CN101638795B - Method for transferring electrically-deposited Co-P catalyst - Google Patents
Method for transferring electrically-deposited Co-P catalyst Download PDFInfo
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- CN101638795B CN101638795B CN2009101485672A CN200910148567A CN101638795B CN 101638795 B CN101638795 B CN 101638795B CN 2009101485672 A CN2009101485672 A CN 2009101485672A CN 200910148567 A CN200910148567 A CN 200910148567A CN 101638795 B CN101638795 B CN 101638795B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention provides a method for transferring an electrically-deposited Co-P catalyst, comprising the following steps: using an alkaline water solution with the pH value of above 13 to process the electrically-deposited Co-P catalyst on a conductive substrate so that the Co-P catalyst is separated from the conductive substrate. By adopting the method, the electrically-deposited Co-P catalyst can be easily transferred without affecting the activity of the catalyst.
Description
Technical field
The present invention relates to a kind of method that is used to shift the Co-P catalyzer of galvanic deposit.
Background technology
Hydrogen production process by water electrolysis is very ancient hydrogen production process.Along with people carry out widely to the deep day by day of hydrogen energy source research, the brine electrolysis technology has obtained swift and violent development.Electrolyzer is the key equipment of brine electrolysis, according to the difference of its structure, mainly is divided into alkaline electrolytic bath, solid polymer electrolyte (SPE) electrolyzer, means of solid oxide electrolytic cell.Alkaline electrolytic bath is the most ancient, the most sophisticated electrolyzer of technology.Its advantage is to use non-precious metal as catalyzer, easy to operate, low price, and shortcoming is that efficient is not high, and about 70%～80%.The SPE electrolyzer is based on the effective electrolysis of ion exchange technique.This technology is that GE began one's study in the fifties, the sixties, first Application was in the hydrogen-oxygen fuel cell of Gemmi spaceship, be used for water electrolysis with this technology the seventies again, become solid polymer water electrolysis technology, be called for short SPE (Solid Polymer Electrolyte, solid polymer electrolyte) water electrolysis technology.Along with the continuous development of SPE water electrolysis technology is perfect, this technology is progressively expanded to commercial field by military, national defence, and along with the arriving of hydrogen energy era, it has represented new vitality again.
The principal feature of SPE water electrolysis technology is to replace traditional caustic alkali liquid ionogen with solid polymer electrolyte, and hydrogen and oxygen generate at the negative electrode and the anode of ionogen both sides respectively.The core component of SPE electrolyzer is the film (Catalyst Coated Membrane, i.e. CCM) that scribbles catalyst layer, promptly coats anode catalyst layer and the cathode catalyst layer with katalysis respectively on the two sides of solid polymer dielectric film.The method for preparing CCM generally has direct spraying method and chemical deposition etc.It is the powder of nanometric particles with high-specific surface area that spraying method requires catalyzer.
(Science 321 for U.S.'s " science " magazine, 2008,1072-1075, DOI:10.1126/science.1162018, exercise question are " In Situ Formation of anOxygen-Evolving Catalyst in Neutral Water Containing Phosphate andCo2+ ") reported a kind of in the potassiumphosphate that contains the weakly alkaline of Co2+ (pH=7 ~ 9) or other buffered soln the preparation of the method by galvanic deposit analyse the oxygen anodes catalyzer.Make in this way the catalyzer that contains Co of preparation, it is low to have an overpotential, advantages such as reaction conditions gentleness.And do not use noble metal fully, the catalysagen material is cheap and easy to get.
Aforesaid method is in the mixing solutions that contains phosphoric acid salt and cobalt salt, and Means of Electrodeposition arrives catalyst deposit on ITO (indium tin oxide, the tin indium oxide) layer of conductive glass.Subsequently with this conductive glass be anode contain Co2+ do not contain the potassiumphosphate of pH=7～9 of Co2+ or potassium borate buffered soln in carry out water electrolysis, can observe separating out of a large amount of oxygen at anode, anode voltage is 1.29Vvs.NHE (standard hydrogen electrode).
The catalyzer of preparing as stated above firmly on the ITO layer attached to conductive glass, promptly uses blade to scrape and also is difficult to wipe off, therefore is difficult to shift being prepared on other base materials.And, require a certain amount of corresponding catalyst of load on other ion-exchange membranees such as thin as a wafer layer proton exchange membrane or hydroxide radical for the preparation of membrane electrode in the SPE brine electrolysis technology.Therefore ion-exchange membrane insulation itself can not the sedimentary method of electricity consumption directly be prepared in catalyzer on the film.In addition, because Co-P catalyzer and substrate adhere firmly, can not will be deposited on Co-P catalyzer on the conductive substrates with the method for direct spraying and directly transfer to dielectric base for example on the ion-exchange membrane.And combine closely with Co-P catalyzer and conductive substrates material that electrodip process is prepared, prior art also can't be transferred to it on ion-exchange membrane.In addition, even can catalyzer be scraped, adopt this method also can destroy the configuration of surface even the structure of catalyzer, and the granules of catalyst that this sample loading mode obtains is generally bigger with hard things such as blades, promptly use the method for spraying to prepare membrane electrode, catalytic performance also can variation.Therefore the catalyzer for preparing with this method is difficult to prepare the membrane electrode in the SPE brine electrolysis technology, also is inconvenient to use other base material, thereby has limited the use field of this catalyzer greatly.
Summary of the invention
Technical problem
The purpose of this invention is to provide a kind of method that is used to shift the Co-P catalyzer of galvanic deposit, adopt this method, can under the situation that does not influence activity of such catalysts, easily shift the Co-P catalyzer of galvanic deposit.
Technical scheme
In order to address the above problem, the invention provides a kind of method that is used to shift the Co-P catalyzer of galvanic deposit, said method comprising the steps of: using pH value is that alkaline aqueous solution processing more than 13 is at the conductive substrates sedimentary Co-P catalyzer that powers on, so that it breaks away from from conductive substrates.If the pH value of alkaline aqueous solution is lower than 13, the Co-P catalyzer of galvanic deposit will be broken away from from conductive substrates.In addition, the pH value of alkaline aqueous solution is big more, helps making the Co-P catalyzer of galvanic deposit to break away from more.Described alkaline aqueous solution for example comprises mineral alkali, oxyhydroxide such as potassium hydroxide, sodium hydroxide, ammoniacal liquor, carbonate such as yellow soda ash, salt of wormwood, and the organic bases aqueous solution of oxyhydroxide such as tetraethyl ammonium hydroxide for example.The concentration of described alkaline aqueous solution is generally 0.1M to saturation concentration (peak concentration, 25 ℃), and concentration is big more, helps making the Co-P catalyzer of galvanic deposit to break away from more.
The method according to this invention also comprises transfers to the suprabasil step different with conductive substrates with the catalyzer that breaks away from.This step is undertaken by dropping, spraying, silk screen printing or hot pressing.The described substrate different with conductive substrates is preferably the substrate that can not prepare catalyzer by electro-plating method, that is, and and dielectric base, more preferably ion-exchange membrane.
Technique effect
The method according to this invention, the Co-P catalyzer that is deposited on securely on the conductive substrates can be transferred to other substrate at an easy rate, the substrate that particularly can not prepare catalyzer by electro-plating method, ion-exchange membrane for example, comprise proton exchange membrane, and the catalyzer after shifting can keep its structure that forms in electrodeposition process not to be destroyed, make activity of such catalysts unaffected, for example for the catalyzer before and after shifting, current density almost remains unchanged in the scope of 0.3-2mA (different because of experiment condition).
Embodiment
Further specify the present invention according to specific embodiment below, but the invention is not restricted to described embodiment.
Embodiment 1
Prepare the 200ml electroplating solution as follows: the concentration of potassiumphosphate and potassium primary phosphate is 0.1M, and the two the pH value of solution is adjusted to 7.0, adds the 0.5mM Xiao Suangu to solution, makes electroplating solution.With conductive glass ITO is working electrode, and platinum guaze is a counter electrode, and plated conductive glass is 15 hours under 1.29V (vs.NHE), is firmly covered the black cobalt phosphorus catalyst on the conductive glass ITO.
Test before shifting: with the conductive glass ITO that has catalyzer as working electrode, with the platinum guaze is counter electrode, in the pH value is to carry out Electrolytic Water Experiment in 7.0 potassiumphosphate and the potassium dihydrogen phosphate mixed solution, setting current potential is under the situation of 1.29V (vs.NHE), and can observe conductive glass surface and platinum guaze all has a large amount of gases to separate out.Current density can reach 0.45mA/cm
2
The conductive glass of the band catalyzer that will obtain with electro-plating method is immersed in the potassium hydroxide of 1M, and (the pH value: 14) in the solution 30 minutes, the black catalyzer all came off from conductive glass ITO, is deposited in the potassium hydroxide solution.
Test after the transfer: an above-mentioned sedimentary part is transferred in the ethanolic soln with centrifugation method, be added drop-wise in another piece conductive glass substrate, treat that ethanol volatilization rear catalyst is attached to conductive glass ITO laminar surface, with this conductive glass is working electrode, platinum guaze is a counter electrode, repeat Electrolytic Water Experiment, can observe conductive glass surface and platinum guaze all has a large amount of gases to separate out.Current density can reach 0.40mA/cm
2, to compare with the catalyzer before shifting, current density change is very little, and this shows that surperficial transfer processing does not influence catalyst activity.
Preparation membrane electrode: with centrifugation method an above-mentioned sedimentary part is transferred in the 20mL dehydrated alcohol, used ultrasonic 30 minutes of cell pulverization ultrasound probe.Filter, dry under the room temperature behind the absolute ethanol washing several, get the black catalyst fines.This powder can directly apply to the preparation of membrane electrode.Take by weighing the 5mgCo-P catalyst fines, with QAPS coating solution (QAPS (quaternary ammoniumpolysulphone, the quaternary ammonium polysulfones) DMF of film (dimethyl formamide) solution) with 7: 1 mixed, ultrasonic 40 minutes to be uniformly dispersed, with spray gun mixing solutions is sprayed on the carbon paper substrate, be prepared into the anode of Ф 20mm.Anode, QAPS ion-exchange membrane, negative electrode (spraying platinum C catalyst on the carbon paper substrate) are assembled by hot pressing on thermocompressor, can be prepared membrane electrode.
Embodiment 2
With specific embodiment 1, difference is for (the pH value: 14) sodium hydroxide solution (is 8.6M 25 ℃ saturation concentrations) separates the Co-P catalyzer with conductive glass ITO substrate with 7.5M.As a result, black Co-P catalyzer all comes off from conductive glass ITO, is deposited in the sodium hydroxide solution.
With with embodiment 1 in identical method detecting catalyst before shifting and current density data afterwards, obtain following result: the current density before shifting is 0.45mA/cm
2, and the current density after shifting is 0.39mA/cm
2This shows that the current density change of catalyzer is very little before and after shifting, this shows that surperficial transfer processing does not influence catalyst activity.
Embodiment 3
With specific embodiment 1, (the pH value: 14) the tetraethyl ammonium hydroxide aqueous solution separates the Co-P catalyzer difference with conductive glass ITO substrate in order to use 1.36M.As a result, black Co-P catalyzer all comes off from conductive glass ITO, is deposited in the tetraethyl ammonium hydroxide aqueous solution.
With with embodiment 1 in identical method detecting catalyst before shifting and current density data afterwards, obtain following result: the current density before shifting is 0.45mA/cm
2, and the current density after shifting is 0.41mA/cm
2This shows that the current density change of catalyzer is very little before and after shifting, this shows that surperficial transfer processing does not influence catalyst activity.
Embodiment 4
With specific embodiment 1, difference is separated the Co-P catalyzer for using 0.3M (pH=13.4) potassium hydroxide aqueous solution with conductive glass ITO substrate.As a result, black Co-P catalyzer all comes off from conductive glass ITO, is deposited in the potassium hydroxide aqueous solution.
With with embodiment 1 in identical method detecting catalyst before shifting and current density data afterwards, obtain following result: the current density before shifting is 0.45mA/cm
2, and the current density after shifting is 0.40mA/cm
2This shows that the current density change of catalyzer is very little before and after shifting, this shows that surperficial transfer processing does not influence catalyst activity.
Comparative example 5
With specific embodiment 1, difference is separated the Co-P catalyzer for using 0.05M (pH=12.7) potassium hydroxide aqueous solution with conductive glass ITO substrate.As a result, the long-time immersion down, black Co-P catalyzer can not come off from conductive glass ITO.
Claims (7)
1. a method that is used to shift the Co-P catalyzer of galvanic deposit is characterized in that, said method comprising the steps of: using pH value is that alkaline aqueous solution processing more than 13 is at the conductive substrates sedimentary Co-P catalyzer that powers on, so that it breaks away from from conductive substrates.
2. method according to claim 1 is characterized in that: described alkaline aqueous solution comprises hydroxide aqueous solution.
3. method according to claim 1 and 2 is characterized in that: the concentration of described alkaline aqueous solution is more than the 0.1M.
4. method according to claim 1 is characterized in that: described method also comprises transfers to the suprabasil step different with conductive substrates with the catalyzer that breaks away from.
5. method according to claim 4 is characterized in that: the catalyzer that breaks away from is transferred to the suprabasil step different with conductive substrates undertaken by dropping, spraying, silk screen printing or hot pressing.
6. method according to claim 4 is characterized in that: the described substrate different with conductive substrates is dielectric base.
7. method according to claim 6 is characterized in that: described dielectric base is an ion-exchange membrane.
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| CN101638795B true CN101638795B (en) | 2011-01-05 |
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Non-Patent Citations (2)
| Title |
|---|
| Keun Woo Cho et al.Effects of electrodeposited Co and Co–P catalysts on the hydrogen generation properties from hydrolysis of alkaline sodium borohydride solution.《Catalysis Today》.2006,第120卷298–304. * |
| 郎庆成.镀锡铜线脱锡工艺.《再生资源研究》.2004,(第1期),40. * |
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