CN103878027B - 4-vinylpridine-co-acrylonitrile and platinum composite nano-line preparation method - Google Patents
4-vinylpridine-co-acrylonitrile and platinum composite nano-line preparation method Download PDFInfo
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- CN103878027B CN103878027B CN201410152432.4A CN201410152432A CN103878027B CN 103878027 B CN103878027 B CN 103878027B CN 201410152432 A CN201410152432 A CN 201410152432A CN 103878027 B CN103878027 B CN 103878027B
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- vinylpridine
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Abstract
4-vinylpridine-co-acrylonitrile and platinum composite nano-line preparation method, relate to DMFC anodic composite film catalyst preparation technical field.4-vinylpridine and acrylonitrile monemer is free-radical polymerized is prepared into random copolymer 4-vinylpridine-co-acrylonitrile; Random copolymer 4-vinylpridine-co-acrylonitrile is dissolved in DMF; Electrospinning process is adopted by polymer solution to obtain P (VP-co-AN) nano fibrous membrane; After finally P (VP-co-AN) nano fibrous membrane being immersed chloroplatinic acid aqueous solution, take out after immersing sodium borohydride aqueous solution after drying, obtain 4-vinylpridine-co-acrylonitrile and platinum composite nano-line.The product that the present invention obtains adsorbs chloroplatinic acid root equably, and the 4-vinylpridine-co-acrylonitrile made and platinum composite nano-line can be used for the anode catalyst of DMFC.
Description
Technical field
The present invention relates to a kind of preparing technical field of DMFC anodic composite film catalyst.
Background technology
DMFC has broad application prospects due to advantages such as its energy density are high, volume is little, raw material sources are extensive, operating temperature is low and product is clean in the field such as automobile and portable electric appts.At present, the electrochemical oxidation of methyl alcohol is mainly based on Pt catalyst, and the catalytic activity that research proves catalyst is not only relevant with the shape of catalyst particle, size, distribution, also with the kind of carrier and character closely related.In carbon supported platinum catalyst, apply maximum carriers is carbon black.Research in recent years shows, many novel nano-materials with graphite-structure, as: CNT, carbon nano-fiber etc. can improve the catalytic activity of catalyst effectively, thus reduce the use amount of platinum.
Summary of the invention
The object of the invention is to study a kind of 4-vinylpridine-co-acrylonitrile and platinum composite nano-line preparation method improving catalytic effect.
Comprise the following steps:
1) 4-vinylpridine (4-VP) and the copolymerization of acrylonitrile (AN) monomer radical are prepared random copolymer 4-vinylpridine-co-acrylonitrile (P (VP-co-AN));
2) random copolymer 4-vinylpridine-co-acrylonitrile is dissolved in DMF (DMF), forms polymer solution;
3) electrospinning process is adopted by polymer solution to obtain P (VP-co-AN) nano fibrous membrane;
4) P (VP-co-AN) nano fibrous membrane is immersed chloroplatinic acid (H
2ptCl
6) take out after 8h in the aqueous solution, immerse sodium borohydride (NaBH after drying
4) take out after 8 ~ 12min in the aqueous solution, with dry after intermediate water washing, namely obtain 4-vinylpridine-co-acrylonitrile and platinum composite nano-line.
P (VP-co-AN) spinning restores to make fiber, at HAuCl by the present invention
4soak obtained 4-vinylpridine-co-acrylonitrile and platinum composite nano-line after restoring in solution and be used as the anode catalyst of methanol fuel cell, and have good catalytic oxidation effect to methyl alcohol, feature is that (the electronegative chloroplatinic acid root in the pyridine groups of P (VP-co-AN) side base and solution attracts each other for the method for self assembly, thus obtained nanofiber adsorbs chloroplatinic acid root uniformly, and the 4-vinylpridine-co-acrylonitrile made and platinum composite nano-line can be used for the anode catalyst of DMFC.
In addition, the concrete grammar that the present invention prepares random copolymer 4-vinylpridine-co-acrylonitrile is: be dissolved in toluene by 4-vinylpridine and acrylonitrile, vacuumize with liquid nitrogen frozen under stirring condition, then under the condition of nitrogen protection, azodiisobutyronitrile is added, under magnetic agitation, mixed system is warming up to 70 DEG C to react, obtains the random copolymer 4-vinylpridine-co-acrylonitrile crude product of pale yellow precipitate; Again that crude product is dry with toluene and ether cleaning and filtering final vacuum, obtain random copolymer 4-vinylpridine-co-acrylonitrile.Wherein, the rate of charge of described 4-vinylpridine, acrylonitrile and azodiisobutyronitrile is 7.54mL ︰ 4.2mL ︰ 0.032g.Particularly wherein 4-vinylpridine obtained polymer monomer mol ratio different from acrylonitrile monomer ratio is also different.
Described vacuum drying temperature is 50 DEG C, and vacuum is-100KPa, and drying time is 48 ± 2 hours.This vacuum drying effect is faster, better, and the temperature of vacuum drying is simultaneously lower, makes the stable of random copolymerization properties.
Described step 2) in, the mass ratio that feeds intake of random copolymer 4-vinylpridine-co-acrylonitrile and DMF is 7 ~ 9.5 ︰ 100.During this rate of charge, spinning fibre film is of moderate size and distribution of SMD is comparatively even, and the catalytic effect of obtained catalyst is also best.
In described step 3), in electrospinning process, electrostatic spinning voltage is 15kv, and accepting distance is 15cm, ambient humidity≤50%.Fibre diameter obtained is under these conditions of moderate size and distributes average.
In described step 4), chloroplatinic acid (H
2ptCl
6) concentration of the aqueous solution is 20mmol/L, soak time is 8h.The catalyst effect that this solubility and time prepare is optimum, and the reaction time is fully 8 hours.
Accompanying drawing explanation
Fig. 1 is electrostatic spinning apparatus schematic diagram.
Fig. 2 is the scanning electron microscope (SEM) photograph of P (VP-co-AN)/Pt nano wire.
Fig. 3 x-ray photoelectron power spectrum is to carrying out qualitative analysis energy spectrogram for P (VP-co-AN)/Pt nano wire.
Fig. 4 is the cyclic voltammogram to anodic oxidation of methanol of P (VP-co-AN)/Pt nano wire.
Fig. 5 is the cyclic voltammogram to anodic oxidation of methanol of P (VP-co-AN)/Pt nano wire.
Detailed description of the invention
1, random copolymer 4-vinylpridine-co-acrylonitrile P (VP-co-AN) is prepared:
P (VP-co-AN) is through 4-vinylpridine (4-VP) and acrylonitrile (AN) monomer radical copolymerization preparation.
Before monomer 4-vinylpridine (4-VP) and acrylonitrile (AN) use, decompression distillation purification is carried out to it, and initator azodiisobutyronitrile (AIBN) is before use also through recrystallizing methanol.
Get 7.54mL 4-VP, 4.2mL AN and 20mL toluene solvant to be added in reaction bulb and to mix; then repeatedly vacuumize with liquid nitrogen frozen under stirring; then under the condition of nitrogen protection, 0.032g initator azodiisobutyronitrile (AIBN) is added; under magnetic agitation; system is warming up to 70 DEG C of reaction 2h, obtains the crude product of pale yellow precipitate.
By thick product toluene and ether cleaning and filtering twice, the vacuum tank that vacuum is-100KPa is placed in by filtering the solid particle obtained, under 50 DEG C of conditions, drying two days, obtains random copolymer 4-vinylpridine-co-acrylonitrile P (VP-co-AN).
2, glass-carbon electrode electrode pretreatment:
Glass-carbon electrode is used specific area successively: 5 ~ 12cm
2/ g, 30 ~ 50 cm
2nano aluminium oxide (α-the Al of/g
2o
3) powder polishing, then ultrasonic cleaning 3min in ethanolic solution and distilled water successively; Glass-carbon electrode after cleaning is placed in 0.8mol/L H
2sO
4in solution, controlling potential scope-0.25 ~ 1.25 V carries out cycle potentials scanning, until obtain stable standard cycle voltammogram, for subsequent use.
This is the general step that electrode uses front activating, at H
2sO
4in solution, cycle potentials scanning is the impurity removing electrode surface remnants, and stable cyclic voltammogram is exactly that the registration of the line of front and back two circle is higher.
3, P (VP-co-AN) nano fibrous membrane is prepared:
The P (VP-co-AN) of 7 ~ 9.5g being dissolved in preparation quality mark in 100gN, dinethylformamide (DMF) is the faint yellow polymer solution of 7 ~ 9.5%, after stirring 3 ~ 5h, obtain yellow spinning solution.
As shown in Figure 1, be equipped with in the 1mL plastic injector of firm syringe needle, collect electricity spinning fibre with platinum carbon electrode as receiver by part spinning solution dislocation, wherein, electrostatic spinning Control of Voltage is at 15kv, and accepting distance is 15cm, and humidity environment controls below 50%.
4, P (VP-co-AN)/Pt nano wire is prepared:
Obtained P (VP-co-AN) nano fibrous membrane is immersed chloroplatinic acid (H
2ptCl
6) aqueous solution 8 ~ 10h, dry in drier, processed nano fibrous membrane is immersed the sodium borohydride (NaBH that concentration is 20mmol
4) in the aqueous solution, after 20min, NaBH4 reduction, washs secondary with intermediate water, then dry in drier, namely obtains P (VP-co-AN)/Pt nano wire.
5, from the scanning electron microscope (SEM) photograph of P (the VP-co-AN)/Pt nano wire of Fig. 2: nano platinum particle wraps up fiber uniformly and forms Pt nano wire.
6, from the x-ray photoelectron power spectrum of Fig. 3 to carrying out for P (VP-co-AN)/Pt nano wire the existence that qualitative analysis energy spectrogram obviously can observe feature Pt element.
7, with 0.5mol/LH
2sO
4/ L and 1.0mol/L MeOH forms mixed aqueous solution, makes when potential scan rate is 2-80mVs
-1time, the cyclic voltammogram to anodic oxidation of methanol of P (VP-co-AN)/Pt nano wire.
As seen from Figure 4: in anodic scan direction, the oxidation peak current of methyl alcohol increases along with the increase of sweeping speed, and oxidation peak current is to the displacement of positive potential direction, simultaneously in cathodic scan direction, can find that the reduction peak current of the metal oxide produced in catalytic oxidation process also increases thereupon, reduction peak current is to losing side potential displacement.
8, with 0.5mol/L H
2sO
4form mixed aqueous solution with 1.0mol/L MeOH, make when potential scan rate is 100mVs
-1, Na
2sO
4be 0.1 ~ 0.8molL
-1time, the cyclic voltammogram to anodic oxidation of methanol of P (VP-co-AN)/Pt nano wire.
As seen from Figure 5: along with Na
2sO
4solubility larger, is more conducive to the electrochemical oxidation of methyl alcohol.
Claims (7)
1.4-vinylpyridine-co-acrylonitrile and platinum composite nano-line preparation method, is characterized in that comprising the following steps:
1) by 4-vinylpridine with acrylonitrile monemer is free-radical polymerized prepares random copolymer 4-vinylpridine-co-acrylonitrile;
2) random copolymer 4-vinylpridine-co-acrylonitrile is dissolved in DMF, forms polymer solution;
3) electrospinning process is adopted by polymer solution to obtain P (VP-co-AN) nano fibrous membrane;
4) take out in P (VP-co-AN) nano fibrous membrane immersion chloroplatinic acid aqueous solution after 8h, immerse in sodium borohydride aqueous solution after drying and take out after 8 ~ 12min, with dry after intermediate water washing, namely obtain 4-vinylpridine-co-acrylonitrile and platinum composite nano-line.
2. preparation method according to claim 1, it is characterized in that in described step 1), 4-vinylpridine and acrylonitrile are dissolved in toluene, vacuumize with liquid nitrogen frozen under stirring condition, then under the condition of nitrogen protection, azodiisobutyronitrile is added, under magnetic agitation, mixed system is warming up to 70 DEG C and reacts, obtain the random copolymer 4-vinylpridine-co-acrylonitrile crude product of pale yellow precipitate; Again that crude product is dry with toluene and ether cleaning and filtering final vacuum, obtain random copolymer 4-vinylpridine-co-acrylonitrile.
3. preparation method according to claim 2, is characterized in that the rate of charge of described 4-vinylpridine, toluene and azodiisobutyronitrile is 7.54mL ︰ 4.2mL ︰ 0.032g.
4. preparation method according to Claims 2 or 3, it is characterized in that described vacuum drying temperature is 50 DEG C, vacuum is-100KPa, and drying time is 48 ± 2 hours.
5. preparation method according to claim 1, is characterized in that described step 2) in, the mass ratio that feeds intake of random copolymer 4-vinylpridine-co-acrylonitrile and DMF is 7 ~ 9.5 ︰ 100.
6. preparation method according to claim 1, it is characterized in that in described step 3), in electrospinning process, electrostatic spinning voltage is 15kv, and receiving range is 15cm, ambient humidity≤50%.
7. preparation method according to claim 1, is characterized in that in described step 4), chloroplatinic acid (H
2ptCl
6) concentration of the aqueous solution is 20mmol/L, soak time is 8h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884643A (en) * | 2006-07-10 | 2006-12-27 | 浙江大学 | Polyacrylonitrile mesopore-macropore ultrafine carbon fiber and its preparation method |
| CN103208635A (en) * | 2013-03-29 | 2013-07-17 | 扬州大学 | Poly(4-vinylpyridine-co-acrylonitrile)-based pH-sensitive electrochemical switch and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080274036A1 (en) * | 2005-06-28 | 2008-11-06 | Resasco Daniel E | Microstructured catalysts and methods of use for producing carbon nanotubes |
| US7608478B2 (en) * | 2005-10-28 | 2009-10-27 | The Curators Of The University Of Missouri | On-chip igniter and method of manufacture |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884643A (en) * | 2006-07-10 | 2006-12-27 | 浙江大学 | Polyacrylonitrile mesopore-macropore ultrafine carbon fiber and its preparation method |
| CN103208635A (en) * | 2013-03-29 | 2013-07-17 | 扬州大学 | Poly(4-vinylpyridine-co-acrylonitrile)-based pH-sensitive electrochemical switch and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Physicochemical and catalytic properties of Pt-poly(4-vinylpyridine) composites;A.Drelinkiewicz et al.;《Materials Chemistry and Physics》;20091231;第114卷;第763-773页 * |
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