CN104043453B - A kind of support type cobaltosic oxide nano composite catalyst and application - Google Patents
A kind of support type cobaltosic oxide nano composite catalyst and application Download PDFInfo
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- CN104043453B CN104043453B CN201410003963.7A CN201410003963A CN104043453B CN 104043453 B CN104043453 B CN 104043453B CN 201410003963 A CN201410003963 A CN 201410003963A CN 104043453 B CN104043453 B CN 104043453B
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Abstract
The invention provides a kind of support type cobaltosic oxide Catalysts and its preparation method, described support type cobaltosic oxide catalyst is pressed powder, particle diameter in the cobaltosic oxide uniform particles load of about 10nm at acidifying carbon blacksurface, cobaltosic oxide is 20% ~ 100% in the preload rate scope of carbon blacksurface, it has high catalytic activity to redox reactions, 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 preparing is become gas-diffusion electrode, be applied in chlorine industry oxygen cathode technology.This electrode shows lower tank voltage in electrolytic saltwater performance test, has excellent redox reactions electro catalytic activity, keeps good durability and stability in alkaline medium simultaneously.
Description
Technical field
The present invention relates to the preparation of a kind of transition metal oxide nano-material, and the method for gas-diffusion electrode is prepared into as chlorine industry Oxygen Cathode Catalyst, a particularly support type cobaltosic oxide Catalysts and its preparation method, and be applied in chlorine industry ionic membrane electrolytic saline solution oxygen cathode technology.
Background technology
Chlorine industry, as one of national basis industry, occupies 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), original evolving hydrogen reaction is replaced by negative electrode carrying out redox reactions, comparable general ion-exchange membrane electrolyzer economize on electricity 40%, improves in output in reduction energy consumption and has broad application prospects in theory.
As the key factor of chlorine industry electrolytic saltwater oxygen cathode technology, choosing of cathod catalyst is most important, require that the gas-diffusion electrode of catalyst preparing has excellent oxygen reduction catalyst on the one hand under actual electrolysis operating mode 80-90 DEG C basic conditions active, guarantee that there is higher catalytic stability and durability on the other hand.At present, the dominant cathode catalyst being applied in oxygen cathode technology is silver powder catalyst, but due to silver powder costly, cause electrode production with high costs, thus be badly in need of find new catalyst.Research finds that the gas-diffusion electrode of carbon black loadings cobaltosic oxide catalyst preparing has excellent oxygen reduction catalyst Activity and stabill under 80-90 DEG C of basic conditions, 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 the non-Pt series catalysts of one, there is excellent redox reactions catalytic performance and known by the mankind gradually, and Co
3o
4belong to transition metal oxide, aboundresources, cheap, application is also expanded to polytropism by unicity gradually.Research proves the highly active Co of exploitation
3o
4oxygen reduction eelctro-catalyst, and be prepared into gas-diffusion electrode and be applied in chlorine industry electrolytic saltwater oxygen cathode technology, show excellent electrocatalysis characteristic, there is far-reaching Research Significance.
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, it has high catalytic activity to redox reactions, 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 preparing is become gas-diffusion electrode, be applied in chlorine industry oxygen cathode technology.This electrode shows lower tank voltage in electrolytic saltwater performance test, has excellent redox reactions electro catalytic activity, keeps good durability and stability in alkaline medium simultaneously.
Carbon black loadings cobaltosic oxide catalyst of the present invention is pressed powder, and particle diameter is in the cobaltosic oxide uniform particles load of about 10nm at acidifying carbon blacksurface, and cobaltosic oxide is 20% ~ 100% in the preload rate scope of carbon blacksurface.Utilize the gas-diffusion electrode of above-mentioned catalyst preparing, in ionic membrane electrolytic saline solution oxygen cathode technology, there is very high redox reactions electro catalytic activity and useful life longevity.
The preparation method of above-mentioned catalyst comprises the steps:
(1) ethanol or the ethylene glycol solution of the soluble cobalt of 0.05mol/L ~ 0.2mol/L is configured, the carbon black of nitric acid acidification is added in solution, ultrasonic disperse 5min ~ 30min, the pH value regulating mixed solution is 8 ~ 12, ultrasonic disperse 5min ~ 30min, obtains the suspension containing cobalt salt and carbon black-supported;
(2) above-mentioned suspension is poured in round-bottomed flask, carry out condensing reflux under magnetic stirring, control oil bath temperature at 50 ° of C ~ 160 ° C, the reaction time is 8 ~ 12h, after reaction terminates, suction filtration is carried out to reactant liquor, 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 obtained is heat-treated in air atmosphere, treatment conditions are: be warming up to 200 ° of C ~ 400 ° C with the heating rate of 3 ~ 10 ° of C/min, insulation roasting time is 1 ~ 4h, with stove cooling, finally obtain support type cobaltosic oxide nano composite catalyst.
In a preferred embodiment of the present invention, described soluble cobalt 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 VulcanXC-72, and is on nitric acid treatment basis, carry out again WITH AMMONIA TREATMENT Graphon and VulcanXC-72.
In a preferred embodiment of the present invention, in step (1), utilize concentrated ammonia solution as pH adjusting agent.
The present invention also relates to the preparation of the gas-diffusion electrode of support type cobaltosic oxide nano composite catalyst and is applied in chlorine industry electrolytic saltwater oxygen cathode technology on the other hand.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, in the test of chlorine industry electrolytic saltwater, show lower tank voltage, there is excellent redox reactions 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: a certain amount of Graphon is joined concentration be 2% ~ 6% song draw in water flowing solution, add appropriate isopropyl alcohol again, dispersion 0.5h ~ 1h is sheared with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min, be applied on silver-coated nickel foam by joined slurry, colding pressing after drying under 50 ° of C ~ 90 ° C obtains 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, shear dispersion 0.3h ~ 1h with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min; Joined Catalytic Layer slurry is coated onto step (1) electrode diffusion layer surface and forms Catalytic Layer, cold pressing after being placed in ° C baking oven drying of 50 ° of C ~ 90 and obtain gas-diffusion electrode;
(3) hot-forming: gas-diffusion electrode prepared by step (2) 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, the volume ratio that feeds intake of step (2) water and isopropyl alcohol in slurry layoutprocedure is 1:0.1 ~ 1.5.
In a preferred embodiment of the present invention, step (2) Qu Latong in slurry layoutprocedure be 2% ~ 6% song draw 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 redox reactions 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 preparing to go out 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 redox reactions electro catalytic activity and useful life longevity.This catalyst preparation process is simple, and with low cost, be prepared into gas-diffusion electrode and be applied in chlorine industry oxygen cathode technology, 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 embodiment 1, the XRD collection of illustrative plates of 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 embodiment 1, the redox reactions polarization curve of 2 gained catalyst;
Fig. 5 is the tank voltage test curve that embodiment 1 gained catalyst preparing becomes electrode.
Detailed description of the invention
Illustrate that the invention will be further described with embodiment below in conjunction with accompanying drawing:
Embodiment 1
(1) utilize ethanol to prepare carbon black as solvent and carry cobaltosic oxide nano composite catalyst
the soluble cobalt ethanolic solution of configuration 0.05mol/L ~ 0.2mol/L, nitric acid acidifying carbon black after 2g WITH AMMONIA TREATMENT is added in solution, ultrasonic disperse 5min ~ 30min, concentrated ammonia liquor is utilized to regulate the pH value of mixed solution to be 8 ~ 12, ultrasonic disperse 5min ~ 30min, obtains the suspension containing cobalt salt and carbon black-supported;
solution is poured in flask, carries out condensing reflux under magnetic stirring, controlling oil bath temperature is 50 ° of C ~ 90 ° C, and the reaction time is 8 ~ 12h, after reaction terminates, carries out suction filtration to reactant liquor, washing, and dry, drying condition is 80 ° of C, dry 12h.The cobaltosic oxide catalyst precursor pressed powder obtained;
the cobaltosic oxide catalyst precursor pressed powder obtained is heat-treated in air atmosphere, treatment conditions are: be warming up to 200 ° of C ~ 400 ° C with the heating rate of 3 ~ 10 ° of C/min, insulation roasting time is 1 ~ 4h, with stove cooling, obtain the brilliant composite catalyst of support type cobaltosic oxide nano.
(2) the gas-diffusion electrode preparation of cobaltosic oxide nano composite catalyst is carried containing carbon black
the preparation of diffusion layer: a certain amount of Graphon is joined concentration be 2% ~ 6% song draw in water flowing solution, add appropriate isopropyl alcohol again, dispersion 0.5h ~ 1h is sheared with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min, be applied on silver-coated nickel foam by joined slurry, colding pressing after drying under 50 ° of C ~ 90 ° C obtains 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, shear dispersion 0.3h ~ 1h with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min; Joined Catalytic Layer slurry is coated onto step
electrode diffusion layer surface forms Catalytic Layer, colds pressing and obtain gas-diffusion electrode after being placed in ° C baking oven drying of 50 ° of C ~ 90;
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 prepared by XRD spectra (Fig. 1) susceptible of proof is Co really
3o
4.TEM picture (Fig. 2) clearly can find out Co
3o
4uniform load is at carbon blacksurface, and particle diameter is at about 10nm.Redox reactions polarization curve (Fig. 4) shows, the hydrogen reduction onset current potential calibration of the catalyst in the basic conditions under alcohol solvent, known Co
3o
4catalyst oxygen reduction catalytic performance is excellent.Nano-composite catalyst is prepared into the tank voltage test curve (Fig. 4) of gas-diffusion electrode, can judge that tank voltage is lower under actual working conditions by figure, 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
the soluble cobalt ethylene glycol solution of configuration 0.05mol/L ~ 0.2mol/L, nitric acid acidifying carbon black after 2g WITH AMMONIA TREATMENT is added in solution, ultrasonic disperse 5min ~ 30min, concentrated ammonia liquor is utilized to regulate the pH value of mixed solution to be 8 ~ 12, ultrasonic disperse 5min ~ 30min, obtains the suspension containing cobalt salt and carbon black-supported;
solution is poured in flask, in magnetic agitation oil bath pan, carries out condensing reflux, controlling oil bath temperature is 80 ° of C ~ 160 ° C, and the reaction time is 8 ~ 12h, after reaction terminates, carries out suction filtration to reactant liquor, and washing is dry, and drying condition is the dry 12h of 80 ° of C.The cobaltosic oxide catalyst precursor pressed powder obtained;
the cobaltosic oxide catalyst precursor pressed powder obtained is heat-treated in air atmosphere, treatment conditions are: be warming up to 200 ° of C ~ 400 ° C with the heating rate of 3 ~ 10 ° of C/min, insulation roasting time is 1 ~ 4h, with stove cooling, obtain the brilliant composite catalyst of support type cobaltosic oxide nano.
(2) the gas-diffusion electrode preparation of cobaltosic oxide nano composite catalyst is carried containing carbon black
the preparation of diffusion layer: a certain amount of Graphon is joined concentration be 2% ~ 6% song draw in water flowing solution, add appropriate isopropyl alcohol again, dispersion 0.5h ~ 1h is sheared with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min, be applied on silver-coated nickel foam by joined slurry, colding pressing after drying under 50 ° of C ~ 90 ° C obtains 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, shear dispersion 0.3h ~ 1h with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min; Joined Catalytic Layer slurry is coated onto step
electrode diffusion layer surface forms Catalytic Layer, colds pressing and obtain gas-diffusion electrode after being placed in ° C baking oven drying of 50 ° of C ~ 90;
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 prepared by XRD spectra (Fig. 1) susceptible of proof is Co really
3o
4.By TEM(Fig. 3) susceptible of proof Co
3o
4the uniform load of nano particle is at carbon blacksurface, and particle diameter is at about 10nm.Found by hydrogen reduction performance test, glycol system catalyst activity is 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 display and describe general 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; what describe in above-described embodiment and description just illustrates principle of the present invention; instead of 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 (8)
1. a support type cobaltosic oxide nano composite catalyst, described catalyst is pressed powder, particle diameter is in the cobaltosic oxide uniform particles load of 10nm at acidifying carbon blacksurface, and cobaltosic oxide is 20% ~ 100% in the preload scope of carbon blacksurface, and its preparation method comprises the following steps:
(1) ethanol or the ethylene glycol solution of the soluble cobalt of 0.05mol/L ~ 0.2mol/L is configured, the carbon black of nitric acid treatment is added in solution, ultrasonic disperse 5min ~ 30min, the pH value regulating mixed solution is 8 ~ 12, ultrasonic disperse 5min ~ 30min, obtains the suspension containing cobalt salt and carbon black-supported;
(2) solution is poured in round-bottomed flask, carry out condensing reflux under magnetic stirring, control oil bath temperature at 50 DEG C ~ 160 DEG C, the reaction time is 8 ~ 12h, after reaction terminates, suction filtration is carried out to reactant liquor, washing, dry, drying condition is 80 DEG C, dry 12h, obtains cobaltosic oxide catalyst precursor pressed powder;
(3) the cobaltosic oxide catalyst precursor pressed powder obtained is heat-treated in air atmosphere, treatment conditions are: be warming up to 200 DEG C ~ 400 DEG C with the heating rate of 3 ~ 10 DEG C/min, insulation roasting time is 1 ~ 4h, with stove cooling, finally obtain support type cobaltosic oxide nano composite catalyst.
2. support type cobaltosic oxide nano composite catalyst according to claim 1, it is characterized in that soluble cobalt is cobalt nitrate, described carbon black is Graphon and VulcanXC-72, and is on nitric acid treatment basis, carry out again WITH AMMONIA TREATMENT Graphon and VulcanXC-72.
3. a gas-diffusion electrode, is characterized in that adopting following methods to prepare:
(1) preparation of diffusion layer: a certain amount of Graphon is joined concentration be 2% ~ 6% song draw in water flowing solution, add appropriate isopropyl alcohol again, dispersion 0.5h ~ 1h is sheared with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min, be applied on silver-coated nickel foam by joined slurry, colding pressing after drying at 50 DEG C ~ 90 DEG C obtains 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 any one of claim 1-2, Qu Latong, water, isopropyl alcohol is mixed, dispersion 0.3h ~ 1h is sheared with refiner, add the PTFE emulsion of concentration 50% ~ 70% afterwards, shear dispersion 8min ~ 15min; Joined Catalytic Layer slurry is coated onto step (1) electrode diffusion layer surface and forms Catalytic Layer, cold pressing after being placed in 50 DEG C ~ 90 DEG C baking oven dryings and obtain gas-diffusion electrode;
(3) hot-forming: gas-diffusion electrode prepared by step (2) heat treatment 0.5h ~ 2h at 200 DEG C ~ 300 DEG C, hot-forming at 320 DEG C ~ 380 DEG C bottom electrodes afterwards.
4. gas-diffusion electrode according to claim 3, 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.
5. gas-diffusion electrode according to claim 3, is characterized in that the volume ratio that feeds intake of step (2) water and isopropyl alcohol in slurry layoutprocedure is 1:0.1 ~ 1.5.
6. gas-diffusion electrode according to claim 3, it is characterized in that step (2) Qu Latong in slurry layoutprocedure be 2% ~ 6% song draw water flowing solution.
7. gas-diffusion electrode according to claim 3, is characterized in that step (1) mass ratio of PTFE emulsion and Graphon in slurry layoutprocedure is 1:2 ~ 5.
8. the arbitrary described application of gas-diffusion electrode in chlorine industry oxygen cathode technology of claim 3-7.
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| CN104307526B (en) * | 2014-10-11 | 2016-08-31 | 北京化工大学 | A kind of support type lithium doping cobaltosic oxide nano 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 |
| CN109585860B (en) * | 2018-11-07 | 2021-11-09 | 三峡大学 | Preparation method of sulfur-doped cobalt oxide and sulfur, nitrogen and oxygen-doped carbon in-situ composite electrode |
| CN109898093B (en) * | 2019-04-25 | 2021-03-30 | 上海应用技术大学 | 3D structure composite hydrogen evolution electrode and preparation method thereof |
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| 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 |
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| 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 |
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