CN103240080A - Application of manganese oxide/graphene catalyst - Google Patents
Application of manganese oxide/graphene catalyst Download PDFInfo
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- CN103240080A CN103240080A CN2012100301071A CN201210030107A CN103240080A CN 103240080 A CN103240080 A CN 103240080A CN 2012100301071 A CN2012100301071 A CN 2012100301071A CN 201210030107 A CN201210030107 A CN 201210030107A CN 103240080 A CN103240080 A CN 103240080A
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Abstract
The invention relates to an electrode catalyst, specifically to an application of manganese oxide/graphene catalyst. The manganese oxide/graphene catalyst is used in an air electrode. According to the catalyst, graphene and manganese oxide are respectively prepared by chemical reduction of graphite oxide and hydro-thermal synthesis, and modification of manganese oxide on the surface of a graphene film is realized by a physical dispensing method so as to obtain the manganese oxide/graphene air electrode catalyst. The prepared catalyst has excellent catalytic performance. By the adoption of the catalyst, overpotential of an oxygen reduction reaction can be reduced and reaction current can be increased.
Description
Technical field
The present invention relates to electrode catalyst, specifically a kind of application of manganese oxide/graphen catalyst.
Background technology
Air electrode is played the part of in power conversion system (as fuel cell and metal-air battery) the key player, and the reaction on it is oxygen reduction reaction.Oxygen reduction reaction has characteristics such as process complexity, dynamics be slow, and this has just reduced the efficient of power conversion system.Therefore, can make that the development of the high performance catalyst that the quadrielectron reduction of oxygen takes place is significant under lower overpotential.Platinum (Pt) sill is the present maximum oxygen reduction reaction catalyst of research, however its cost height, scarcity of resources, and this has just limited its commercial application.
Manganese oxide is familiar with by people very early to the catalytic action of oxygen reduction reaction.Advantage with low cost makes people carry out big quantity research to it, comprises catalytic mechanism, and pattern, crystal formation, doped chemical etc. are to influence of catalytic performance etc.ZL01107488.4 mixes metallic elements such as lithium, cobalt in electrolytic manganese dioxide, improve its catalytic performance; ZL200410013631.3 adopts the method for solid phase calcination to make the carbon that contains manganese dioxide and lead oxides and carries air electrode catalyst; ZL20110065766.4 has prepared with MnO, Mn
2O
3And Mn
3O
4Be active main body, cobalt oxide or nickel oxide are the air electrode catalyst of adulterant; ZL02133309.2 has prepared MnO
2-Mn
3O
4/ Mn
2O
3Air electrode catalyst.Be one to have the air electrode catalyst of application prospect by above-mentioned explanation manganese oxide.
Since Geim seminar in 2004 found Graphene, the application of Graphene received much concern always.Graphene has potential using value owing to have high specific area and high edge defect in the electro-catalysis field.Graphene is often used as catalyst carrier material, is applied in the oxygen reduction reaction catalysis.Existing a lot of patents relate to the compound of Graphene and noble metal, disclose the preparation method that a kind of proton fuel cell is used the Pt/ graphen catalyst respectively as ZL201010149141.1 and ZL201110177035.9.ZL201110135866.X adopts the method for Graphene and potassium permanganate reaction to prepare the composite of Graphene and manganese oxide, but its oxygen reduction reaction catalytic performance is not characterized.Simultaneously, also do not have by physical method and prepare Graphene and manganese oxide compound as the report of air electrode catalyst.
Summary of the invention
The object of the invention is to provide a kind of application of manganese oxide/graphen catalyst.
For achieving the above object, the technical solution used in the present invention is:
A kind of application of manganese oxide/graphen catalyst, described manganese oxide/graphen catalyst is used for air electrode.Described manganese oxide/graphen catalyst is used for the hydrogen reduction air electrode.Described manganese oxide/graphen catalyst is used for fuel cell or metal-air battery.
Described manganese oxide/Graphene air electrode catalyst is prepared as:
(1) preparation of graphene film
Get 0.5～2mg mL of 10-30 μ L
-1Graphene colloidal solution drip and be coated onto working electrode surface, place under the nitrogen atmosphere dryly in room temperature, obtain graphene film;
(2) preparation of manganese oxide/Graphene air electrode catalyst
Get 1～4mg mL of 10-30 μ L
-1Manganese oxide colloidal solution drip on the graphene film that is coated in step (1) preparation, place under the nitrogen atmosphere dryly in room temperature, obtain manganese oxide/Graphene air electrode catalyst.
From the angle of catalytic performance, if a kind of material can make that the electric current of goal response increases or overpotential reduces, it is exactly a kind of effective catalyst so.The catalyst of the present invention's preparation can make the overpotential of oxygen reduction reaction reduce, and can make peak current increase again, this explanation, and its catalytic effect is good.
The advantage that the present invention has:
1. the present invention's method of adopting physics to drip to be coated with has realized the compound of Graphene and manganese oxide, and is simple to operate, and the composite that obtains has good catalytic performance to oxygen reduction reaction.
2. apply the present invention in the oxygen reduction reaction, the half wave potential of oxygen reduction reaction is obviously moved to right, electric current is significantly increased, realized the mutual supplement with each other's advantages of Graphene and manganese oxide.
3. apply the present invention in the oxygen reduction reaction, can make the quadrielectron reduction of oxygen under lower overpotential, take place.
4. apply the present invention to show good catalytic stability in the oxygen reduction reaction.
5. from the preparation method, the present invention adopts physics to drip coating method and is prepared, and by the performance of regulation and control manganese oxide, is easy to optimize the performance of prepared manganese oxide/Graphene, and simple to operate, be easy to suitability for industrialized production.
6. from the angle of economy, the catalyst of the present invention's preparation is raw material with graphite powder, potassium permanganate, manganese sulfate etc., and cheap, the wide material sources of these costs of material make that the cost of catalyst is low, is easy to commercialization and promotes.
Description of drawings
The stereoscan photograph (wherein A is macrograph, and B is the high power photo) of the prepared manganese oxide that Fig. 1 provides for the embodiment of the invention.
The rotating disk electrode (r.d.e) volt-ampere curve figure of the manganese oxide that Fig. 2 provides for the embodiment of the invention/Graphene modified electrode in potassium hydroxide solution (0.1M) (wherein, the glass carbon resistance rod that curve a correspondence is not modified, the glass carbon resistance rod that the corresponding Graphene of curve b is modified, the glass carbon resistance rod that the corresponding manganese oxide of curve c is modified, the curve d glass carbon resistance rod that corresponding manganese oxide/Graphene is modified).
The electron transfer number of oxygen with the change curve of current potential (wherein on the manganese oxide that Fig. 3 provides for the embodiment of the invention/Graphene modified electrode, the glass carbon resistance rod that curve a correspondence is not modified, the glass carbon resistance rod that the corresponding Graphene of curve b is modified, the glass carbon resistance rod that the corresponding manganese oxide of curve c is modified, the curve d glass carbon resistance rod that corresponding manganese oxide/Graphene is modified)
The manganese oxide that Fig. 4 provides for the embodiment of the invention/Graphene modified electrode in potassium hydroxide solution (0.1M) in electric current-time changing curve figure of-0.4V (with respect to the Ag/AgCl electrode) (wherein curve a is the glass carbon resistance rod that manganese oxide is modified, and curve b is the glass carbon resistance rod that manganese oxide/Graphene is modified).
The specific embodiment
The present invention will be further described below by embodiment.
Embodiment 1
The preparation of manganese oxide/graphen catalyst: at first adopt the method for physical modification to modify one deck graphene film at working electrode surface, to be dripped by the colloidal solution of the manganese oxide of hydrothermal synthesis method preparation then and be coated in the graphene film surface, obtain manganese oxide/Graphene oxygen reduction reaction catalyst.
Its concrete steps are,
Get the 1g graphite powder, 1g sodium nitrate joins in the 46mL concentrated sulfuric acid, ice bath stirs 4h.Under stirring condition, slowly add 6g potassium permanganate (guaranteeing that temperature maintenance is below 10 ℃) then.Subsequently it is transferred to stirring in water bath 2h in 35 ℃ the water-bath, add the 92mL ultra-pure water then, temperature is transferred to 98 ℃ of stirring in water bath 2h, this moment, solution was vivid yellow.Add the warm water of 200mL and 30% hydrogen peroxide of 20mL at last, stir 1h, this moment, solution was brown.
The colloidal solution that obtains is centrifugal, then with mass concentration be the washing of 15% hydrochloric acid solution once, clean three times with ultra-pure water again, clean once with absolute ethyl alcohol at last, obtain the lotion of graphite oxide.Lotion grinds with mortar after 60 ℃ of oven dry, obtains the graphite oxide of powdery.Graphite oxide is dissolved in the ultra-pure water, obtains 0.5mg mL
-1Graphite oxide colloidal solution, ultrasonic back is used for follow-up electronation and prepares Graphene colloidal solution.
Get the prepared graphite oxide colloidal solution of 10mL and join in the vial of 20mL, then to the ammoniacal liquor that wherein adds 70 μ L (28%) and 4 μ L hydrazines (85%), in stirring is placed on 95 ℃ water-bath, react 1h, obtain the Graphene colloidal solution of black.
Get 2mmo l potassium permanganate solid, add ultra-pure water and be mixed with 40mL solution, the manganese sulfate solid that other gets 3mmol is made into 40mL solution, both are mixed, reaction at once generates the precipitation of brownish black, be stirred to the suspension that forms homogeneous, then the mixed solution that obtains transferred in the 100mL teflon-lined autoclave, place 160 ℃ baking oven to react 4h.Reaction finishes the back and takes out reactor, naturally cools to room temperature, filters, and spends deionised water for several times, takes out 80 ℃ of dry backs, grinds and obtains the manganese oxide powder.Get prepared manganese oxide powder and be scattered in 0.05% the Nafion ethanolic solution, be made into 2mg mL
-1Colloidal solution stand-by.
Get the prepared Graphene colloidal solution of 20 μ L and drip and be coated in glass carbon resistance rod surface, dry under the room temperature nitrogen atmosphere, obtain the glass carbon resistance rod that graphene film is modified.Get 20 μ L manganese oxide colloidal solution then and drip and be coated in prepared graphene film surface, after room temperature nitrogen atmosphere drying, obtain manganese oxide/graphene composite material.Adopt and use the same method, obtain the glass carbon resistance rod (referring to Fig. 1) that glass carbon resistance rod that Graphene modifies and manganese oxide are modified respectively.
The stereoscan photograph of prepared manganese oxide as shown in Figure 1, therefrom manganese oxide is the one dimension wire as can be seen, and diameter is 40-50nm.High draw ratio is conducive to fully contacting of catalyst and reactant.
Then adopt the rotating disk electrode (r.d.e) voltammetry to detect the glass carbon resistance rod of the above-mentioned manganese oxide that makes and graphene composite material modification to the catalytic performance of oxygen reduction reaction.Working electrode is the glass carbon resistance rod that composite is modified, and is the Pt electrode to electrode, and reference electrode is Ag/AgCl (KCl is saturated) electrode, and electrolyte is potassium hydroxide solution (0.1M).The potential scan scope is-0.1V--1.1V that sweep speed is 10mVs
-1, the working electrode rotating speed is 800rpm.Keep other condition constant, change working electrode into the glass carbon resistance rod of manganese oxide modification, glass carbon resistance rod and not modified glass carbon resistance rod, (referring to Fig. 2) in contrast that Graphene is modified.
Test result as shown in Figure 2, the modification of Graphene can cause obviously moving to right of oxygen reduction reaction half wave potential, illustrates that it can reduce to react overpotential; Simultaneously, also make electric current increase, this high-specific surface area characteristic with Graphene is relevant.The modification of manganese oxide does not change the current potential of oxygen reduction reaction, but makes electric current obviously increase, and this can this reaction intermediate of catalyzing hydrogen peroxide be caused by manganese oxide.Graphene and cobalt hydroxide compound makes half wave potential obviously move to right, and electric current significantly increases, and has realized the mutual supplement with each other's advantages of two kinds of materials.
Difference from Example 1 is:
Preparing manganese oxide/Graphene oxygen reduction reaction catalyst concrete steps is,
Get the 1g graphite powder, 1g sodium nitrate joins in the 23mL concentrated sulfuric acid, ice bath stirs 4h.Under stirring condition, slowly add 3g potassium permanganate (guaranteeing that temperature maintenance is below 10 ℃) then.Subsequently it is transferred to stirring in water bath 3h in 30 ℃ the water-bath, add the 92mL ultra-pure water then, temperature is transferred to 95 ℃ of stirring in water bath 3h, this moment, solution was vivid yellow.Add the warm water of 300mL and 30% hydrogen peroxide of 30mL at last, stir 1h, this moment, solution was brown.
The colloidal solution that obtains is centrifugal, then with mass concentration be the washing of 25% hydrochloric acid solution once, clean three times with ultra-pure water again, clean once with absolute ethyl alcohol at last, obtain the lotion of graphite oxide.Lotion grinds with mortar after 70 ℃ of oven dry, obtains the graphite oxide of powdery.Graphite oxide is dissolved in the ultra-pure water, obtains 1mg mL
-1Graphite oxide colloidal solution, ultrasonic back is used for follow-up electronation and prepares Graphene colloidal solution.
Getting the prepared graphite oxide colloidal solution of 10mL joins in the vial of 20mL, then to the ammoniacal liquor that wherein adds 90 μ L (28%) and 3 μ L hydrazines (85%), in stirring is placed on 90 ℃ water-bath, react 1.5h, obtain the Graphene colloidal solution of black.
Get 3mmol potassium permanganate solid, add ultra-pure water and be mixed with 40mL solution, the manganese sulfate solid that other gets 4.5mmol is made into 40mL solution, both are mixed, reaction at once generates the precipitation of brownish black, be stirred to the suspension that forms homogeneous, then the mixed solution that obtains transferred in the 100mL teflon-lined autoclave, place 170 ℃ baking oven to react 4h.Reaction finishes the back and takes out reactor, naturally cools to room temperature, filters, and spends deionised water for several times, takes out 80 ℃ of dry backs, grinds and obtains the manganese oxide powder.Get prepared manganese oxide powder and be scattered in 0.5% the Nafion ethanolic solution, be made into 1mg mL
-1Colloidal solution stand-by.
Get the prepared Graphene colloidal solution of 10 μ L and drip and be coated in glass carbon resistance rod surface, dry under the room temperature nitrogen atmosphere, obtain the glass carbon resistance rod that graphene film is modified.Get 10 μ L manganese oxide colloidal solution then and drip and be coated in prepared graphene film surface, after room temperature nitrogen atmosphere drying, obtain manganese oxide/graphene composite material.Adopt and use the same method, obtain the glass carbon resistance rod that glass carbon resistance rod that Graphene modifies and manganese oxide are modified respectively.
Adopt with embodiment 1 in identical method obtain the volt-ampere curve of oxygen reduction reaction on the glass carbon resistance rod of embodiment 2 prepared Graphenes and the modification of manganese oxide composite.In conjunction with Koutechy-Levich (K-L) equation 1/i=1/i
k+ 1/0.62nFC
0D
0 2/3v
-1/6ω
1/2Obtain the K-L curve, can calculate the electron transfer number of oxygen according to slope of a curve.
Result of calculation as shown in Figure 3, as can be seen, electron transfer number can be near 4 at-0.4V on the glass carbon resistance rod that manganese oxide and graphene composite material are modified, illustrate prepared air electrode catalyst effectively the quadrielectron of Catalytic Oxygen reduce.
Embodiment 3
Be with embodiment 1 and 2 differences:
Preparing manganese oxide/Graphene oxygen reduction reaction catalyst concrete steps is,
Get the 1g graphite powder, 1g sodium nitrate joins in the 23mL concentrated sulfuric acid, ice bath stirs 4h.Under stirring condition, slowly add 6g potassium permanganate (guaranteeing that temperature maintenance is below 10 ℃) then.Subsequently it is transferred to stirring in water bath 1.5h in 40 ℃ the water-bath, add the 100mL ultra-pure water then, temperature is transferred to 93 ℃ of stirring in water bath 4h, this moment, solution was vivid yellow.Add the warm water of 150mL and 60% hydrogen peroxide of 25mL at last, stir 1h, this moment, solution was brown.
The colloidal solution that obtains is centrifugal, then with mass concentration be the washing of 20% hydrochloric acid solution once, clean three times with ultra-pure water again, clean once with absolute ethyl alcohol at last, obtain the lotion of graphite oxide.Lotion grinds with mortar after 55 ℃ of oven dry, obtains the graphite oxide of powdery.Graphite oxide is dissolved in the ultra-pure water, obtains 2mg mL
-1Graphite oxide colloidal solution, ultrasonic back is used for follow-up electronation and prepares Graphene colloidal solution.
Get the prepared graphite oxide colloidal solution of 10mL and join in the vial of 20mL, then to the ammoniacal liquor that wherein adds 100 μ L (28%) and 5 μ L hydrazines (85%), in stirring is placed on 80 ℃ water-bath, react 2h, obtain the Graphene colloidal solution of black.
Get 6mmol potassium permanganate solid, add ultra-pure water and be mixed with 40mL solution, the manganese sulfate solid that other gets 9mmol is made into 40mL solution, both are mixed, reaction at once generates the precipitation of brownish black, be stirred to the suspension that forms homogeneous, then the mixed solution that obtains transferred in the 100mL teflon-lined autoclave, place 170 ℃ baking oven to react 5h.Reaction finishes the back and takes out reactor, naturally cools to room temperature, filters, and spends deionised water for several times, takes out 80 ℃ of dry backs, grinds and obtains the manganese oxide powder.Get prepared manganese oxide powder and be scattered in 0.5% the Nafion ethanolic solution, be made into 4mg mL
-1Colloidal solution stand-by.
Get the prepared Graphene colloidal solution of 30 μ L and drip and be coated in glass carbon resistance rod surface, dry under the room temperature nitrogen atmosphere, obtain the glass carbon resistance rod that graphene film is modified.Get 30 μ L manganese oxide colloidal solution then and drip and be coated in prepared graphene film surface, after room temperature nitrogen atmosphere drying, obtain manganese oxide/graphene composite material.Adopt and use the same method, obtain the glass carbon resistance rod that glass carbon resistance rod that Graphene modifies and manganese oxide are modified respectively.
Obtain prepared manganese oxide/Graphene according to electric current-time graph and modify the glass carbon resistance rod to the catalytic stability information of oxygen reduction reaction.Working electrode is the glass carbon resistance rod that composite is modified, and is the Pt electrode to electrode, and reference electrode is Ag/AgCl (KCl is saturated) electrode, and electrolyte is potassium hydroxide solution (0.1M).Test potential is-0.4V, and the testing time is 10Ks, and the working electrode rotary speed is 800rpm.In whole test process, electrolyte keeps the oxygen saturation state.Keep other condition constant, change working electrode into glass carbon resistance rod that manganese oxide is modified, in contrast.
Test result is modified the glass carbon resistance rod with manganese oxide and is compared as shown in Figure 4, and manganese oxide/Graphene is modified the glass carbon resistance rod and had bigger current density, and has good stability.
Claims (4)
1. the application of a manganese oxide/graphen catalyst is characterized in that: described manganese oxide/graphen catalyst is used for air electrode.
2. by the application of the described manganese oxide/graphen catalyst of claim 1, it is characterized in that: described manganese oxide/graphen catalyst is used for the hydrogen reduction air electrode.
3. by the application of claim 1 or 2 described manganese oxide/graphen catalysts, it is characterized in that: described manganese oxide/graphen catalyst is used for fuel cell or metal-air battery.
4. by the application of the described manganese oxide/graphen catalyst of claim 1, it is characterized in that: described manganese oxide/Graphene air electrode catalyst is prepared as:
(1) preparation of graphene film
Get 0.5～2mg mL of 10-30 μ L
-1Graphene colloidal solution drip and be coated onto working electrode surface, place under the nitrogen atmosphere dryly in room temperature, obtain graphene film;
(2) preparation of manganese oxide/Graphene air electrode catalyst
Get 1～4mg mL of 10-30 μ L
-1Manganese oxide colloidal solution drip on the graphene film that is coated in step (1) preparation, place under the nitrogen atmosphere dryly in room temperature, obtain manganese oxide/Graphene air electrode catalyst.
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| CN103854877A (en) * | 2013-12-23 | 2014-06-11 | 燕山大学 | Self-supporting grapheme-manganese oxide combined electrode material and manufacturing method thereof |
| CN104415758A (en) * | 2013-09-06 | 2015-03-18 | 中国科学院大连化学物理研究所 | Preparation method and applications of non-noble metal electrocatalyst |
| CN105244483A (en) * | 2015-09-16 | 2016-01-13 | 常州大学 | Preparation method modified manganese-based composite material used for lithium ion battery |
| CN106159289A (en) * | 2016-07-05 | 2016-11-23 | 张启辉 | Composite of Mn oxide Surface coating graphite and preparation method thereof |
| CN114976062A (en) * | 2020-10-15 | 2022-08-30 | 昆明理工大学 | Preparation method of nitrogen-doped rGO-supported MnO nanoparticle catalyst |
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Cited By (6)
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| CN104415758A (en) * | 2013-09-06 | 2015-03-18 | 中国科学院大连化学物理研究所 | Preparation method and applications of non-noble metal electrocatalyst |
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| CN105244483A (en) * | 2015-09-16 | 2016-01-13 | 常州大学 | Preparation method modified manganese-based composite material used for lithium ion battery |
| CN106159289A (en) * | 2016-07-05 | 2016-11-23 | 张启辉 | Composite of Mn oxide Surface coating graphite and preparation method thereof |
| CN114976062A (en) * | 2020-10-15 | 2022-08-30 | 昆明理工大学 | Preparation method of nitrogen-doped rGO-supported MnO nanoparticle catalyst |
| CN114976062B (en) * | 2020-10-15 | 2024-01-26 | 昆明理工大学 | Preparation method of nitrogen-doped rGO loaded MnO nanoparticle catalyst |
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Application publication date: 20130814 |