 1) in, relative to the described slaine of 3-6mmol, the consumption of described surfactant activity agent is 1-3mmol, and the consumption of described ethanol is 15-60ml, and the consumption of described water is 15-60ml.
4. preparation method according to claim 3, wherein, in described slaine, the mol ratio of described soluble manganese salt and soluble cobalt is 1:2.
5. preparation method according to claim 4, wherein, described surfactant activity agent be selected from the surfactant of dodecyl sodium sulfate, neopelex and trade mark P123 one or more.
6. according to the preparation method in claim 1-5 described in any one, wherein, in step 2) in, described thermal decomposition at least meets the following conditions: heat decomposition temperature is 480-700 DEG C.
7. preparation method according to claim 6, wherein, in step 3) in, described calcining at least meets the following conditions: calcining heat is 500-700 DEG C, and calcination time is 2-6h.
8. carry out under being blended in ultrasonic condition according to the preparation method in claim 1-5 described in any one, wherein.
9. according to the preparation method in claim 1-5 described in any one, wherein, before described calcining, described method also comprises: by the system drying and processing 1-6h at 60-80 DEG C after washing.
10. a porous MnCo as claimed in claim 1
2o
4application in oxygen reduction and oxygen evolution reaction.
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Cited By (7)
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| CN107069025A (en) * | 2017-04-21 | 2017-08-18 | 哈尔滨工业大学 | Sour manganese material of a kind of stratiform cobalt and preparation method thereof |
| CN107601579A (en) * | 2017-09-07 | 2018-01-19 | 盐城工学院 | A kind of preparation method of high-performance porous C o Mn O nanometer sheet materials and its resulting materials and application |
| CN108238648A (en) * | 2018-03-26 | 2018-07-03 | 淮北师范大学 | A kind of preparation method of lithium ion battery negative material |
| CN108607615A (en) * | 2016-12-10 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of CoMn2O4@PAni catalyst and its preparation and application |
| WO2020032256A1 (en) * | 2018-08-09 | 2020-02-13 | 国立研究開発法人理化学研究所 | Method and apparatus for water electrolysis, and method for determining drive potential of water electrolysis |
| CN112371127A (en) * | 2020-11-17 | 2021-02-19 | 惠州学院 | Preparation method of cobaltate nanocomposite with bell-shaking structure and application of cobaltate nanocomposite in catalyzing ammonia borane hydrolysis to produce hydrogen |
| CN114497588A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Flow battery anode catalyst and preparation method and application thereof |
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| CN108607615A (en) * | 2016-12-10 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of CoMn2O4@PAni catalyst and its preparation and application |
| CN107069025A (en) * | 2017-04-21 | 2017-08-18 | 哈尔滨工业大学 | Sour manganese material of a kind of stratiform cobalt and preparation method thereof |
| CN107601579A (en) * | 2017-09-07 | 2018-01-19 | 盐城工学院 | A kind of preparation method of high-performance porous C o Mn O nanometer sheet materials and its resulting materials and application |
| CN107601579B (en) * | 2017-09-07 | 2019-05-10 | 盐城工学院 | The preparation method and its resulting materials of a kind of high-performance porous C o-Mn-O nanometer sheet material and application |
| CN108238648A (en) * | 2018-03-26 | 2018-07-03 | 淮北师范大学 | A kind of preparation method of lithium ion battery negative material |
| US11572630B2 (en) | 2018-08-09 | 2023-02-07 | Riken | Method and apparatus for water electrolysis, and method for determining drive potential of water electrolysis |
| WO2020032256A1 (en) * | 2018-08-09 | 2020-02-13 | 国立研究開発法人理化学研究所 | Method and apparatus for water electrolysis, and method for determining drive potential of water electrolysis |
| JP7284519B2 (en) | 2018-08-09 | 2023-05-31 | 国立研究開発法人理化学研究所 | Water electrolysis method and apparatus, and method for determining driving potential for water electrolysis |
| JPWO2020032256A1 (en) * | 2018-08-09 | 2021-08-12 | 国立研究開発法人理化学研究所 | Water electrolysis method and equipment, and method for determining the driving potential of water electrolysis |
| CN114040996A (en) * | 2018-08-09 | 2022-02-11 | 国立研究开发法人理化学研究所 | Method and apparatus for electrolyzing water, and method for determining driving potential of electrolyzed water |
| CN114497588A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Flow battery anode catalyst and preparation method and application thereof |
| CN112371127A (en) * | 2020-11-17 | 2021-02-19 | 惠州学院 | Preparation method of cobaltate nanocomposite with bell-shaking structure and application of cobaltate nanocomposite in catalyzing ammonia borane hydrolysis to produce hydrogen |
| CN112371127B (en) * | 2020-11-17 | 2023-07-14 | 惠州学院 | Preparation method of cobaltate nanocomposite with bell structure and application of cobaltate nanocomposite in catalyzing ammonia borane hydrolysis to produce hydrogen |
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