CN101191237B - Method for preparing hydrogen-preparing hydrogen-storing integrated electrode - Google Patents
Method for preparing hydrogen-preparing hydrogen-storing integrated electrode Download PDFInfo
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- CN101191237B CN101191237B CN2006101441774A CN200610144177A CN101191237B CN 101191237 B CN101191237 B CN 101191237B CN 2006101441774 A CN2006101441774 A CN 2006101441774A CN 200610144177 A CN200610144177 A CN 200610144177A CN 101191237 B CN101191237 B CN 101191237B
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Abstract
The invention relates to a hydrogen making, hydrogen storing combination electrode method of preparation which is applied to electrolyzed water hydrogen making and organic electrocatalysis hydrogen storing technologies. In the invention, the electrocatalyst silver amalgam is plated on the ion exchange membrane based on the multiple step chemical method and combined with the ion exchange membrane, forming a composite electrode, wherein the multiple step chemical method is that the ion exchange membrane is plated with the silver based on the impregnation reduction method and combined with the silver based on the chemical deposit method or the impregnation reduction method, forming the silver amalgam. The process of the electrolyzed water hydrogen making and the organic hydrogenation storing, in which the electrode of the invention is adopted, makes use of mild conditions under which the silver and the mercury are alloyed, the hydrogen overvoltage of the mercury is relatively high, thereby well restricting the hydrogen evolution and improving the reaction velocity, along with easy preparation; moreover, the current efficiency of the alloy electrode prepared based on the method of the invention reaches 30 to 40 percent and is obviously improved.
Description
Technical field
The present invention relates to a kind of a kind of method for preparing hydrogen-preparing hydrogen-storing integrated electrode that can in water electrolysis hydrogen production and organism electrocatalysis hydrogen storage technology, use.
Background technology
Hydrogen Energy is because of its cleaning, efficient, abundant, is considered to tool potentiality of new millennium, pollution-free, the environment-friendly energy.The research of various development and utilization Hydrogen Energies is subjected to attention in the industry always.And the development and utilization of Hydrogen Energy is the prerequisite that is stored as with Hydrogen Energy.With water electrolysis hydrogen producing and organism electrocatalysis storage hydrogen compound be one, utilize exchange membrane electrode to realize by electrochemical process, in electrochemical process, the electrolytic reaction of anode generation water, the proton that water electrolysis is produced reacts and the storage of realization hydrogen at negative electrode and unsaturated compounds generation electrochemical hydrogenation.
Patent application 200410033882.8 discloses a kind of electrolysis with water as anode, carry out the reaction of organism electrocatalytic hydrogenation at negative electrode, with hydrogen " load " on organism, the proton that utilizes exchange membrane electrode that water electrolysis is produced is utilized by original position on negative electrode, thus the method that adopts " accurate original position " synthetic technology that hydrogen manufacturing and storage hydrogen are combined.But ion-exchange membrane is the organic polymer of a class efficient transfer proton, the ability (its ionic conductance and dilution heat of sulfuric acid are similar) of its transmission proton is strong, in exchange membrane electrode, proton is at positive and negative interpolar transitive dependency ionic membrane, therefore to the electrolysis in the middle of the non-aqueous media, help reducing the transport resistance of electric charge.
Normally used electrode is organism hydrogenation eelctro-catalyst and the membrane-bound combined electrode of ion-exchange in above-mentioned hydrogen manufacturing and the storage hydrogen coupling technique, electrode selectivity, current efficiency remain further to be improved, suppressing liberation of hydrogen, improve the speed of main reaction, improve the current efficiency aspect and remain to be improved.
Summary of the invention
The object of the invention is to provide a kind of and is suppressing liberation of hydrogen, and the speed of main reaction improves, the method for preparing hydrogen-preparing hydrogen-storing integrated electrode that the current efficiency aspect is improved.
The present invention realizes by the following technical solutions:
Utilize the step chemical method that the eelctro-catalyst silver amalgam is plated on the ion-exchange membrane, being combined as a whole with ion-exchange membrane forms combined electrode.
Wherein the step chemical method is meant and plates silver by immersion reduction method on ion-exchange membrane earlier, and then adopts chemical deposition or immersion reduction method to form silver amalgam.
The present invention also realizes by the following technical solutions:
Wherein immersion reduction method silver plated condition on ion-exchange membrane is [Ag (NH
3)
2]
+Concentration 0.002-0.02mol/L, dipping temperature 50-90 ℃, dipping time 30-60 minute, concentration of formaldehyde 0.1-2%, reduction temperature 50-90 ℃, recovery time 5-120 minute.
Wherein the condition of immersion reduction method formation silver amalgam is HgCl
2Concentration 0.002-0.02mol/L, dipping temperature 30-90 ℃, dipping time 30-90 minute, SnCl
2Concentration 0.1-6%, reduction temperature 20-90 ℃, recovery time 5-120 minute.
Wherein the condition of chemical deposition formation silver amalgam is HgCl
2Concentration 0.005-0.02mol/L, SnCl
2Concentration 1-6%, temperature of reaction 20-90 ℃, reaction times 2-6 hour.
Electrode of the present invention is used for the process that water electrolysis hydrogen production-organism adds storing hydrogen, utilized argental mercury to form the mild condition of alloy, and the hydrogen overvoltage of mercury is higher, can well suppress liberation of hydrogen, improve the speed of main reaction, be easy to preparation, the alloy electrode current efficiency of the present invention's preparation can reach 35-40%, and current efficiency is significantly improved.
Embodiment
The preparation method of the used electrode of the present invention is that the method for fractional steps prepares alloy electrode.At first silver-plated on ion-exchange membrane by immersion reduction method, and then adopt chemical deposition or immersion reduction method to form silver amalgam.
Immersion reduction method silver-plated process on ion-exchange membrane is: prepare certain density silver-colored ammonium complex salt solution, and certain density formaldehyde solution; Selected ionic membrane is assemblied in the reactor, and the silver-colored ammonium complex salt solution good preheating joins in the reactor, makes the metallic complex salt oxygenant at film surface constant temperature dipping; After dipping finishes, pour out solution, wash the reactor internal surface a little with deionized water after, the good formaldehyde solution of preheating is poured into reactor reduces; After recovery time finishes, take out from reactor that film cleans successively, drying, weighing, preservation.
The technical parameter for preparing electrode with immersion reduction method is preferably: [Ag (NH
3)
2]
+Concentration 0.002-0.02mol/L, dipping temperature 50-90 ℃, dipping time 30-60 minute, concentration of formaldehyde 0.1-2%, reduction temperature 50-90 ℃, recovery time 5-120 minute.。
Chemical deposition silver amalgam process is mainly: prepare the ion-exchange membrane of the good silver of plating, dispose certain density metal salt solution and reductant solution and be heated to temperature of reaction in advance; Under the certain reaction temperature, carry out the electroless plating reaction, after the reaction times finishes, take out membrane electrode and clean (be generally about 5min and get final product) with ultrasonic cleaner; Reaction conditions is preferably: HgCl
2Concentration 0.005-0.02mol/L, SnCl
2Concentration 1-6%, temperature of reaction 20-90 ℃, reaction times 2-6 hour.
The process that immersion reduction method prepares electrode is: prepare certain density metallic complex salt solution, and certain density NaBH
4Solution; Selected ionic membrane is assemblied in the reactor, and the metallic complex salt solution good preheating joins in the reactor, makes the metallic complex salt oxygenant at film surface constant temperature dipping; After dipping finishes, pour out solution, wash the reactor internal surface a little with deionized water after, the good NaBH of preheating
4Solution is poured reactor into and is reduced; After recovery time finishes, take out from reactor that film cleans successively, drying, weighing, preservation.
The technical parameter for preparing the silver amalgam electrode with immersion reduction method is preferably: HgCl
2Concentration 0.002-0.02mol/L, dipping temperature 30-90 ℃, dipping time 30-90 minute, SnCl
2Concentration 0.1-6%, reduction temperature 20-90 ℃, recovery time 5-120 minute.
The present invention also provides following specific embodiment.
The unsaturated compounds that is used for hydrogenation reaction in the example is a benzene, and the condition of this gas-liquid reaction is:
20-90 ℃ of benzene tank temperature;
20-90 ℃ of water storage tank temperature;
Electrolysis temperature 20-90 ℃;
Feed the flow rate of carrier gas 40-100ml/min of benzene, feed the flow rate of carrier gas 40-100ml/min of water;
The electrolysis tested media: concentration is the sulphuric acid soln of 0.005-1mol/l;
Reference electrode: saturated calomel electrode;
Embodiment 1:
Adopt immersion reduction method silver-plated on ion-exchange membrane: to prepare silver-colored ammonium complex salt solution [Ag (NH
3)
2]
+Concentration 0.01mol/L, and 1% formaldehyde solution; Nafion film through weighing is assemblied in the reactor, and the metallic complex salt solution good preheating joins in the reactor, and temperature control is at 60 ℃, and ultrasonic constant temperature flooded about 40 minutes, made the metallic complex salt oxygenant at the film surface impregnation; After dipping finishes, pour out solution, wash the reactor internal surface a little with deionized water after, the formaldehyde solution that is preheating to 60 ℃ is poured into reactor reduces, 1.0 hours reduction reaction time; After reduction finishes, take out from reactor that film cleans successively, drying, weighing, preservation.
Adopt chemical deposition to prepare silver amalgam: to prepare the ion-exchange membrane of the good silver of plating, dispose certain density metal salt solution and reductant solution and be heated to temperature of reaction in advance; Under the certain reaction temperature, carry out the electroless plating reaction, after the reaction times finishes, take out membrane electrode and clean (be generally about 5min and get final product) with ultrasonic cleaner; Reaction conditions is preferably: HgCl
2Concentration 0.01mol/L, SnCl
2Concentration 4%, 50 ℃ of temperature of reaction, 3 hours reaction times.
The silver amalgam electrode that above method obtains utilizes gas/liquid phase benzene hydrogenation-water electrolysis reaction device to carry out electrochemical reaction, and electrolysis temperature and humidification water steam are 70 ℃ in the reaction, and reference electrode is a saturated calomel electrode; The electrolysis tested media: negative electrode is a benzene vapor, is carried from inlet mouth by nitrogen and enters negative electrode, flow velocity 60ml/min; The anolyte compartment is a 0.5mol/L sulfuric acid.
Reaction product is utilized chromatogram analysis, can obtain the product hexanaphthene and the tetrahydrobenzene of benzene hydrogenation, also has by product hydrogen simultaneously, and current efficiency reaches 35%.
Embodiment 2:
Adopt the immersion reduction method identical with embodiment 1 silver-plated on ion-exchange membrane: getting other condition is: silver-colored ammonium complex salt solution [Ag (NH
3)
2]
+Concentration 0.015mol/L, 0.8% formaldehyde solution; The reactor temperature control is at 50 ℃, and ultrasonic constant temperature flooded about 40 minutes, is preheating to 50 ℃ formaldehyde solution and pours reactor into and reduce 0.5 hour reduction reaction time.
Adopt immersion reduction method to prepare the silver amalgam electrode: to prepare certain density HgCl
2Solution and SnCl
2Solution; Selected ionic membrane is assemblied in the reactor, the good HgCl of preheating
2Solution joins in the reactor, the constant temperature dipping; After dipping finishes, pour out solution, wash the reactor internal surface a little with deionized water after, the good SnCl of preheating
2Solution is poured reactor into and is reduced; After recovery time finishes, take out from reactor that film cleans successively, drying, weighing, preservation.
The technical parameter for preparing the silver amalgam electrode with immersion reduction method is preferably: HgCl
2Concentration 0.01mol/L, 60 ℃ of dipping temperatures, dipping time 50 minutes, SnCl
2Concentration 4%, 60 ℃ of reduction temperatures, 40 minutes recovery times.
The ion-exchange membrane top electrode that above method obtains utilizes gas/liquid phase benzene hydrogenation-water electrolysis reaction device to carry out electrochemical reaction, and electrolysis temperature and humidification water steam are 70 ℃ in the reaction, and reference electrode is a saturated calomel electrode; The electrolysis tested media: negative electrode is a benzene vapor, is carried from inlet mouth by nitrogen and enters negative electrode, flow velocity 60ml/min; The anolyte compartment is a 0.5mol/L sulfuric acid.
Reaction product is utilized chromatogram analysis, can obtain the product hexanaphthene and the tetrahydrobenzene of benzene hydrogenation, also has by product hydrogen simultaneously, and current efficiency reaches 40%.
Embodiment 3
Adopt the immersion reduction method identical with embodiment 1 silver-plated on ion-exchange membrane: getting other condition is: silver-colored ammonium complex salt solution [Ag (NH
3)
2]
+Concentration 0.002mol/L, 2% formaldehyde solution; The reactor temperature control is at 90 ℃, and ultrasonic constant temperature flooded about 30 minutes, is preheating to 50 ℃ formaldehyde solution and pours reactor into and reduce 5 minutes reduction reaction time.
Adopt chemical deposition to prepare silver amalgam: prepare the ion-exchange membrane of the good silver of plating, reaction conditions is preferably: HgCl
2Concentration 0.005mol/L, SnCl
2Concentration 6%, 20 ℃ of temperature of reaction, 6 hours reaction times.
Embodiment 4
Adopt the immersion reduction method identical with embodiment 1 silver-plated on ion-exchange membrane: getting other condition is: silver-colored ammonium complex salt solution [Ag (NH
3)
2]
+Concentration 0.2mol/L, 0.1% formaldehyde solution; The reactor temperature control is at 50 ℃, and ultrasonic constant temperature flooded about 40 minutes, is preheating to 50 ℃ formaldehyde solution and pours reactor into and reduce 2 hours reduction reaction time.
Adopt the immersion reduction method identical with embodiment 1 to prepare the silver amalgam electrode: parametric optimization is: HgCl
2Concentration 0.002mol/L, 90 ℃ of dipping temperatures, dipping time 30 minutes, SnCl
2Concentration 6%, 20 ℃ of reduction temperatures, 120 minutes recovery times.
Embodiment 5
Adopt the immersion reduction method identical with embodiment 4 silver-plated on ion-exchange membrane: getting other condition is: silver-colored ammonium complex salt solution [Ag (NH
3)
2]
+Concentration 0.2mol/L, 0.1% formaldehyde solution; The reactor temperature control is at 50 ℃, and ultrasonic constant temperature flooded about 40 minutes, is preheating to 50 ℃ formaldehyde solution and pours reactor into and reduce 2 hours reduction reaction time.
Adopt the immersion reduction method identical with embodiment 4 to prepare the silver amalgam electrode: parametric optimization is: HgCl
2Concentration 0.02mol/L, 30 ℃ of dipping temperatures, dipping time 90 minutes, SnCl
2Concentration 0.1%, 90 ℃ of reduction temperatures, 5 minutes recovery times.
The present invention has supplied silver amalgam research electrode at the similarity condition lower body.When above electrochemical reaction was liquid-liquid reactions, the principle of design of reaction unit was identical, just made the negative plate outside communicate with cathode reaction chambers.
Experiment serves as the research electrode with platinized exchange membrane electrode, and the preparation method is close with embodiment 1, is reference electrode with the saturated calomel electrode, and the metal platinized platinum is a supporting electrode.Electrolytic solution is the H of 0.5mol/L
2SO
4Solution.N
2As carrier gas (80mL/min), 70 ℃ of experimental temperatures.
Stratographic analysis shows, can obtain the product hexanaphthene and the tetrahydrobenzene of benzene hydrogenation, also has by product hydrogen simultaneously, and current efficiency reaches 15%, compares with the result of embodiment 1,2, and current efficiency is very low.
Claims (1)
1. a method for preparing hydrogen-preparing hydrogen-storing integrated electrode is characterized in that, utilizes the step chemical method that the eelctro-catalyst silver amalgam is plated on the ion-exchange membrane, and being combined as a whole with ion-exchange membrane forms combined electrode; Earlier on ion-exchange membrane, plate silver, and then adopt immersion reduction method to form silver amalgam by immersion reduction method; Wherein immersion reduction method silver plated condition on ion-exchange membrane is [Ag (NH
3)
2]
+Concentration 0.002-0.02mol/L, dipping temperature 50-90 ℃, dipping time 30-60 minute, concentration of formaldehyde 0.1-2%, reduction temperature 50-90 ℃, recovery time 5-120 minute; Wherein the condition of immersion reduction method formation silver amalgam is HgCl
2Concentration 0.002-0.02mol/L, dipping temperature 30-90 ℃, dipping time 30-90 minute, SnCl
2Concentration 0.1-6%, reduction temperature 20-90 ℃, recovery time 5-120 minute.
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| CN111468054A (en) * | 2020-04-16 | 2020-07-31 | 南京西浦储能技术研究院有限公司 | Unsaturated organic matter circulating hydrogenation energy storage device and method |
Citations (2)
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| CN1526179A (en) * | 2001-06-23 | 2004-09-01 | ���֪�� | Method for producing gas diffusion electrodes |
| CN1683596A (en) * | 2004-04-15 | 2005-10-19 | 石油大学(北京) | Method for producing hydrogen and storaging hydrogen integrately |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526179A (en) * | 2001-06-23 | 2004-09-01 | ���֪�� | Method for producing gas diffusion electrodes |
| CN1683596A (en) * | 2004-04-15 | 2005-10-19 | 石油大学(北京) | Method for producing hydrogen and storaging hydrogen integrately |
Non-Patent Citations (2)
| Title |
|---|
| N. Itoh，etc.Electrochemical coupling of benzene hydrogenation andwater electrolysis.Catalysis Today56.2000,56307-314. * |
| 黄海燕等.电催化苯加氢Ag/Nafion电极制备研究.武汉理工大学学报28.2006,28574-577. * |
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