CN1743072A - Method for increasing platinum activity through surface modification - Google Patents
Method for increasing platinum activity through surface modification Download PDFInfo
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- CN1743072A CN1743072A CNA200510086584XA CN200510086584A CN1743072A CN 1743072 A CN1743072 A CN 1743072A CN A200510086584X A CNA200510086584X A CN A200510086584XA CN 200510086584 A CN200510086584 A CN 200510086584A CN 1743072 A CN1743072 A CN 1743072A
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- lauryl sodium
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to a preparation of high-activity direct fuel cell. It utilizes surface modification method to treat electrode and catalyst surface, and said method includes the following steps: in the acidic solution of methyl alcohol adding two surfactants of sodium dodecanesulphonate or hydrogen diamine citrate, also can mix two solutions in which the sodium dodecanesulphonate or hydrogen diamine citrate is respectively added according to a certain ratio. The adoption of said method not only can raise electric catalytic capability of platinum for acidic solution of the methyl alcohol so as to raise oxidation speed of methyl alcohol, but also the application of surfactant can reduce adsorption quantity of carbon monoxide on the platinum electrode, so that the toxicant action of carbon monoxide to platinum electrode can be reduced.
Description
Technical field
The present invention relates to the alternative fuel and the additive of fuel cell, refer more particularly to the preparation of the direct fuel cell of high activity.
Background technology
It is few that DMFC (DMFC) fuel obtains energy loss, the low pollution, and energy density height, compact conformation, volume is little, serviceability temperature is low etc.In addition, it also has fuel diversity, exhaust is clean, and noise is low, and characteristics such as good reliability are considered to electric powered motor and the most promising electrochmical power source of other civilian occasion.At present, the preparation key technology of DMFC is ripe, and the biggest obstacle that limits its application is that cost of manufacture is too high.DMFC uses the Pt series catalysts substantially, because Pt is a noble metal, and resource-constrained, costing an arm and a leg, is the main direction of studying of DMFC so reduce the eelctro-catalyst cost, promptly improves the utilization rate of platinum, reduce the platinum load amount of unit are electrode, reduce the poisoning effect of carbon monoxide.In the invention of CN1564356A " a kind of method for preparing alcohols fuel cell anode platinum ruthenium/carbon binary catalyst ", mainly be the active site that improves platinum, and improve the ability that its anti-carbon monoxide is poisoned.M.Watanabe and for example, et.al., Preparation ofhighly dispersed Pt+Ru alloy clusters and the activity for electrocoxidation ofmethanol, J.Electroanal.Chem., 229 (1987) 395 report, be to use the synthetic platinum ruthenium catalyst of colloid method, reduce the use of platinum by using ruthenium.But their subject matter all is just to have reduced departmental cost, but production cost is still higher, is difficult to extensive use.
Summary of the invention
The present invention handles the surface of electrode and catalyst by the method for surface modification, promptly use the poisoning effect that the method for adding lauryl sodium sulfate or these two kinds of surfactants of diammonium hydrogen citrate improves the active site of platinum and reduces carbon monoxide, thereby in the use amount that fundamentally reduces platinum, improve and recycle the life-span, and make the price comparison of surfactant cheap, application process is also fairly simple.
Implementation step of the present invention is:
In the acid solution of methyl alcohol, add the lauryl sodium sulfate of 0.055g/ml～0.08g/ml or add 0.015g/ml～0.03g/ml diammonium hydrogen citrate according to stoichiometry, again or will add the lauryl sodium sulfate of 0.055g/ml～0.08g/ml and add these two kinds of solution of 0.015g/ml～0.03g/ml diammonium hydrogen citrate and mixed according to 1: 100～100: 1 according to stoichiometry.
Advantage of the present invention is owing to added lauryl sodium sulfate or diammonium hydrogen citrate surfactant respectively in the acid solution of methyl alcohol, make the surface have the characteristic of automatic selection absorption or desorption to methyl alcohol and carbon monoxide, improved the active site of platinum, and reduced the poisoning effect of carbon monoxide, and the oxidation susceptibility before not having to damage, realized modification, obtained the fuel of better performances for catalyst or electrode surface.Compared with prior art, reduce the use amount of platinum, and kept the ability of its catalytic oxidation alcohol, had economy, characteristic of simple.
Description of drawings
Fig. 1 is the acid cyclic voltammogram of methanol solution on platinum electrode
Fig. 2 is for adding the cyclic voltammogram of acidic methanol solution on platinum electrode of lauryl sodium sulfate
Fig. 3 is the change curve of the oxidation peak current of 0.62V with the addition of lauryl sodium sulfate
Fig. 4 is the AC impedance figure when not adding lauryl sodium sulfate
AC impedance figure when Fig. 5 is 0.05g/ml for adding lauryl sodium sulfate
AC impedance figure when Fig. 6 is 0.09g/ml for adding lauryl sodium sulfate
Fig. 7 is for adding the cyclic voltammogram of acidic methanol solution on platinum electrode of diammonium hydrogen citrate
Fig. 8 is the change curve of the flyback peak current of the oxidation peak current of 0.62V and 0.41V with the addition of diammonium hydrogen citrate
Fig. 9 is for adding and the cyclic voltammogram of acidic methanol solution on platinum electrode that does not add lauryl sodium sulfate and diammonium hydrogen citrate
The specific embodiment
In application cycle volt-ampere research oxidization of methanol process, think that 1 peak in the cyclic voltammogram (seeing accompanying drawing 1) is the oxidization of methanol peak, 2 peaks are the flyback peak, wherein the flyback peak is considered to relevant with the absorption of carbon monoxide.So improving oxidation peak and obtaining relatively low flyback peak is to be considered to optimal results.
Embodiment 1:
Use 1M methyl alcohol+1M sulfuric acid as reaction solution, drip the surfactant solution of 1M methyl alcohol+1M sulfuric acid+lauryl sodium sulfate therein gradually.Working electrode and auxiliary electrode are platinum electrode, result that application cycle volt-ampere method obtains such as accompanying drawing 2.Oxidation peak is in continuous rising as seen from Figure 2, and this explanation oxidation current is increasing, and oxidization of methanol speed is improved, and under the situation that does not all have to change in any other condition, this active site that proves absolutely platinum has increased.
Oxidation peak analysis to 0.62V obtains accompanying drawing 3.Can be analyzed by Fig. 3 and to draw, when addition was less than 0.055g/ml, oxidation current was along with the increase of addition increases.And at 0.055g/ml to having occurred a platform between the 0.08g/ml, this illustrates that in these interpolation processes the increase of lauryl sodium sulfate is to not influence of electric current.Electric current reduces rapidly after 0.08g/ml, and this is because a large amount of surface that is adsorbed on electrode of surfactant causes methyl alcohol to be difficult to arrive electrode surface, thereby reduced current value.
Addition in lauryl sodium sulfate is respectively 0,0.05, and that has carried out AC impedance on the A of 0.09g/ml, B, the C position respectively measures accompanying drawing 4,5,6.The equivalent circuit of accompanying drawing 4,5 is R (C (R (C (RW)))), and this is the electrochemical reaction process that contains absorption, and table 1 is respectively 0, the electrochemical impedance of 0.05g/ml for the addition of lauryl sodium sulfate.Faraday's resistance has reduced as can be seen, and this illustrates that wherein adsorption process should be the absorption of methyl alcohol.The absorption of having added the later methyl alcohol of lauryl sodium sulfate has increased this active site that platinum just in time is described have been increased.The equivalent circuit of accompanying drawing 6 is R (C (R (C (RTW)))), after adding excess surface active agent, occurred T-obstruction type diffusion in the equivalent circuit, this has illustrated the layer of substance that has occurred hindering methyl alcohol on the surface of electrode, and this is just in time consistent with the result that analyzes among Fig. 3.
The addition of table 1 lauryl sodium sulfate is respectively 0, the electrochemical impedance of 0.05g/ml
| Sequence number | Circuit impedance | Do not add | Addition is 0.05g/ml |
| 1 | R | 28.47 | 28.06 |
| 2 | C | 1.337E-5 | 1.134E-5 |
| 3 | R | 1704 | 1120 |
| 4 | C | 1.415E-5 | 1.787E-5 |
| 5 | R | 2615 | 1508 |
| 6 | W | 0.000506 | 0.0005641 |
Embodiment 2:
Use 1M methyl alcohol+1M sulfuric acid as reaction solution, drip the surfactant solution of 1M methyl alcohol+1M sulfuric acid+diammonium hydrogen citrate therein gradually.Working electrode and auxiliary electrode are platinum electrode, result that application cycle volt-ampere method obtains such as accompanying drawing 7.By obtaining such result among Fig. 7: under the situation that does not have to change in oxidation peak, the flyback peak has reduced.This explanation is under the situation of the active site that does not destroy platinum, and the absorption of carbon monoxide has reduced.
The oxidation peak of 0.62V and the flyback peak analysis of 0.41V are obtained accompanying drawing 8.Can be obtained when addition is 0.015g/ml by accompanying drawing 8, the electric current of oxidation peak changes little, and the electric current at flyback peak reduces rapidly, and essentially identical platform occurred at the electric current of 0.015 to 0.035g/ml this section oxidation peak and the electric current at flyback peak.After continuing to add diammonium hydrogen citrate, the electric current at oxidation peak current and flyback peak all reduces rapidly.
Embodiment 3:
As reaction solution, working electrode and auxiliary electrode are platinum electrode with 1M methyl alcohol+1M sulfuric acid of adding the lauryl sodium sulfate of 0.08g/ml and adding the 0.015g/ml diammonium hydrogen citrate.This system is carried out cyclic voltammetric test and compared with the cyclic voltammogram of the 1M methyl alcohol+1M sulfuric acid that does not add any other reagent, obtain Fig. 9.Can obtain to draw a conclusion from Fig. 9: oxidation peak has increased, and the flyback peak has reduced.This is just in time corresponding with the result of example 1 and example 2, illustrates that having added these two kinds of surfactants has played the effect that improves the active site of platinum equally.
Claims (1)
1, a kind of surface modification improves the method for platinum activity, it is characterized in that: in the acid solution of methyl alcohol, add the lauryl sodium sulfate of 0.055g/ml～0.08g/ml according to stoichiometry, perhaps add 0.015g/ml～0.03g/ml diammonium hydrogen citrate, again or will add the lauryl sodium sulfate of 0.055g/ml～0.08g/ml and add these two kinds of solution of 0.015g/ml～0.03g/ml diammonium hydrogen citrate and mixed according to 1: 100～100: 1 according to stoichiometry.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102592837A (en) * | 2012-03-12 | 2012-07-18 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
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2005
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102592837A (en) * | 2012-03-12 | 2012-07-18 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
| CN102592837B (en) * | 2012-03-12 | 2014-01-15 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
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