CN105363448B - A kind of charcoal/silver/manganese dioxide three-phase composite catalyst and preparation method thereof - Google Patents
A kind of charcoal/silver/manganese dioxide three-phase composite catalyst and preparation method thereof Download PDFInfo
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Abstract
Charcoal/silver/manganese dioxide three-phase composite catalyst simple and suitable for chlorine industry and preparation method thereof is prepared the present invention relates to a kind of, charcoal is carried into silver catalyst with being prepared after charcoal load α type manganese dioxide-catalysts by physical mixed.Charcoal, which carries silver catalyst, to be used as a kind of effective catalyst to be applied in salt electrolysis, the catalytic activity of its catalytic oxygen reduction reaction can not only be improved after adding charcoal and carrying α type manganese dioxide-catalysts, while the hydrogen peroxide yield in reaction can be reduced so as to improve its stability.
Description
Technical field
The invention belongs to catalyst field, and in particular to a kind of charcoal supported noble metal catalyst and charcoal carry metal oxide oxidation catalyst
The preparation and application of agent, particularly charcoal carry silver and charcoal carries what α types manganese dioxide was prepared into by certain quality than physical mixed
The method of catalyst, and applied to the salt electrolysis in chlorine industry.
Background technology
Redox reactions（ORR）In fuel cell, metal-air battery, chlorine industry and corrosion protection etc.
With particularly important meaning.Be most widely used at present for redox reactions at the same it is most outstanding be platinum catalyst
And its platinoid catalyst.But because the expensive while reserves of noble metal platinum are limited, non-platinum-type catalyst turns into existing
Study hotspot.One of silver-colored optimal candidate catalyst as instead of platinum, not only catalytic activity is higher, while in alkalescence condition
Stability inferior is high, thus causes widely studied.The charcoal that superelevation load capacity can be prepared using chemical reduction method carries silver catalyst, but
It is that its hydrogen peroxide yield is higher, the decline of its stability can be further resulted in.In order to reduce the peroxidating in redox reactions
Hydrogen yield further improves the activity of catalyst simultaneously, and at a low price, environment-friendly while catalytic activity also urge by preferable manganese dioxide
Agent receives the pay attention to day by day of people.Manganese bioxide material is a kind of material with certain redox reactions electric catalyticing characteristic
Material, it is especially desirable to which, it is noted that in the application in terms of electrochemistry, manganese bioxide material has outstanding decomposition to hydrogen peroxide
Effect.Therefore, this silver and the compound catalyst of manganese dioxide are prepared and carries silver catalyst in oxygen reduction for reducing foregoing charcoal
Hydrogen peroxide yield in reaction, it is significant so as to improve the stability of catalyst.
Research finds, the manganese element in Mn oxide has a variety of valence states, with titanium dioxide in the Mn oxide of different valence state
The catalytic performance of manganese is optimal.Further, manganese dioxide has 5 kinds of different oikocrysts, and more than 30 plant different para-crystals, not the isomorphous
The catalytic activity of the manganese dioxide of type also differs, wherein optimal with α type manganese dioxide.Salt electricity in current chlorine industry
Solve in catalyst, it is a kind of conventional and efficient catalyst that charcoal, which carries silver catalyst,.Charcoal is carried into α types manganese dioxide and charcoal carries silver catalysis
Agent physical mixed, this preparation method is simple, while the high catalyst of catalytic activity can substantially reduce the cost of catalyst.Cause
This is based on the commercialized active demands of new energy such as chlorine industry or fuel cell, and the charcoal for developing high activity carries silver and charcoal load α
Type manganese dioxide mixed catalyst will have very big prospects for commercial application.
The content of the invention
The invention aims to solve problem of the prior art, there is provided one kind prepares simply and is applied to chlorine industry
In high performance catalyst and preparation method thereof, charcoal is carried after silver catalyst carries α type manganese dioxide-catalysts with charcoal and passes through physics
It is prepared by mixing.Charcoal, which carries silver catalyst, to be used as a kind of effective catalyst to be applied in salt electrolysis, and α types are carried adding charcoal
The catalytic activity of its catalytic oxygen reduction reaction can not only be improved after manganese dioxide-catalyst, while the peroxide in reaction can be reduced
Change hydrogen yield so as to improve its stability.
The present invention is achieved through the following technical solutions：
A kind of charcoal/silver/manganese dioxide three-phase composite catalyst, charcoal is carried into silver catalyst and charcoal carries the catalysis of α types manganese dioxide
The physical mixed of agent, the catalyst after physical mixed is solid powder, and wherein charcoal carries silver catalyst and charcoal carries α type manganese dioxide and urged
The mass ratio of agent is 1:2~2:1.
In a preferred embodiment of the present invention, it is solid powder that the charcoal, which carries silver catalyst, and particle diameter is 3~10nm's
The dispersed surface for being supported on acidifying carbon black of Argent grain, silver-colored load factor are 300%~400%, silver and acidifying carbon black
Mass ratio is 3~4: 1.
In a preferred embodiment of the present invention, it is solid powder that charcoal, which carries α types manganese dioxide-catalyst, diameter about 50nm
α type manganese dioxide nano-rods be supported on acidifying carbon black on, the load factor of α type manganese dioxide nano-rods is 10%~70%, α types
The mass ratio of manganese dioxide nano-rod and acidifying carbon black is 0.1~0.7: 1.
In a preferred embodiment of the present invention, the charcoal carries silver catalyst and is prepared via a method which：
(1) carbon black is added in concentrated nitric acid, the mass ratio of carbon black and concentrated nitric acid is 0.01~0.04: 1；Temperature control
At 120 DEG C~160 DEG C, 3~5h of condensing reflux, room temperature is cooled to, filters and be washed with deionized water to neutral, vacuum drying and obtain
The carbon black of acidifying；
(2) by the carbon black of acidifying and 10~30min of ethylene glycol mixing ultrasonic disperse；The carbon black of acidifying and the matter of ethylene glycol
Amount is than being 0.0001~0.01: 1；
(3) 0.01mol/L~1mol/L silver nitrate solution is mixed with 0.01mol/L~1mol/L ammonia spirit,
The volume ratio 0.1~0.4: 1 of silver nitrate solution and ammonia spirit, by the silver ammino solution configured and 0.01mol/L~5mol/L
Sodium hydroxide solution good dissolved with the carbon black of acidifying and the three-neck flask of ethylene glycol, the silver nitrate solution that is poured into ultrasound successively
With the volume ratio 1~10: 1 of sodium hydroxide solution, the mass ratio of silver nitrate and the carbon black of acidifying is 0.629~6.29: 1, stirring,
At 110 DEG C~140 DEG C, condensing reflux, the reaction time controls in 0.5h~3h temperature control；
(4) above-mentioned reaction product is centrifuged or filtered and be washed to neutrality, dried, obtain charcoal load silver catalyst solid
Powder.
In a preferred embodiment of the present invention, the charcoal carries α type manganese dioxide-catalysts and is prepared via a method which：
(1) mixed solution of potassium permanganate and Manganous sulfate monohydrate is configured, the molar concentration of wherein potassium permanganate is
0.001mol/L~0.01mol/L, the molar concentration of Manganous sulfate monohydrate is 0.001mol/L~0.01mol/L, adds acid
Change carbon black and neopelex is stirred at room temperature 1~3 hour；
(2) solution is transferred in hydrothermal reaction kettle, and places heating response in an oven, reaction temperature 140 °C~
180 °C, the reaction time is 10~16h, and after reaction terminates, solution is centrifuged, and is washed, and is dried, and drying condition is 60 °C true
Sky dries 12h, obtains charcoal and carries α type manganese dioxide-catalyst solid powders.
In a preferred embodiment of the present invention, the physical mixed is：By the charcoal being prepared carry silver catalyst and
What charcoal carried α type manganese dioxide-catalysts is 1 according to mass ratio:2~2:1 ratio physical mixed, grinding are uniform.
In a preferred embodiment of the present invention, the charcoal being prepared is carried into silver catalyst and charcoal carries α type manganese dioxide
Catalyst is 1 according to mass ratio:1 ratio physical mixed.
In a preferred embodiment of the present invention, described carbon black is Graphon.
The present invention also protects the application that above-mentioned composite catalyst is prepared in redox reactions in the basic conditions.
The charcoal of preparation is carried into silver catalyst using a kind of simple physical means by the present invention and charcoal carries α types manganese dioxide and is catalyzed
Agent is mixed with out efficient redox reactions catalyst, by long term test, adjusts the structure of the component of catalyst（As led to
Preparation method, load factor etc. is crossed to be adjusted）, the parameter such as content so that the catalyst is in the basic conditions for catalytic oxygen
Reduction reaction has higher electro-chemical activity and stability.It is former compared with the original precious metal based catalysts of salt electrolysis technology
Material cost substantially reduces, and method is simple, superior performance, has a extensive future.
Brief description of the drawings
Below in conjunction with accompanying drawing, the invention will be further described；
Fig. 1 is the scanning electron microscope diagram piece that charcoal carries silver catalyst in embodiment 1,2,3；
Fig. 2 is the XRD spectrum that charcoal carries silver catalyst in embodiment 1,2,3；
Fig. 3 is the scanning electron microscope diagram piece that charcoal carries α type manganese dioxide-catalysts in embodiment 1,2,3；
Fig. 4 is the XRD spectrum that charcoal carries α type manganese dioxide-catalysts in embodiment 1,2,3；
Fig. 5 is the electro-chemical activity test and implementation of gained physics mixed catalyst at room temperature in embodiment 1,2,3
The stability test of catalyst is prepared under the conditions of example 1, test condition is carried out in the 1mol/L sodium hydroxides of oxygen saturation, is turned
Speed is 1600rpm.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, without structure
Into limitation of the present invention.
Embodiment 1
It is 1 to prepare charcoal and carry silver catalyst to carry α type manganese dioxide-catalysts mass ratio with charcoal:1 physical mixed catalyst
(1) 1g carbon blacks are added in the concentrated nitric acid that 50ml mass fractions are 68%, ultrasonic half an hour, reaction temperature is
120 DEG C, condensing reflux 3h, it is cooled to room temperature, filters and be washed till the charcoal that neutral, vacuum drying is acidified with a large amount of deionized waters
It is black.
(2) carbon black for weighing 100mg acidifyings is put into ultrasonic disperse 30min in three-neck flask with 100g ethylene glycol.
(3) silver nitrate is dissolved in water, is made into silver nitrate solution, the molar concentration of silver nitrate is 0.1mol/L；Will be dense
Ammoniacal liquor is diluted to ammonia spirit, and the molar concentration of ammoniacal liquor is 0.1mol/L；Above-mentioned 37ml silver nitrate solutiones and 111ml ammoniacal liquor is molten
Liquid mixes, and forms the silver ammino solution of water white transparency, sodium hydroxide is dissolved in water, be made into sodium hydroxide solution, sodium hydroxide
Molar concentration be 1mol/L, the volume of sodium hydroxide solution is 4ml；By the silver ammino solution configured and sodium hydroxide solution according to
It is secondary to be poured into that ultrasound is good dissolved with the carbon black of acidifying and the three-neck flask of ethylene glycol, the mass ratio of silver nitrate and the carbon black of acidifying
For 6.29: 1, stirring, at 120 DEG C, condensing reflux, the reaction time controls in 1h temperature control.By the centrifugation point of above-mentioned reaction product
From or filtering be washed to neutrality, dry, obtain charcoal and carry silver catalyst solid powder.Loaded by TG-DTA thermal weight loss instruments
Rate is 400%.
(4) above-mentioned reaction product is centrifuged or filtered and be washed to neutrality, dried, obtain charcoal load silver catalyst solid
Powder.
(5) mixed solution of potassium permanganate and Manganous sulfate monohydrate is configured, the molar concentration of wherein potassium permanganate is
0.005mol/L, the molar concentration of Manganous sulfate monohydrate is 0.005mol/L, adds 75mg acidifying carbon blacks and 500mg dodecanes
Base benzene sulfonic acid sodium salt, it is stirred at room temperature 2 hours.
(6) solution is transferred in hydrothermal reaction kettle, and places heating response in an oven, reaction temperature at 160 °C,
Reaction time is 12h, and after reaction terminates, solution is centrifuged, and is washed, and is dried, and drying condition is 60 °C of vacuum drying 12h,
Obtain charcoal and carry α type manganese dioxide-catalyst solid powders.Load factor is obtained as 30% by TG-DTA thermal weight loss instruments.
(7) charcoal for preparing above-mentioned two step respectively carries silver catalyst and charcoal carries α type manganese dioxide-catalysts according to 1:1
Quality is more uniform than physical mixed, grinding.
It will be seen from figure 1 that Argent grain is evenly distributed on acidifying carbon black, and can from Fig. 2 XRD diffracting spectrums
Go out obviously silver-colored characteristic diffraction peak.From figure 3, it can be seen that the pattern of the α type manganese dioxide prepared is wire, while from
The characteristic diffraction peak occurred in Fig. 4 XRD diffracting spectrums is corresponding with the diffraction maximum of α type manganese dioxide.Finally from the rotation in Fig. 5
Turn disk test curve it can be seen from the figure that mass ratio as 1:The half wave potential of 1 catalyst most just, while limiting diffusion current
Maximum, it is suitable as the effective catalyst of catalytic oxygen reduction reaction.
Embodiment 2
It is 1 to prepare charcoal and carry silver catalyst to carry α type manganese dioxide-catalysts mass ratio with charcoal:2 physical mixed catalyst
(1) 1g carbon blacks are added in the concentrated nitric acid that 50ml mass fractions are 68%, ultrasonic half an hour, reaction temperature is
120 DEG C, condensing reflux 3h, it is cooled to room temperature, filters and be washed till the charcoal that neutral, vacuum drying is acidified with a large amount of deionized waters
It is black.
(2) carbon black for weighing 100mg acidifyings is put into ultrasonic disperse 30min in three-neck flask with 100g ethylene glycol.
(3) silver nitrate is dissolved in water, is made into silver nitrate solution, the molar concentration of silver nitrate is 0.1mol/L；Will be dense
Ammoniacal liquor is diluted to ammonia spirit, and the molar concentration of ammoniacal liquor is 0.1mol/L；Above-mentioned 37ml silver nitrate solutiones and 111ml ammoniacal liquor is molten
Liquid mixes, and forms the silver ammino solution of water white transparency, sodium hydroxide is dissolved in water, be made into sodium hydroxide solution, sodium hydroxide
Molar concentration be 1mol/L, the volume of sodium hydroxide solution is 4ml；By the silver ammino solution configured and sodium hydroxide solution according to
It is secondary to be poured into that ultrasound is good dissolved with the carbon black of acidifying and the three-neck flask of ethylene glycol, the mass ratio of silver nitrate and the carbon black of acidifying
For 6.29: 1, stirring, at 120 DEG C, condensing reflux, the reaction time controls in 1h temperature control.By the centrifugation point of above-mentioned reaction product
From or filtering be washed to neutrality, dry, obtain charcoal and carry silver catalyst solid powder.Loaded by TG-DTA thermal weight loss instruments
Rate is 400%.
(4) above-mentioned reaction product is centrifuged or filtered and be washed to neutrality, dried, obtain charcoal load silver catalyst solid
Powder.
(5) mixed solution of potassium permanganate and Manganous sulfate monohydrate is configured, the molar concentration of wherein potassium permanganate is
0.005mol/L, the molar concentration of Manganous sulfate monohydrate is 0.005mol/L, adds 75mg acidifying carbon blacks and 500mg dodecanes
Base benzene sulfonic acid sodium salt, it is stirred at room temperature 2 hours.
(6) solution is transferred in hydrothermal reaction kettle, and places heating response in an oven, reaction temperature at 160 °C,
Reaction time is 12h, and after reaction terminates, solution is centrifuged, and is washed, and is dried, and drying condition is 60 °C of vacuum drying 12h,
Obtain charcoal and carry α type manganese dioxide-catalyst solid powders.Load factor is obtained as 30% by TG-DTA thermal weight loss instruments.
(7) charcoal for preparing above-mentioned two step respectively carries silver catalyst and charcoal carries α type manganese dioxide-catalysts according to 1:2
Quality is more uniform than physical mixed, grinding.
It will be seen from figure 1 that Argent grain is evenly distributed on acidifying carbon black, and can from Fig. 2 XRD diffracting spectrums
Go out obviously silver-colored characteristic diffraction peak.From figure 3, it can be seen that the pattern of the α type manganese dioxide prepared is wire, while from
The characteristic diffraction peak occurred in Fig. 4 XRD diffracting spectrums is corresponding with the diffraction maximum of α type manganese dioxide.Finally from the rotation in Fig. 5
Turn disk test curve it can be seen from the figure that mass ratio as 1:Although 2 catalyst take-off potential is 1 with mass ratio:1 catalysis
Agent is more or less the same, but the relatively negative limiting diffusion current simultaneously of its half wave potential is smaller, mass ratio 1:1 catalyst is more suitable for making
For the effective catalyst of catalytic oxygen reduction reaction.
Embodiment 3
It is 2 to prepare charcoal and carry silver catalyst to carry α type manganese dioxide-catalysts mass ratio with charcoal:1 physical mixed catalyst
(1) 1g carbon blacks are added in the concentrated nitric acid that 50ml mass fractions are 68%, ultrasonic half an hour, reaction temperature is
120 DEG C, condensing reflux 3h, it is cooled to room temperature, filters and be washed till the charcoal that neutral, vacuum drying is acidified with a large amount of deionized waters
It is black.
(2) carbon black for weighing 100mg acidifyings is put into ultrasonic disperse 30min in three-neck flask with 100g ethylene glycol.
(3) silver nitrate is dissolved in water, is made into silver nitrate solution, the molar concentration of silver nitrate is 0.1mol/L；Will be dense
Ammoniacal liquor is diluted to ammonia spirit, and the molar concentration of ammoniacal liquor is 0.1mol/L；Above-mentioned 37ml silver nitrate solutiones and 111ml ammoniacal liquor is molten
Liquid mixes, and forms the silver ammino solution of water white transparency, sodium hydroxide is dissolved in water, be made into sodium hydroxide solution, sodium hydroxide
Molar concentration be 1mol/L, the volume of sodium hydroxide solution is 4ml；By the silver ammino solution configured and sodium hydroxide solution according to
It is secondary to be poured into that ultrasound is good dissolved with the carbon black of acidifying and the three-neck flask of ethylene glycol, the mass ratio of silver nitrate and the carbon black of acidifying
For 6.29: 1, stirring, at 120 DEG C, condensing reflux, the reaction time controls in 1h temperature control.By the centrifugation point of above-mentioned reaction product
From or filtering be washed to neutrality, dry, obtain charcoal and carry silver catalyst solid powder.Loaded by TG-DTA thermal weight loss instruments
Rate is 400%.
(4) above-mentioned reaction product is centrifuged or filtered and be washed to neutrality, dried, obtain charcoal load silver catalyst solid
Powder.
(5) mixed solution of potassium permanganate and Manganous sulfate monohydrate is configured, the molar concentration of wherein potassium permanganate is
0.005mol/L, the molar concentration of Manganous sulfate monohydrate is 0.005mol/L, adds 75mg acidifying carbon blacks and 500mg dodecanes
Base benzene sulfonic acid sodium salt, it is stirred at room temperature 2 hours.
(6) solution is transferred in hydrothermal reaction kettle, and places heating response in an oven, reaction temperature at 160 °C,
Reaction time is 12h, and after reaction terminates, solution is centrifuged, and is washed, and is dried, and drying condition is 60 °C of vacuum drying 12h,
Obtain charcoal and carry α type manganese dioxide-catalyst solid powders.Load factor is obtained as 30% by TG-DTA thermal weight loss instruments.
(7) charcoal for preparing above-mentioned two step respectively carries silver catalyst and charcoal carries α type manganese dioxide-catalysts according to 2:1
Quality is more uniform than physical mixed, grinding.
It will be seen from figure 1 that Argent grain is evenly distributed on acidifying carbon black, and can from Fig. 2 XRD diffracting spectrums
Go out obviously silver-colored characteristic diffraction peak.From figure 3, it can be seen that the pattern of the α type manganese dioxide prepared is wire, while from
The characteristic diffraction peak occurred in Fig. 4 XRD diffracting spectrums is corresponding with the diffraction maximum of α type manganese dioxide.Finally from the rotation in Fig. 5
Turn disk test curve it can be seen from the figure that mass ratio as 2:The catalytic activity of 1 catalyst is not so good as the former, mass ratio 1:1
Catalyst is more suitable for the effective catalyst of catalytic oxygen reduction reaction.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described in above example.The industry
Technical staff it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification simply
Illustrate the principle of the present invention, rather than the scope limiting the invention in any way, without departing from the scope of the invention,
Various changes and modifications of the present invention are possible, and these changes and improvements are both fallen within claimed scope.
Claims (5)
1. a kind of charcoal/silver/manganese dioxide three-phase composite catalyst, it is characterised in that be prepared via a method which to obtain：Charcoal is carried
Silver catalyst and charcoal carry α type manganese dioxide-catalyst physical mixeds, and the catalyst after physical mixed is solid powder, and wherein charcoal carries
The mass ratio that silver catalyst and charcoal carry α type manganese dioxide-catalysts is 1:2~2:1；Wherein,
The charcoal carries silver catalyst and is prepared via a method which：
(1) carbon black is added in concentrated nitric acid, the mass ratio of carbon black and concentrated nitric acid is 0.01~0.04: 1；Temperature control is 120
DEG C~160 DEG C, 3~5h of condensing reflux, room temperature is cooled to, filters and be washed with deionized water to neutral, vacuum drying and be acidified
Carbon black；
(2) by the carbon black of acidifying and 10~30min of ethylene glycol mixing ultrasonic disperse；The carbon black of acidifying and the mass ratio of ethylene glycol
For 0.0001~0.01: 1；
(3) 0.01mol/L~1mol/L silver nitrate solution is mixed with 0.01mol/L~1mol/L ammonia spirit, nitric acid
The volume ratio 0.1~0.4: 1 of silver-colored solution and ammonia spirit, by the silver ammino solution configured and 0.01mol/L~5mol/L hydrogen
It is good dissolved with the carbon black of acidifying and the three-neck flask of ethylene glycol that sodium hydroxide solution is poured into ultrasound successively, silver nitrate solution and hydrogen
The mass ratio of the volume ratio 1~10: 1 of sodium hydroxide solution, silver nitrate and the carbon black of acidifying is 0.629~6.29: 1, stirring, temperature
At 110 DEG C~140 DEG C, condensing reflux, the reaction time is controlled in 0.5h~3h for control；
(4) above-mentioned reaction product is centrifuged or filtered and be washed to neutrality, dried, obtain charcoal load silver catalyst solid powder；
The charcoal carries α type manganese dioxide-catalysts and is prepared via a method which：
(1) mixed solution of potassium permanganate and Manganous sulfate monohydrate is prepared, the molar concentration of wherein potassium permanganate is
0.001mol/L~0.01mol/L, the molar concentration of Manganous sulfate monohydrate is 0.001mol/L~0.01mol/L, adds acid
The carbon black and neopelex of change are stirred at room temperature 1~3 hour；
(2) solution is transferred in hydrothermal reaction kettle, and places heating response in an oven, reaction temperature is at 140 °C~180 °
C, reaction time are 10~16h, and after reaction terminates, solution is centrifuged, and are washed, and are dried, and obtain charcoal load α type manganese dioxide and urge
Agent solid powder.
2. composite catalyst according to claim 1, it is characterised in that it is solid powder that the charcoal, which carries silver catalyst, grain
Footpath is the dispersed surface for being supported on acidifying carbon black of 3~10nm Argent grain, and silver-colored load factor is 300%~400%, silver
Mass ratio with being acidified carbon black is 3~4: 1.
3. composite catalyst according to claim 1, it is characterised in that it is solid powder that charcoal, which carries α types manganese dioxide-catalyst,
End, diameter 50nm α type manganese dioxide nano-rods are supported on acidifying carbon black, and the load factor of α type manganese dioxide nano-rods is
The mass ratio of 10%~70%, α type manganese dioxide nano-rod and acidifying carbon black is 0.1~0.7: 1.
4. composite catalyst according to claim 1, it is characterised in that described carbon black is Graphon.
5. composite catalyst any one of the claim 1-4 application in redox reactions in the basic conditions.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101745390A (en) * | 2010-01-29 | 2010-06-23 | 北京化工大学 | Supported silver-carbon catalyst for salt electrolysis and preparation method thereof |
| CN102476054A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Ag/MnyOx/C catalyst and preparation and application thereof |
| CN103545122A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Preparation method for manganese dioxide/carbon composite materials used for super capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745390A (en) * | 2010-01-29 | 2010-06-23 | 北京化工大学 | Supported silver-carbon catalyst for salt electrolysis and preparation method thereof |
| CN102476054A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Ag/MnyOx/C catalyst and preparation and application thereof |
| CN103545122A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Preparation method for manganese dioxide/carbon composite materials used for super capacitor |
Non-Patent Citations (1)
| Title |
|---|
| 可控合成纳米MnO2及电化学性能研究;汤念等;《中国锰业》;20090531;第27卷(第2期);32-36 * |
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