CN104087969A - Anode for alleviating oxidation of formic acid on electrode and preparation method thereof - Google Patents
Anode for alleviating oxidation of formic acid on electrode and preparation method thereof Download PDFInfo
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- CN104087969A CN104087969A CN201410315897.7A CN201410315897A CN104087969A CN 104087969 A CN104087969 A CN 104087969A CN 201410315897 A CN201410315897 A CN 201410315897A CN 104087969 A CN104087969 A CN 104087969A
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Abstract
The invention discloses an anode for alleviating oxidation of formic acid on an electrode and a preparation method of the anode. The anode is wrapped with a semipermeable membrane which allows water, protons and electrolytes to pass through but limiting formic acid to pass through. According to the preparation method of the anode, a dip-coating method, a hot-pressing method or a method with the combination of the dip-coating method and the hot-pressing method is adopted to wrap the semipermeable membrane onto the anode. The anode has the advantages that by wrapping the semipermeable membrane which does not allow or limits formic acid to pass through but allowing water, protons and other electrolytes to pass through onto the anode, then the oxidation of formic acid on the anode is effectively alleviated, the Faraday efficiency of the process that formic acid is generated from carbon dioxide through electrochemical reduction is effectively improved, and meanwhile the allowable concentration of formic acid in the electrolytes is greatly improved.
Description
Technical field
The present invention relates to a kind of electrochemical reducting reaction, relate in particular to and a kind ofly can effectively reduce formic acid oxidized anode and preparation method thereof on electrode.
Background technology
Carbonic acid gas is the final product of all carbonaceous fuel burnings.After the Industrial Revolution, the carbonaceous fuel, particularly coal that cause the mankind to be burnt to craving for of the energy due to commercial run, oil, timber etc. continue to increase, and cause the content of carbonic acid gas in atmosphere to continue to raise.The rising of atmospheric carbon dioxide levels can produce some negative consequences, for example Greenhouse effect, vegetation period, change etc., therefore, must find by carbon dioxide conversion to be the process of useful chemical or carbonaceous fuel, thereby the artificial carbon cycle process that produces strengthening, makes up natural deficiency.
As everyone knows, natural carbon cycle process comprises that the organism such as biomass combustion, vegeto-animal breathing and metabolism change the process of carbonic acid gas into, and plant changes into carbonic acid gas and water by photosynthesis the process of organism and oxygen.The former consumes organism and oxygen generates carbonic acid gas and water, and the latter consumes carbonic acid gas and water generates organism and oxygen, has formed end to end working cycle.Photosynthesis of plant mild condition, efficiency are very high, and the solar energy density needing is low, but its speed is slow, can only rely on the plant of spreading all over all earth surfaces to produce total amount.In contrast, the matter and energy that the energy density of the mankind's industrialization action need is high, produce in unit surface is high, and dependence speed makes up the problem of insufficient space.
In recent years, the sustainable natural energy resources such as photoelectricity, wind-powered electricity generation, tide-electricity progressively and effectively enters human lives.There is a serious even fatal problem in these natural energy resources, is exactly that peak valley is ordinary, cuts in and out.At present, address this problem and need intelligent grid and complicated power storage system, therefore cost is very high, and therefore inefficiency finds that effective thermal energy storage process is very important.
The process that carbonic acid gas electrochemical reduction generates formic acid just in time can meet as above demand.Reason has four: (1) carbonic acid gas is present in atmosphere thinly, is also present in to high density in the tail gas of various combustion processeses and bio-metabolic process, and what we needed is that a kind of high efficiency separation process is obtained it; (2) faradic efficiency that carbonic acid gas electrochemical reduction produces formic acid process can reach 80% even more than 90% easily, and the formic acid of generation is convenient to store, and both can be used as industrial chemicals, also can be used as energy storage material.For example, in direct methanoic acid fuel cell, for generating, can solve the peak valley problem of natural energy resources.Therefore relevant technologies has huge market; (3) carbonic acid gas electro-reduction process required voltage is not high, and all natural energy power generation systems can meet easily, and reduction process start and stop at any time; (4) natural energy especially sun power and wind energy have everywhere, the tellurian any area even outer space all can utilize solar electrical energy generation.
Research finds, in potassium bicarbonate aqueous solution system, the reduzate of the upper carbonic acid gas of the metal electrode (negative electrode) such as tin, lead is mainly formic acid, its oxidising process to the upper main generation water of electrode (anode), and product is oxygen.Like this, total reaction is:
CO
2+H
2O＝HCOOH+1/2?O
2
In fact this process is similar to photosynthesis, has both consumed CO
2obtain useful material, also obtained the oxygen that animals and plants respiratory needs.This process also exists as next fatal problem, and the formic acid that reaction produces is easy on to electrode anode oxidized, thereby has a strong impact on the faraday efficiency of this process.This phenomenon is very outstanding in the time that formic acid concn is higher, must manage stop or delay.Because only, in the time that formic acid concn is higher, the sepn process of formic acid just has economy; Only, in the time that formic acid safe level is higher, electrolytic solution just can be recycled.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide and a kind ofly can effectively reduces formic acid oxidized anode on electrode; The second object of the present invention is to provide the preparation method of this anode.
Technical scheme: coated water, proton and the ionogen of allowing of anode of the present invention passes through, but the semi-permeable membranes that restriction formic acid passes through.
Wherein, described semi-permeable membranes is that proton exchange is touched.This proton exchange membrane is preferably Nafion film.
The preparation method of anode of the present invention, adopts method coated water, proton and ionogen of allowing on anode of dip coating, pressure sintering or both combinations to pass through, but the semi-permeable membranes that restriction formic acid passes through.
Wherein, described dip coating comprises anode is immersed in semi-permeable membranes film-forming soln, then takes out and dries up.Described semi-permeable membranes film-forming soln is Nafion film-forming soln, and wherein, the mass concentration of this Nafion film-forming soln is 1-5%.
, after the described anode taking-up in immersion semi-permeable membranes film-forming soln can also being dried up, again immerse in semi-permeable membranes film-forming soln, dipping number of times determines according to electrode performance meanwhile.
Described pressure sintering comprises semi-permeable membranes is fixed on to anode surface, and then under vacuum environment, hot pressing makes semi-permeable membranes together with anode seamless binding.
Can also first adopt dip coating at the coated semi-permeable membranes of described anode surface, then adopt the coated semi-permeable membranes of pressure sintering at the anode surface of overlay film.Described semi-permeable membranes can have different compositions and performance.
Beneficial effect: compared with prior art of the present invention, its remarkable advantage is: do not allowed or limited formic acid and pass through by coated on an anode, but allow water, proton and the freely through semi-permeable membranes of other electrolyte ingredient, effectively reduce the oxidation of formic acid on anode, the faraday efficiency that makes carbonic acid gas electrochemical reduction generate formic acid process is effectively improved, and also makes the safe level of formic acid in electrolytic solution obtain promoting significantly simultaneously.
Brief description of the drawings
Fig. 1 is that electrochemically reducing carbon dioxide of the present invention is prepared the faradic efficiency of formic acid process and the graph of a relation of anode overlay film and film thickness.
Embodiment
Below technical scheme of the present invention is described further.
Prepare in the process of formic acid at electrochemically reducing carbon dioxide, formic acid produces on the negative electrode of electrolyzer:
CO
2+2H
++2e＝HCOOH
Water is oxidized on anode:
H
2O＝1/2?O
2+2H
++2e
Total reaction is:
CO
2+H
2O＝HCOOH+1/2?O
2
The formic acid that reaction generates can be diffused on anode naturally, can consume because following side reaction is oxidized:
HCOOH＝CO
2+2H
++2e
Therefore, the electrochemical oxidation process of formic acid on this anode is disadvantageous, must be prevented from.It is oxidized on electrode that anode disclosed by the invention can effectively reduce formic acid.Its principle is, utilizes the characteristic of semi-permeable membranes, and the reactant that allowing needs sees through, but do not allow or material permeance that significantly restriction can produce side reaction.Particularly, the anode of coated semi-permeable membranes, allows water, proton and ionogen freely pass through, but does not allow or significantly limit formic acid to see through.Therefore, formic acid is difficult to arrive anode surface, and makes its oxidising process at anode suppressed.
This above-mentioned semi-permeable membranes is preferably proton exchange membrane, more preferably commercial Nafion film.
The preparation method of above-mentioned anode is the method that adopts dip coating, pressure sintering or both combinations, can be also vapour deposition process conventional in this area etc.They can be coated the semi-permeable membranes that can realize above-mentioned functions on anode.
In view of a lot of as the anode of carbonic acid gas electrochemical reduction generation formic acid process, can allow water, proton and ionogen freely pass through, but the semi-permeable membranes that does not allow or limit formic acid to see through is also a lot, the present invention only describes as an example of the platinum electrode commonly used and Nafion film example, and the electrode of other kind or semi-permeable membranes also can be prepared according to method disclosed by the invention.
Before overlay film, can be according to the characteristic of electrode, electrode surface is cleaned and processed to devise optimum scheme, removes objectionable impurities on the one hand, makes on the other hand described semi-permeable membranes easily adhere in its surface.For cleaning and the treating processes of platinum electrode, first, platinum electrode is soaked with the grease above removing in alkali, can be aided with if desired temperature and the means such as ultrasonic of rising alkali lye; After cleaning up with water purification, then platinum electrode is placed in to hydrochloric acid or dilute nitric acid solution washes away the metal oxide or the oxyhydroxide that on it, adhere to; With clean water, the acid solution of adhering on electrode is washed away again.For the electrode of other type, can design cleaning program targetedly according to the physicochemical property of electrode materials.
Can use dip coating, pressure sintering, or after the dip-coating reusable heat platen press, or repeatedly use dip coating, pressure sintering, or their combination obtains the composite membrane of multiple semi-permeable membranes composition, to reach best effect.
Described dip-coating film is as follows: cleaned electrode is immersed to the solution of semi-permeable membranes filmogen, for example commodity Nafion solution, took out after approximately 5 seconds, blew away the drop adhering to cleaned air above, then used the not hot blast drying higher than 150 DEG C.In the process drying up, semi-permeable membranes closely seamlessly forms on electrode surface.As required, as above process can be repeatedly to obtain needing the film of thickness.For example, the electrode that has wrapped up one deck semi-permeable membranes can immerse in this solution again, wraps up new one deck with method again, forms thicker film, and multiplicity can be determined as required.
Described to be hot pressed into membrane method as follows: the Nafion film that needs thickness is cut into the shape that is slightly larger than electrode, get two above-mentioned Nafion films be placed in cleaned platinum electrode sheet upper and lower surface and be fixed up, then they are placed in to vacuum chamber together, with two hot surfaces or ultrasonic auxiliary thermocompressor electrode together with Nafion film seamless binding.
The technique that described dip coating and pressure sintering are combined to form composite membrane is as follows: first form a skim with dip coating at electrode surface, then another tunic is got on pressure sintering hot pressing.This technique can arbitrary combination to obtain having the semi-permeable membranes of best effects.Certainly for some special electrodes, the electrode of for example being made by Powdered active substance, can be first on electrode coated one deck prevent the film that electrode composition runs off, more coated one deck has the proton exchange membrane that stops formic acid to enter, and then carries out subsequent disposal.
Study electrochemically reducing carbon dioxide below and prepare the relation of faradic efficiency and anode overlay film and the film thickness of formic acid process.
After the coated Nafion film of platinum anode, in a single compartment electrolytic cell when electrolysis, electrochemical reduction CO
2prepare formic acid.In experiment, platinized platinum is immersed to the Nafion solution (concentration is respectively 1%, 2.5% and 5%) of different concns, or immerse repeatedly (n represents to flood number of times, n=1-3) of 5%Nafion solution, prepare the Nafion film of different thickness.In figure, 0% represents not coated Nafion film, as a control group.
As seen from Figure 1, Nafion film can significantly improve the faradic efficiency that carbonic acid gas electrochemical reduction is prepared formic acid, and along with the increase of thickness, and faradic efficiency can increase gradually and finally reaches a stationary value.This research shows to wrap up Nafion film on anode can effectively reduce the electrochemical oxidation speed of formic acid on anode, and therefore formic acid is effectively suppressed at the electrochemical oxidation process of anode.
Claims (9)
1. reduce formic acid oxidized anode on electrode, it is characterized in that: on described anode, coated water, proton and the ionogen of allowing freely passes through, but limits the semi-permeable membranes that formic acid passes through.
2. reduce according to claim 1 formic acid oxidized anode on electrode, it is characterized in that: described semi-permeable membranes is that proton exchange is touched.
3. reduce according to claim 1 formic acid oxidized anode on electrode, it is characterized in that: described proton exchange membrane is Nafion film.
4. reduce according to claim 1 the preparation method of formic acid oxidized anode on electrode, it is characterized in that: adopt method coated water, proton and ionogen of allowing on anode of dip coating, pressure sintering or both combinations freely to pass through, but the semi-permeable membranes that restriction formic acid passes through.
5. the preparation method who reduces according to claim 4 formic acid oxidized anode on electrode, is characterized in that: described dip coating comprises anode is immersed in semi-permeable membranes film-forming soln, then takes out and dries up.
6. the preparation method who reduces according to claim 5 formic acid oxidized anode on electrode, is characterized in that: described semi-permeable membranes film-forming soln is Nafion film-forming soln, and wherein, the mass concentration of this Nafion film-forming soln is 1-5%.
7. according to the preparation method who reduces formic acid oxidized anode on electrode described in claim 5 or 6, it is characterized in that: after the described anode taking-up in immersion semi-permeable membranes film-forming soln is dried up, again immerse in semi-permeable membranes film-forming soln, dipping number of times determines according to electrode performance.
8. the preparation method who reduces according to claim 4 formic acid oxidized anode on electrode, is characterized in that: described pressure sintering comprises semi-permeable membranes is fixed on to anode surface, and then under vacuum environment, hot pressing makes semi-permeable membranes together with anode seamless binding.
9. the preparation method who reduces according to claim 4 formic acid oxidized anode on electrode, is characterized in that: first adopt dip coating at the coated semi-permeable membranes of described anode surface, then adopt the coated semi-permeable membranes of pressure sintering at the anode surface of overlay film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974690A (en) * | 2017-11-24 | 2018-05-01 | 盐城工学院 | Electrode and its preparation method and application and the method for preparing formic acid |
| CN109972162A (en) * | 2019-05-13 | 2019-07-05 | 中国人民解放军军事科学院防化研究院 | A kind of electro-chemistry oxygen-producing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974690A (en) * | 2017-11-24 | 2018-05-01 | 盐城工学院 | Electrode and its preparation method and application and the method for preparing formic acid |
| CN107974690B (en) * | 2017-11-24 | 2019-10-11 | 盐城工学院 | Electrode and its preparation method and application and the method for preparing formic acid |
| CN109972162A (en) * | 2019-05-13 | 2019-07-05 | 中国人民解放军军事科学院防化研究院 | A kind of electro-chemistry oxygen-producing method |
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| CN104087969B (en) | 2017-02-01 |
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