CN104043453A - Supported cobaltosic oxide nanometer composite catalyst and use thereof - Google Patents
Supported cobaltosic oxide nanometer composite catalyst and use thereof Download PDFInfo
- Publication number
- CN104043453A CN104043453A CN201410003963.7A CN201410003963A CN104043453A CN 104043453 A CN104043453 A CN 104043453A CN 201410003963 A CN201410003963 A CN 201410003963A CN 104043453 A CN104043453 A CN 104043453A
- Authority
- CN
- China
- Prior art keywords
- cobaltosic oxide
- composite catalyst
- diffusion electrode
- gas
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a supported cobaltosic oxide nanometer composite catalyst and a use thereof. The supported cobaltosic oxide nanometer composite catalyst comprises solid powder. Cobaltosic oxide particles having particle diameters of about 10nm are uniformly loaded on the surface of acidified carbon black. A pre-loading rate of cobaltosic oxide on the surface of carbon black is in a range of 20-100%. The supported cobaltosic oxide nanometer composite catalyst has the advantages of high catalytic activity to the oxygen reduction reaction, simple preparation processes, low cost, easy control of cobaltosic oxide particle diameter and easy industrial production. The supported cobaltosic oxide nanometer composite catalyst can be used for preparation of a gas diffusion electrode and the gas diffusion electrode is used in the chlor-alkali industrial oxygen cathode technology. In salt water electrolysis-based performance test, the gas diffusion electrode has low bath voltage, has excellent oxygen reduction reaction electrocatalytic activity and retains good endurance and stability in an alkaline medium.
Description
Technical field
The present invention relates to a kind of transition metal oxide nano-material preparation, and as chlorine industry Oxygen Cathode Catalyst, be prepared into the method for gas-diffusion electrode, a support type cobaltosic oxide Catalysts and its preparation method particularly, and be applied in chlorine industry ionic membrane electrolytic saline solution oxygen cathode technology.
Background technology
Chlorine industry, as one of national basis industry, is occupied very consequence in national economy.At present, because the power saving capability of traditional ion-exchange membrane electrolyzer reaches capacity, and electrolytic saltwater oxygen cathode technology is as emerging technology, this technology replaces the activated cathode of conventional ion membrane electrolysis cells with oxygen diffusion electrode (oxygen cathode), by carrying out the original evolving hydrogen reaction of oxygen reduction substituted in reaction on negative electrode, comparable general ion-exchange membrane electrolyzer economize on electricity 40% in theory, is having broad application prospects aspect reduction energy consumption raising output.
Key factor as chlorine industry electrolytic saltwater oxygen cathode technology, choosing of cathod catalyst is most important, require gas-diffusion electrode prepared by catalyst under 80-90 ℃ of highly basic condition of actual electrolysis operating mode, to there is excellent oxygen reduction catalytic activity on the one hand, guarantee on the other hand to there is higher catalytic stability and durability.At present, the main flow cathod catalyst that is applied in oxygen cathode technology is silver powder catalyst, but because silver powder is more expensive, causes electrode production with high costs, so be badly in need of finding new catalyst.Research finds that gas-diffusion electrode prepared by carbon black loadings cobaltosic oxide catalyst has excellent oxygen reduction catalytic activity and stability under 80-90 ℃ of highly basic condition, and it is with low cost, preparation technology is simple, if suitability for industrialized production can reduce electrode cost greatly, therefore, Co
3o
4as potential new catalyst, there is very high researching value.
Co
3o
4as a kind of non-Pt series catalysts, there is excellent oxygen reduction reacting catalytic performance and by the mankind, known gradually, and Co
3o
4belong to transition metal oxide, aboundresources, cheap, application is also expanded to polytropism by unicity gradually.Studies have shown that the highly active Co of exploitation
3o
4oxygen reduction eelctro-catalyst, and be prepared into gas-diffusion electrode and be applied to, in chlorine industry electrolytic saltwater oxygen cathode technology, show excellent electrocatalysis characteristic, far-reaching Research Significance there is.
Summary of the invention
The object of the invention provides a kind of carbon black loadings cobaltosic oxide Catalysts and its preparation method on the one hand, to oxygen reduction, reaction has high catalytic activity for it, and preparation technology is simple, with low cost, cobaltosic oxide grain diameter is easy to control, and catalyst is easy to suitability for industrialized production.On the other hand, this catalyst is prepared into gas-diffusion electrode, is applied in chlorine industry oxygen cathode technology.This electrode shows lower tank voltage in electrolytic saltwater performance test, has excellent oxygen reduction reaction electro catalytic activity, keeps good durability and stability simultaneously in alkaline medium.
Carbon black loadings cobaltosic oxide catalyst of the present invention is pressed powder, and particle diameter loads on acidifying carbon blacksurface in the cobaltosic oxide uniform particles of 10nm left and right, and cobaltosic oxide is 20%～100% in the preload rate scope of carbon blacksurface.The gas-diffusion electrode of utilizing above-mentioned catalyst to prepare has very high oxygen reduction reaction electro catalytic activity and useful life longevity in ionic membrane electrolytic saline solution oxygen cathode technology.
The preparation method of above-mentioned catalyst comprises the steps:
(1) ethanol or the ethylene glycol solution of the solubility cobalt salt of configuration 0.05 mol/L～0.2 mol/L, the carbon black of nitric acid acidification is added in solution, ultrasonic dispersion 5min～30min, regulating the pH value of mixed solution is 8～12, ultrasonic dispersion 5min～30min, obtains the suspension that contains cobalt salt and carbon black carrier;
(2) above-mentioned suspension is poured in round-bottomed flask, under magnetic agitation, carry out condensing reflux, control oil bath temperature at 50 ° of C～160 ° C, the reaction time is 8～12h, after reaction finishes, reactant liquor is carried out to suction filtration, washing, dry, drying condition is 80 ° of C, dry 12h, obtains cobaltosic oxide catalyst precursor pressed powder;
(3) the cobaltosic oxide catalyst precursor pressed powder obtaining is heat-treated in air atmosphere, treatment conditions are: the heating rate with 3～10 ° of C/min is warming up to 200 ° of C～400 ° C, insulation roasting time is 1～4h, cooling with stove, finally obtain support type cobaltosic oxide nano composite catalyst.
In a preferred embodiment of the present invention, described solubility cobalt salt is cobalt nitrate.
In a preferred embodiment of the present invention, described dicyandiamide solution is ethanol or ethylene glycol.
In a preferred embodiment of the present invention, described carbon black is Graphon and Vulcan XC-72, and is Graphon and the Vulcan XC-72 that carries out again WITH AMMONIA TREATMENT on nitric acid treatment basis.
In a preferred embodiment of the present invention, in step (1), utilize concentrated ammonia solution as pH adjusting agent.
The present invention also relate on the other hand support type cobaltosic oxide nano composite catalyst gas-diffusion electrode preparation and be applied in chlorine industry electrolytic saltwater oxygen cathode technology.According to Co
3o
4physical property characteristic, by to Catalytic Layer paste composition: water, isopropyl alcohol, Qu Latong, the proportioning adjustment of PTFE emulsion and support type cobaltosic oxide nano composite catalyst consumption, mixes a kind of slurry even, the Catalytic Layer slurry that the applicable industry that viscosity is moderate is smeared, and be prepared into gas-diffusion electrode, and in the test of chlorine industry electrolytic saltwater, show lower tank voltage, there is excellent oxygen reduction reaction electro catalytic activity and useful life longevity.
The preparation method of gas-diffusion electrode provided by the present invention, comprises the following steps:
(1) preparation of diffusion layer: it is that 2% ~ 6% song draws in water flowing solution that a certain amount of Graphon is joined to concentration, add again appropriate isopropyl alcohol, with refiner, shear and disperse 0.5h ~ 1h, the PTFE emulsion that adds afterwards concentration 50% ~ 70%, shear and disperse 8min ~ 15min, joined slurry is applied in silver-plated nickel foam, after being dried under 50 ° of C ~ 90 ° C, colds pressing and obtain electric pole gaseous diffusion layer.
(2) preparation of Catalytic Layer: by a certain amount of above-mentioned support type cobaltosic oxide nano composite catalyst, Qu Latong, water, isopropyl alcohol is mixed, with refiner, shear and disperse 0.3h ~ 1h, add afterwards the PTFE emulsion of concentration 50% ~ 70%, shear and disperse 8min ~ 15min; Joined Catalytic Layer slurry is coated onto to step (1) electrode diffusion layer surface and forms Catalytic Layer, be placed in after 50 ° of C ~ 90 ° C baking oven is dried and cold pressing and obtain gas-diffusion electrode;
(3) hot-forming: gas-diffusion electrode prepared by step (2) is heat treatment 0.5h ~ 2h under 200 ° of C ~ 300 ° C, hot-forming at 320 ° of C ~ 380 ° C bottom electrode afterwards.
In a preferred embodiment of the present invention, step (2) support type cobaltosic oxide nano composite catalyst consumption of unit are in slurry layoutprocedure is: 150g/m
2~ 400g/m
2.
In a preferred embodiment of the present invention, step (2) volume ratio that feeds intake of water and isopropyl alcohol in slurry layoutprocedure is 1: 0.1 ~ 1.5.
In a preferred embodiment of the present invention, step (2) song that Qu Latong is 2% ~ 6% in slurry layoutprocedure draws water flowing solution.
In a preferred embodiment of the present invention, step (1) mass ratio of PTFE emulsion and Graphon in slurry layoutprocedure is 1:2 ~ 5.
It is even that the present invention mixes a kind of slurry, the gas-diffusion electrode Catalytic Layer slurry that the applicable industry that viscosity is moderate is smeared.Utilize above-mentioned slurry to be prepared into gas-diffusion electrode, and be applied in chlorine industry oxygen cathode technology.Prepared electrode shows lower tank voltage in the test of chlorine industry electrolytic saltwater, has excellent oxygen reduction reaction electro catalytic activity and useful life longevity.
The present invention adopts a kind of simple and easy to do method to prepare the brilliant composite catalyst of carbon black loadings cobaltosic oxide nano, and utilizes above-mentioned catalyst to prepare gas-diffusion electrode, and is applied in chlorine industry oxygen cathode technology.This electrode shows lower tank voltage in the test of chlorine industry electrolytic saltwater, has excellent oxygen reduction reaction electro catalytic activity and useful life longevity.This catalyst preparation process is simple, with low cost, is prepared into gas-diffusion electrode and is applied in chlorine industry oxygen cathode technology, and performance performance is superior, has a extensive future.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described
Fig. 1 is the XRD collection of illustrative plates of embodiment 1,2 gained catalyst;
Fig. 2 is the transmission electron micrograph of embodiment 1 gained catalyst;
Fig. 3 is the transmission electron micrograph of embodiment 2 gained catalyst;
Fig. 4 is the oxygen reduction reaction polarization curve of embodiment 1,2 gained catalyst;
Fig. 5 is the tank voltage test curve that embodiment 1 gained catalyst is prepared into electrode.
The specific embodiment
Below in conjunction with accompanying drawing explanation and embodiment, the invention will be further described:
Embodiment 1
(1) utilize ethanol to prepare carbon black as solvent and carry cobaltosic oxide nano composite catalyst
configure the solubility cobalt salt ethanolic solution of 0.05 mol/L～0.2 mol/L, nitric acid acidifying carbon black after 2g WITH AMMONIA TREATMENT is added in solution, ultrasonic dispersion 5min～30min, utilizing concentrated ammonia liquor to regulate the pH value of mixed solution is 8～12, ultrasonic dispersion 5min～30min, obtains the suspension that contains cobalt salt and carbon black carrier;
solution is poured in flask, carried out condensing reflux under magnetic agitation, controlling oil bath temperature is 50 ° of C～90 ° C, and the reaction time is 8～12h, after reaction finishes, reactant liquor is carried out to suction filtration, washing, and dry, drying condition is 80 ° of C, dry 12h.The cobaltosic oxide catalyst precursor pressed powder obtaining;
the cobaltosic oxide catalyst precursor pressed powder obtaining is heat-treated in air atmosphere, treatment conditions are: the heating rate with 3～10 ° of C/min is warming up to 200 ° of C～400 ° C, insulation roasting time is 1～4h, cooling with stove, obtain the brilliant composite catalyst of support type cobaltosic oxide nano.
(2) containing carbon black, carry the gas-diffusion electrode preparation of cobaltosic oxide nano composite catalyst
the preparation of diffusion layer: it is that 2% ~ 6% song draws in water flowing solution that a certain amount of Graphon is joined to concentration, add again appropriate isopropyl alcohol, with refiner, shear and disperse 0.5h ~ 1h, the PTFE emulsion that adds afterwards concentration 50% ~ 70%, shear and disperse 8min ~ 15min, joined slurry is applied in silver-plated nickel foam, after being dried under 50 ° of C ~ 90 ° C, colds pressing and obtain electric pole gaseous diffusion layer;
the preparation of Catalytic Layer: the support type cobaltosic oxide nano composite catalyst that a certain amount of step (1) is prepared, Qu Latong, water, isopropyl alcohol is mixed, with refiner, shear and disperse 0.3h ~ 1h, add afterwards the PTFE emulsion of concentration 50% ~ 70%, shear and disperse 8min ~ 15min; Joined Catalytic Layer slurry is coated onto to step
electrode diffusion layer surface forms Catalytic Layer, is placed in after 50 ° of C ~ 90 ° C baking oven is dried and colds pressing and obtain gas-diffusion electrode;
hot-forming: by step
gas-diffusion electrode heat treatment 0.5h ~ 2h under 200 ° of C ~ 300 ° C of preparation, hot-forming at 320 ° of C ~ 380 ° C bottom electrode afterwards.
The support type cobaltosic oxide composite catalyst product of preparing by XRD spectra (Fig. 1) susceptible of proof is Co really
3o
4.TEM picture (Fig. 2) can clearly be found out Co
3o
4load on uniformly carbon blacksurface, particle diameter is in 10nm left and right.Oxygen reduction reaction polarization curve (Fig. 4) shows, the hydrogen reduction onset current potential calibration of the catalyst under alkali condition under alcohol solvent, known Co
3o
4catalyst hydrogen reduction catalytic performance is excellent.Nano-composite catalyst is prepared into the tank voltage test curve (Fig. 4) of gas-diffusion electrode, by figure, can judge that tank voltage is lower under actual working conditions, and catalytic performance is excellent, and stability is high, good endurance.
Embodiment 2
(1) utilize ethylene glycol to prepare carbon black as solvent and carry cobaltosic oxide nano composite catalyst
configure the solubility cobalt salt ethylene glycol solution of 0.05 mol/L～0.2 mol/L, nitric acid acidifying carbon black after 2g WITH AMMONIA TREATMENT is added in solution, ultrasonic dispersion 5min～30min, utilizing concentrated ammonia liquor to regulate the pH value of mixed solution is 8～12, ultrasonic dispersion 5min～30min, obtains the suspension that contains cobalt salt and carbon black carrier;
solution is poured in flask, carried out condensing reflux in magnetic agitation oil bath pan, controlling oil bath temperature is 80 ° of C～160 ° C, and the reaction time is 8～12h, after reaction finishes, reactant liquor is carried out to suction filtration, and washing is dry, and drying condition is the dry 12h of 80 ° of C.The cobaltosic oxide catalyst precursor pressed powder obtaining;
the cobaltosic oxide catalyst precursor pressed powder obtaining is heat-treated in air atmosphere, treatment conditions are: the heating rate with 3～10 ° of C/min is warming up to 200 ° of C～400 ° C, insulation roasting time is 1～4h, cooling with stove, obtain the brilliant composite catalyst of support type cobaltosic oxide nano.
(2) containing carbon black, carry the gas-diffusion electrode preparation of cobaltosic oxide nano composite catalyst
the preparation of diffusion layer: it is that 2% ~ 6% song draws in water flowing solution that a certain amount of Graphon is joined to concentration, add again appropriate isopropyl alcohol, with refiner, shear and disperse 0.5h ~ 1h, the PTFE emulsion that adds afterwards concentration 50% ~ 70%, shear and disperse 8min ~ 15min, joined slurry is applied in silver-plated nickel foam, after being dried under 50 ° of C ~ 90 ° C, colds pressing and obtain electric pole gaseous diffusion layer.
the preparation of Catalytic Layer: the support type cobaltosic oxide nano composite catalyst that a certain amount of step (1) is prepared, Qu Latong, water, isopropyl alcohol is mixed, with refiner, shear and disperse 0.3h ~ 1h, add afterwards the PTFE emulsion of concentration 50% ~ 70%, shear and disperse 8min ~ 15min; Joined Catalytic Layer slurry is coated onto to step
electrode diffusion layer surface forms Catalytic Layer, is placed in after 50 ° of C ~ 90 ° C baking oven is dried and colds pressing and obtain gas-diffusion electrode;
hot-forming: by step
gas-diffusion electrode heat treatment 0.5h ~ 2h under 200 ° of C ~ 300 ° C of preparation, hot-forming at 320 ° of C ~ 380 ° C bottom electrode afterwards.
The support type cobaltosic oxide composite catalyst product of preparing by XRD spectra (Fig. 1) susceptible of proof is Co really
3o
4.By TEM(Fig. 3) susceptible of proof Co
3o
4nano particle loads on carbon blacksurface uniformly, and particle diameter is in 10nm left and right.By hydrogen reduction performance test, find, glycol system catalyst is active similar to ethanol system catalytic activity, and catalytic activity is high, and the gas-diffusion electrode of preparation also has similar electro catalytic activity.
Above embodiment shows and has described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and description, describes just illustrates principle of the present invention; rather than limit the scope of the invention by any way; without departing from the scope of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in claimed scope.
Claims (10)
1. a support type cobaltosic oxide nano composite catalyst, described catalyst is pressed powder, and particle diameter loads on acidifying carbon blacksurface in the cobaltosic oxide uniform particles of 10nm left and right, and cobaltosic oxide is 20%～100% in the preload scope of carbon blacksurface.
2. support type cobaltosic oxide nano composite catalyst according to claim 1, its preparation method comprises the following steps:
(1) ethanol or the ethylene glycol solution of the solubility cobalt salt of configuration 0.05 mol/L～0.2 mol/L, the carbon black of nitric acid treatment is added in solution, ultrasonic dispersion 5min～30min, regulating the pH value of mixed solution is 8～12, ultrasonic dispersion 5min～30min, obtains the suspension that contains cobalt salt and carbon black carrier;
(2) solution is poured in round-bottomed flask, under magnetic agitation, carry out condensing reflux, control oil bath temperature at 50 ° of C～160 ° C, the reaction time is 8～12h, after reaction finishes, reactant liquor is carried out to suction filtration, washing, dry, drying condition is 80 ° of C, dry 12h, obtains cobaltosic oxide catalyst precursor pressed powder;
(3) the cobaltosic oxide catalyst precursor pressed powder obtaining is heat-treated in air atmosphere, treatment conditions are: the heating rate with 3～10 ° of C/min is warming up to 200 ° of C～400 ° C, insulation roasting time is 1～4h, cooling with stove, finally obtain support type cobaltosic oxide nano composite catalyst.
3. support type cobaltosic oxide nano composite catalyst according to claim 2, it is characterized in that solubility cobalt salt is cobalt nitrate, described carbon black is Graphon and Vulcan XC-72, and is Graphon and the Vulcan XC-72 that carries out again WITH AMMONIA TREATMENT on nitric acid treatment basis.
4. support type cobaltosic oxide nano composite catalyst according to claim 2, is characterized in that described dicyandiamide solution is ethanol or ethylene glycol, utilizes concentrated ammonia solution as pH adjusting agent.
5. a gas-diffusion electrode, is characterized in that adopting following methods to prepare:
(1) preparation of diffusion layer: it is that 2% ~ 6% song draws in water flowing solution that a certain amount of Graphon is joined to concentration, add again appropriate isopropyl alcohol, with refiner, shear and disperse 0.5h ~ 1h, the PTFE emulsion that adds afterwards concentration 50% ~ 70%, shear and disperse 8min ~ 15min, joined slurry is applied in silver-plated nickel foam, after being dried under 50 ° of C ~ 90 ° C, colds pressing and obtain electric pole gaseous diffusion layer;
(2) preparation of Catalytic Layer: by the support type cobaltosic oxide nano composite catalyst described in a certain amount of claim 1-4 any one, Qu Latong, water, isopropyl alcohol is mixed, with refiner, shear and disperse 0.3h ~ 1h, the PTFE emulsion that adds afterwards concentration 50% ~ 70%, shears and disperses 8min ~ 15min; Joined Catalytic Layer slurry is coated onto to step (1) electrode diffusion layer surface and forms Catalytic Layer, be placed in after 50 ° of C ~ 90 ° C baking oven is dried and cold pressing and obtain gas-diffusion electrode;
(3) hot-forming: gas-diffusion electrode prepared by step (2) is heat treatment 0.5h ~ 2h under 200 ° of C ~ 300 ° C, hot-forming at 320 ° of C ~ 380 ° C bottom electrode afterwards.
6. gas-diffusion electrode according to claim 5, is characterized in that step (2) support type cobaltosic oxide nano composite catalyst consumption of unit are in slurry layoutprocedure is: 150g/m
2~ 400g/m
2.
7. gas-diffusion electrode according to claim 5, is characterized in that step (2) volume ratio that feeds intake of water and isopropyl alcohol in slurry layoutprocedure is 1: 0.1 ~ 1.5.
8. gas-diffusion electrode according to claim 5, is characterized in that step (2) song that Qu Latong is 2% ~ 6% in slurry layoutprocedure draws water flowing solution.
9. gas-diffusion electrode according to claim 5, is characterized in that step (1) mass ratio of PTFE emulsion and Graphon in slurry layoutprocedure is 1:2 ~ 5.
10. the application of the arbitrary described gas-diffusion electrode of claim 5-9 in chlorine industry oxygen cathode technology.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410003963.7A CN104043453B (en) | 2014-01-06 | 2014-01-06 | A kind of support type cobaltosic oxide nano composite catalyst and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410003963.7A CN104043453B (en) | 2014-01-06 | 2014-01-06 | A kind of support type cobaltosic oxide nano composite catalyst and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104043453A true CN104043453A (en) | 2014-09-17 |
| CN104043453B CN104043453B (en) | 2015-12-09 |
Family
ID=51497141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410003963.7A Active CN104043453B (en) | 2014-01-06 | 2014-01-06 | A kind of support type cobaltosic oxide nano composite catalyst and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104043453B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307526A (en) * | 2014-10-11 | 2015-01-28 | 北京化工大学 | Supported lithium-doped cobaltosic oxide composite catalyst and preparation method thereof |
| CN104492439A (en) * | 2014-12-10 | 2015-04-08 | 北京化工大学 | Carbon-supported iron-doped tricobalt tetraoxide nanocrystal composite catalyst and preparation method thereof |
| WO2016096806A1 (en) * | 2014-12-16 | 2016-06-23 | Fundació Institut Català D'investigació Química (Iciq) | Method for hydrogen production and electrolytic cell thereof |
| CN109585860A (en) * | 2018-11-07 | 2019-04-05 | 三峡大学 | A kind of preparation method of sulfur doping cobalt oxide and sulphur, nitrogen, oxygen doping carbon In-situ reaction electrode |
| CN109898093A (en) * | 2019-04-25 | 2019-06-18 | 上海应用技术大学 | A kind of 3D structure composite hydrogen-precipitating electrode and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728541A (en) * | 2008-10-17 | 2010-06-09 | 北京化工大学 | Method for preparing carbon nano tube loaded cobalt-platinum alloy catalyst |
| CN103055893A (en) * | 2012-12-25 | 2013-04-24 | 北京化工大学 | Supported cobalt-platinum superlattice alloy nano particle composite catalyst and preparation method thereof |
| CN103263905A (en) * | 2013-05-23 | 2013-08-28 | 北京化工大学 | Carbon black loaded lanthanum oxide nanocrystal composite catalyst and preparation method thereof |
-
2014
- 2014-01-06 CN CN201410003963.7A patent/CN104043453B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728541A (en) * | 2008-10-17 | 2010-06-09 | 北京化工大学 | Method for preparing carbon nano tube loaded cobalt-platinum alloy catalyst |
| CN103055893A (en) * | 2012-12-25 | 2013-04-24 | 北京化工大学 | Supported cobalt-platinum superlattice alloy nano particle composite catalyst and preparation method thereof |
| CN103263905A (en) * | 2013-05-23 | 2013-08-28 | 北京化工大学 | Carbon black loaded lanthanum oxide nanocrystal composite catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李赏 等: "Co3O4/C催化氧还原反应的活性及机理", 《催化学报》, vol. 32, no. 4, 20 April 2011 (2011-04-20) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307526A (en) * | 2014-10-11 | 2015-01-28 | 北京化工大学 | Supported lithium-doped cobaltosic oxide composite catalyst and preparation method thereof |
| CN104492439A (en) * | 2014-12-10 | 2015-04-08 | 北京化工大学 | Carbon-supported iron-doped tricobalt tetraoxide nanocrystal composite catalyst and preparation method thereof |
| WO2016096806A1 (en) * | 2014-12-16 | 2016-06-23 | Fundació Institut Català D'investigació Química (Iciq) | Method for hydrogen production and electrolytic cell thereof |
| CN109585860A (en) * | 2018-11-07 | 2019-04-05 | 三峡大学 | A kind of preparation method of sulfur doping cobalt oxide and sulphur, nitrogen, oxygen doping carbon In-situ reaction electrode |
| CN109898093A (en) * | 2019-04-25 | 2019-06-18 | 上海应用技术大学 | A kind of 3D structure composite hydrogen-precipitating electrode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104043453B (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhan et al. | Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media | |
| Xu et al. | Antimony doped tin oxides and their composites with tin pyrophosphates as catalyst supports for oxygen evolution reaction in proton exchange membrane water electrolysis | |
| CN112058293B (en) | Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof | |
| CN104043453B (en) | A kind of support type cobaltosic oxide nano composite catalyst and application | |
| CN109012749A (en) | Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope | |
| CN111244470B (en) | Nano composite cathode and preparation and application thereof | |
| CN111074292A (en) | Electro-catalytic hydrogen production porous high-entropy alloy electrode material and preparation method thereof | |
| CN113388847B (en) | Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof | |
| CN110560141A (en) | Preparation method and application of VN @ WN nanoparticles with electrocatalytic function | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN110304620A (en) | It is a kind of to utilize nitrogen-doped porous carbon material made of bean dregs and its preparation method and application | |
| CN113437314A (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN111013615A (en) | Preparation method of CoP catalyst with hydrogen precipitation and oxygen precipitation high-efficiency dual functions | |
| CN110117797B (en) | Electrolytic cell and application thereof in hydrogen production by electrolyzing water | |
| CN110732331A (en) | method for preparing amorphous iron-nickel-phosphorus compound composite carbon electrocatalytic material | |
| CN110846680A (en) | Preparation method of multi-defect and active site electrocatalyst | |
| CN108048860A (en) | A kind of aza material preparation method of NiO/NiS nano-particles codope carbon and application | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN101511469B (en) | Nanometer powder catalyst and preparation method thereof | |
| CN114725328B (en) | Nitrogen-doped biomass-derived porous carbon-loaded Fe 3 O 4 Fe composite material, preparation method and application thereof | |
| CN103263905B (en) | Carbon black loaded lanthanum oxide nanocrystal composite catalyst and preparation method thereof | |
| CN108179434A (en) | A kind of preparation method and application of NiO/NiS/CN nano-hybrid materials | |
| CN110860301B (en) | Ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst, preparation method thereof and application of dual-functional electrocatalyst in efficient electrolytic hydrogen production | |
| CN114990569B (en) | Electrocatalytic deuterium analysis material of boron carbide loaded ruthenium and preparation method and application thereof | |
| Zhu et al. | NiO coupled with CeO2 as an efficient electrocatalysts for ethanol oxidation in hybrid water splitting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |