CN104701554B - Preparation method of graphene-metal nanoparticle composite - Google Patents
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- CN104701554B CN104701554B CN201510021473.4A CN201510021473A CN104701554B CN 104701554 B CN104701554 B CN 104701554B CN 201510021473 A CN201510021473 A CN 201510021473A CN 104701554 B CN104701554 B CN 104701554B
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Abstract
The invention relates to a method for modifying part of the surface of a metal nanoparticle loaded on graphene through an electrochemical process by using the other metal. A composite prepared by the method is applied to electrocatalysis oxidation reaction of alcohols. The method comprises the following steps: preparing a Pd/graphene composite, carrying out Ag modification on the surface of the Pd/graphene composite, and carrying out electrocatalysis oxidation reaction of 1,2-propylene glycol of the Pd/graphene composite modified by Ag. A preparation method of the Pd/graphene composite is simple; no stabilizer is added; the after-treatment is liable to implement; the silver modification on the surface of the Pd nanoparticle loaded on the graphene is finished by one-step reaction in the modification process; the modification quantity is accurate to control; the modification time is short; the Pd/graphene composite modified by Ag is high in electrocatalysis activity in oxidization reaction of 1,2-propylene glycol in an alkaline solution; the modification effect is highly obvious; the Ag modification quantity is low; the using amount of Ag is reduced.
Description
Technical field
The invention belongs to electrochemical electrode field of material technology, it is combined particularly to a kind of Graphene-metal nanoparticle
The preparation method of material.
Background technology
The electrocatalysis oxidation reaction of alcohol is one of major domain of electrochemical research.People's direct combustion to methanol for a long time
Material battery has carried out numerous studies, and it is abundant, environmental clean etc. excellent that this technology has energy density height, compact, fuel source
Point is it is considered to be one of up-and-coming clean energy resource device.The performance of fuel cell is urged used by depending greatly on
The performance of agent.Platinum (Pt) is one of maximally effective methanol oxidation catalyst.Although the methanol fuel cell based on Pt catalyst
Research has been achieved for remarkable progress, but also a lot of problems need to solve and improve, if desired for the electrode reaction improving methanol
Speed and the problem preventing crossover of methanol barrier film.Additionally, reduce precious metals pt usage amount so that reduce catalyst cost be also
On one side.At present, also extensively carried out with the research that alcohol such as ethanol and ethylene glycol etc. beyond methanol do fuel cell raw material.
In recent years, developing rapidly with anion exchange membrane development, using the alkali of alcohol electrocatalysis oxidation reaction under alkaline medium condition
Property fuel cell studies are also increasingly attracted attention.Compared with acid medium, a significant advantage of alkaline medium is alcohol oxidation
Reaction is easily carried out, and response speed is fast.
The research of the electrocatalytic reaction of alcohol also contributes to the electrochemical synthesis of compound.For example, the oxidation reaction of polyhydric alcohol
The middle compound generating some high added values, by improving selectivity, can obtain some chemical combination therein with preferable yield
Thing.For example, had been reported by the research that acetone electrochemical oxidation process prepares dihydroxy acetone.1,2-PD is also polyhydric alcohol,
Its oxidation reaction can generate many kinds of substance, wherein has lactic acid.The production of lactic acid is mainly biological fermentation process at present.Therefore, 1,2-
The electrocatalysis oxidation reaction of propylene glycol is studied also highly significant.
Surface modification is to improve effective ways of electrode activity.The part surface of basal electrode is carried out with other metals
Modify, by the interaction between adatome and substrate atoms, electrode activity and anti-poisoning capability can be improved.Conventional is several
In kind of surface modification method, electrochemical reducing has in terms of the deposition controlling metal and sediment structure and has great advantage.
Palladium (Pd) is conventional electrode material, is additionally operable to the surface modification to other metal materials, such as to monocrystalline or polycrystalline
Au, Pt and Ag surface modification.Although also having the report to Pd surface modification for the metals such as Cu, Bi, Pt and Au, this kind of report
Very limited, one of reason is that the monocrystalline of Pd is not easy to prepare.Ag is also a kind of electrode material, but Ag itself is to alcohol oxidation reaction
Electro catalytic activity very low.
In recent years, Graphene (Graphene) is widely used in the research of chemistry, material science and physicss field.In electricity
In chemical research, the carrier that Graphene is used as catalyst shows many excellent performances, and Graphene is as all kinds of metal nanos
The carrier of particle, the oxidation for many kinds of substance or reduction reaction, have obtained good effect.
When studying the electrocatalysis oxidation reaction of 1,2-PD, we use Graphene as carrier supported palladium nanometer respectively
Particle and Nano silver grain, are used for this reaction as electrode after preparing composite, result is as shown in Figure 1.Can see, Pd/
Oxidation reaction spike potential in Graphene electrodes is -0.15V vs.SCE, and peak current density is 10mA cm-2, peak ratio is relatively low, and
An oxidation peak in+0.31V vs.SCE during forward scan in Ag/ Graphene electrodes, in 0V during negative sense scanning
Vs.SCE about occur a reduction peak, illustrate that this two peaks are Ag surface oxidation peak and the reduction peak of Ag oxide respectively, this
Mean that Ag does not have catalytic action in the potential areas studied.We have found that Ag precipitation is modified Pd and put down in conventional research
Face electrode can be significantly improved the catalysis activity to allylic alcohol reaction in alkaline medium.Therefore, we modify Pd Ag
It is used for the oxidation reaction of 1,2-PD after plane electrode, and put down with the Pd that Ag modifies in the range of a larger Ag precipitation capacity
Face electrode is reacted, and result shows that the oxidation peak difference of 1,2-PD is smaller, and its peak current density ratio is not repaiied
The Pd electrode of decorations is also low, and wherein representational Ag precipitation capacity is 0.5 μ g cm-2Ag modify Pd electrode on reaction such as Fig. 2
Shown.Therefrom it can be seen that Ag modify Pd plane electrode on 1,2- propylene glycol oxidation reaction spike potential be -0.16V
Vs.SCE, and peak current density is only 0.78mA cm-2.This result shows although Ag modification Pd plane electrode can improve to alkene
The catalysis activity of propanol oxidation reaction, but there is no this effect to 1,2-PD oxidation reaction.
Content of the invention
The technical problem to be solved in the present invention is：Pd/ Graphene is low to 1,2- propylene glycol electrocatalysis oxidation reaction activity
Problem.
The technical scheme that the present invention solves that its technical problem adopted is：There is provided a kind of Ag to modify and be supported on Graphene
On Pd nanoparticle method, that is, adopt constant potential electrochemical deposition method, Ag is deposited on graphene-supported Pd nanoparticle
Surface, prepare Ag modification Pd/ graphene composite material, this composite is as 1,2- third under the conditions of electrode pair alkaline media
The oxidation reaction of glycol has high catalytic activity.
This technical scheme specifically includes following steps：
Prepared by a, Pd/ graphene composite material
Using Hummers method, liquid phase oxidation introduces the hydrophilic such as epoxy radicals, hydroxyl and carboxyl in graphite flake basal plane and edge
Oxy radical, obtains graphite oxide (GO), and then ultrasonic stripping graphite linings obtain GO nanometer sheet.Because GO nanometer sheet is scattered in water
In can be negatively charged because of ionization, precursor Pd (NO3)2After addition, Pd2+Adsorbed in GO table by electrostatic adsorption
Face；Finally, using the NaBH under room temperature4One stage reduction method, adds excessive NaBH4, reduce GO and Pd simultaneously2+, obtain Pd/ stone
Black alkene composite.
Concrete steps：Take appropriate GO and redistilled water, then be added thereto to required Pd (NO3)2Carry out ultrasonic after solution
Ripple shakes, and obtains dark brown transparence liquid.Then add excessive NaBH under magnetic stirring4Carry out redox reaction, raw
Become Pd nanoparticle and be supported on Graphene；After question response is complete, transfers the sample into and in test tube, staticly settle Pd/ graphite
Alkene；After removing most of supernatant, add ethanol in proper amount into test tube and carry out ultrasonic disperse so as to reach after certain volume, obtain
To tusche shape liquid；Pipette the Al that appropriate tusche shape liquid is coated onto priority 0.3um and 0.05um2O3Polishing powder polishing and
The glassy carbon electrode surface being cleaned by ultrasonic in redistilled water, drying at room temperature, that is, obtain Pd/ graphene composite material electrode.
Wherein, above-mentioned GO measures as 1.5～2.5mg.
The volume of above-mentioned dark brown transparence liquid is 14.15～23.58mL, Pd (NO3)2Concentration be 0.25mM.
The above-mentioned ultrasonic wave concussion time is 0.5～1h.
Above-mentioned NaBH4Addition is 0.03～0.05g.
The above-mentioned stirring reaction time is 0.5～1.5h.
Above-mentioned staticly settle the time be 10～12h.
The ultrasonic vibration time after above-mentioned addition ethanol is 5～10min.
Above-mentioned tusche shape liquid volume is 0.75～1.25mL.
The a diameter of 4mm of above-mentioned glass-carbon electrode.
The above-mentioned tusche shape liquid volume being coated onto glassy carbon electrode surface is 5uL.
Above-mentioned room temperature (25 DEG C) drying time is 10～30min.
Pd load capacity on the basis of glass carbon substrate geometric area for the Pd/ graphene composite material obtained above is 20.3 μ g
cm–2.
The Ag on b, Pd/ graphene composite material surface modifies
Prepare Ag precursor solution with silver sulfate, sulphuric acid and redistilled water, then with being coated with of preparing in step a
The glass-carbon electrode of Pd/ graphene composite material is working electrode, and Pt piece is that Pt electrode is reference electrode, in constant potential to electrode
Under the conditions of from Ag precursor solution precipitate reduction Ag to Pd nanoparticle surface, by controlling the sedimentation time to obtain thering is different Ag
The Pd/ graphene composite material of modification amount, with Ag(x)- Pd/ Graphene represents the Pd/ graphene composite material that Ag modifies, wherein x
Represent the Ag precipitation capacity on the basis of glass carbon substrate geometric electrode area, unit μ g cm–2.
Sulphuric acid silver concentration in above-mentioned Ag precursor solution is 1.0mM, and sulfuric acid concentration is 0.05M.
Above-mentioned Ag sedimentation potential takes certain value in the range of -0.15～-0.25V vs.Pt.
The above-mentioned Ag sedimentation time is 1～5s.
Above-mentioned Ag(x)The x value of-Pd/ Graphene is 0.5～1.8 μ g cm–2.
The invention has the beneficial effects as follows：Method of modifying in the present invention is simple, and the precipitation modification time is very short, and precipitation capacity can be accurate
Really control although Ag itself does not have catalytic action in alkaline medium to 1,2-PD oxidation reaction, but obtained Ag(x)-
Pd/ graphene composite material is far above to the electro catalytic activity of 1,2- propylene glycol oxidation reaction before modifying in alkaline medium
Pd/ Graphene electrodes, modification effect is clearly；Ag modification amount seldom, saves the usage amount of Ag.
Brief description
Fig. 1 be the propylene glycol of 1,2- containing 0.1M 0.5M NaOH solution in Ag/ Graphene and Pd/ Graphene cyclic voltammetric
Curve.Scanning speed：50mV s–1.
Fig. 2 be the propylene glycol of 1,2- containing 0.1M 0.5M NaOH solution in the cyclic voltammetric of Pd plane electrode modified of Ag bent
Line.Scanning speed：50mV s–1.
Fig. 3 is Ag(0.9μg)Scanning electron microscope (SEM) figure on-Pd/ graphene composite material surface.
Fig. 4 be the propylene glycol of 1,2- containing 0.1M 0.5M NaOH solution in Ag(0.5μg)- Pd/ Graphene, Ag(0.9μg)- Pd/ stone
Black alkene and Ag(1.8μg)The cyclic voltammetry curve of-Pd/ Graphene.Scanning speed：50mV s–1.
Fig. 5：The Ag of preparation in embodiment 1(0.9μg)- Pd/ graphene composite material, (Ag load capacity is with Ag/ Graphene
20.7μg cm–2), Pd/ Graphene (Pd load capacity be 20.3 μ g cm–2), molten in the 0.5M NaOH containing 0.1M 1,2-PD
Cyclic voltammetry curve in liquid.Scanning speed：50mV s–1.
Specific embodiment
Embodiment 1：
Take 2mg GO and 16.5mL redistilled water, then the 2mM Pd (NO being added thereto to 2.35mL3)2Ultrasonic after solution
Ripple shakes 40min, obtains dark brown transparence liquid；Then add 0.04g NaBH under magnetic stirring4, magnetic agitation 1h, it
After transfer the sample into and staticly settle 10h in test tube and obtain Pd/ Graphene；After removing most of supernatant in test tube plus suitable
Amount ethanol, makes the volume of solution system in test tube reach 1mL, and then ultrasonic disperse 5min obtains tusche shape liquid；Pipette wherein
5uL tusche shape liquid is coated onto the Al of priority 0.3um and 0.05um2O3Polishing powder polishing is simultaneously cleaned by ultrasonic in redistilled water
The glassy carbon electrode surface crossed, room temperature (25 DEG C) is dried 20min, that is, obtain Pd/ graphene composite material.
15mL redistilled water, 5mL 2mM silver sulfate and 53.2 μ L concentrated sulphuric acids (quality purity 98.0%) are successively taken to add
Prepare Ag precursor solution in the 50mL beaker of a dried and clean, be passed through nitrogen in above-mentioned solution, discharge and wherein dissolve
Oxygen.Above-mentioned preparation be coated with the glass-carbon electrode of Pd/ graphene composite material as working electrode, be placed in this Ag presoma
In solution, it is to electrode with Pt piece, Pt electrode is reference electrode, carries out constant potential precipitate reduction under current potential -0.2V vs.Pt
Ag, sedimentation time 2s, that is, obtain Ag(0.9μg)- Pd/ graphene composite material, Ag precipitation capacity is 0.9 μ g cm–2.Due to bearing of Pd
Carrying capacity is 20.3 μ g cm–2, the atomic ratio obtaining Ag and Pd is 1:23.See that Graphene is in sheet by Fig. 3, and observe pleat
Wrinkle.Metallic is supported on Graphene basal plane and edge, have complete wrapped up by Graphene, but distribution uniform, particle aggregation
Phenomenon is fewer.
With Ag prepared above(0.9μg)- Pd/ graphene composite material is checked to 1,2- the third two in sodium hydroxide solution
The catalytic effect of alcohol oxidation reaction.For this reason, successively taking 20mL redistilled water, 147 μ L 1,2-PD (purity >=99.7%)
Prepare alcoholic solution with the 50mL beaker that 0.4g sodium hydroxide (purity >=96.0%) is added to a dried and clean, by above-mentioned system
Standby is coated with Ag(0.9μg)The electrode of-Pd/ graphene composite material redistilled water cleans as working electrode behind surface,
Pt electrode is to electrode, and saturated calomel electrode is reference electrode, carries out in the above-mentioned sodium hydroxide solution containing 1,2-PD
Cyclic voltammetry, result is as shown in Figure 4.Ag(0.9μg)The peak current of 1,2- propylene glycol oxidation reaction in-Pd/ Graphene electrodes
It is worth for 23.6mAcm-2.
Pd/ Graphene electrodes in Fig. 1 are the Pd/ Graphene electrodes before Ag precipitation, and this electrode Pd load capacity is
20.3μg cm–2, the Ag load capacity of Ag/ Graphene is 20.7 μ g cm–2.Pd and Ag of Pd/ Graphene and Ag/ Graphene rubs
Your number is identical, and the reaction condition of Fig. 1 with Fig. 4 is also identical.
Relatively Fig. 1 and Fig. 4 can see, Ag(0.9μg)Peak point current in-Pd/ Graphene electrodes is Pd/ Graphene electrodes
On 2.2 times, and it is basically identical to the corresponding current potential in Pd/ Graphene electrodes to aoxidize take-off potential and spike potential.
Embodiment 2：
Experimental procedure is same as Example 1, and simply the Ag sedimentation time is 1s.Obtain Ag(0.5μg)- Pd/ Graphene compound electric
Pole, Ag precipitation capacity is 0.5 μ g cm–2.
With Ag prepared above(0.5μg)- Pd/ Graphene electrodes are checked to 1,2- propylene glycol oxygen in sodium hydroxide solution
Change the catalytic effect of reaction.Result is as shown in Figure 4.Relatively Fig. 1 and Fig. 4 can see, Ag(0.5μg)1 in-Pd/ Graphene electrodes,
The peak point current of 2- propylene glycol oxidation reaction be Pd/ Graphene electrodes on 1.7 times, and reaction potential (oxidation take-off potential and
Spike potential) basically identical with the reaction potential in Pd/ Graphene electrodes.
Embodiment 3：
Experimental procedure is same as Example 1, and simply the Ag sedimentation time is 5s.Obtain Ag(1.8μg)- Pd/ Graphene compound electric
Pole, Ag precipitation capacity is 1.8 μ g cm–2.
With Ag prepared above(1.8μg)- Pd/ Graphene electrodes are checked to 1,2- propylene glycol oxygen in sodium hydroxide solution
Change the catalytic effect of reaction.Result is as shown in Figure 4.Relatively Fig. 1 and Fig. 4 can see, Ag((1.8μg)1 in-Pd/ Graphene electrodes,
The peak point current of 2- propylene glycol oxidation reaction is 2 times in Pd/ Graphene electrodes, and reaction potential (oxidation take-off potential and peak
Current potential) basically identical with the reaction potential in Pd/ Graphene electrodes.
Comparative example 1：
Prepared electrode in embodiment 1 is used for 1,3-PD oxidation reaction, compares this electrode pair 1,3-PD
Catalytic effect with 1,2- propylene glycol oxidation reaction.For this reason, the 0.5M sodium hydroxide solution containing 0.1M 1,3-PD for the preparation,
Then pass to nitrogen, discharge the oxygen of dissolving.The Ag that embodiment 1 is prepared(0.9μg)- Pd/ Graphene electrodes are placed in above-mentioned solution
In, it is that saturated calomel electrode is reference electrode, with scanning speed 50mV s to electrode with Pt piece–1It is circulated voltammetric determination.
Result shows：Ag((0.9μg)In-Pd/ Graphene electrodes, the peak point current of 1,3- propylene glycol oxidation reaction is 10.4mA
cm–2, Pd/ Graphene electrodes are 9.2mA cm–2.Ag((0.9μg)Peak point current in-Pd/ Graphene electrodes is Pd/ Graphene
1.13 times of peak point current on electrode.The increase with Ag precipitation capacity is also seen that, in the Pd/ Graphene electrodes that Ag modifies in experiment
The peak current of 1,3- propylene glycol oxidation reaction is gradually lowered.The Pd/ Graphene that this explanation is modified compared with Pd/ Graphene electrodes, Ag
The catalytic action of electrode pair 1,3- propylene glycol oxidation reaction is not much advantage.
Comparative example 2：
Graphene carrier in embodiment 1 is replaced with carbon black-supported, checks the shadow to catalyst effect for the different carriers
Ring.For this reason, pressing embodiment 1 step, do carrier with white carbon black, preparation and Pd/ Graphene electrodes have same molal quantity load capacity
Pd/ carbon black composite material, that is, palladium load capacity is 20.3 μ g cm-2.Then, modify by the Ag that embodiment 1 step carries out Pd/ white carbon black,
Obtaining Ag precipitation capacity is 0.9 μ g cm–2Ag(0.9μg)- Pd/ white carbon black combination electrode.This electrode is placed in 1,2- containing 0.1M the third two
In the 0.5M sodium hydroxide solution of alcohol, it is that saturated calomel electrode is reference electrode, with scanning speed 50mV to electrode with Pt piece
s–1It is circulated voltammetric determination.
Result shows：Ag((0.9μg)On-Pd/ white carbon black electrode, the peak point current of 1,2- propylene glycol oxidation reaction is 5.4mA cm–2, Pd/ white carbon black electrode is 6.9mA cm–2.Ag((0.9μg)Peak point current on-Pd/ white carbon black electrode is than on Pd/ white carbon black electrode
Peak point current is low.The increase with Ag precipitation capacity is also seen that, 1,2-PD oxidation on the Pd/ white carbon black electrode that Ag modifies in experiment
The peak current of reaction is gradually lowered.This explanation Ag precipitation is unfavorable for the catalysis of Pd/ white carbon black electrode pair 1,2- propylene glycol oxidation reaction
Effect.
Claims (4)
1. the Pd/ graphene composite material that a kind of Ag modifies application it is characterised in that：Described application is that described Ag modifies
Pd/ graphene composite material as electrode electrocatalytic oxidation 1,2- propylene glycol under alkaline medium condition；
In described composite, Ag is deposited on the surface of graphene-supported Pd nanoparticle, and obtained Ag and Pd's is former
Son is 1 than scope:41～1:11.
2. the Pd/ graphene composite material that Ag as claimed in claim 1 modifies application it is characterised in that：Described Ag modifies
The preparation method of Pd/ graphene composite material be,
Prepared by a, Pd/ graphene composite material
Take 1.5～2.5mg graphite oxide and redistilled water, then be added thereto to Pd (NO3)2Carry out ultrasonic wave concussion after solution,
Obtain Pd (NO3)2Concentration is the dark brown transparence liquid 14.15～23.58mL of 0.25mM；Then under magnetic stirring, to above-mentioned
The NaBH of 0.03～0.05g is added in dark brown transparence liquid4, continue stirring reaction 0.5～1.5h, generate Pd nanoparticle simultaneously
It is supported on Graphene；After question response is complete, reactant liquor is transferred to standing 10～12h in test tube, is settled out Pd/ Graphene；
Remove and add ethanol in test tube after the supernatant, carry out ultrasonic disperse 5～10min, obtain tusche shape liquid 0.75～
1.25mL；Pipette above-mentioned tusche shape liquid 5 μ L and be coated onto and use Al2O3Polishing powder polishes and was cleaned by ultrasonic in redistilled water
Glassy carbon electrode surface, drying at room temperature, that is, obtain Pd/ graphene composite material；
B, Pd/ graphene composite material surface modification
Make Ag precursor solution with silver sulfate, sulphuric acid and redistilled water, be then coated with Pd/ with prepare in step a
The glass-carbon electrode of graphene composite material is working electrode, and Pt piece is that Pt electrode is reference electrode, in constant potential condition to electrode
Under from described Ag precursor solution precipitate reduction Ag to Pd/ graphene composite material surface, by control the sedimentation time obtain
There is the Pd/ graphene composite material of different Ag modification amounts.
3. the Pd/ graphene composite material that Ag as claimed in claim 2 modifies application it is characterised in that：In step b, institute
In the Ag precursor solution stated, sulphuric acid silver concentration is 1.0mM, and sulfuric acid concentration is 0.05M.
4. the Pd/ graphene composite material that Ag as claimed in claim 2 modifies application it is characterised in that：In step b, institute
The constant potential condition stated is the arbitrary value in the range of -0.15～-0.25V vs.Pt.
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| KR101866190B1 (en) * | 2016-05-31 | 2018-06-12 | 가천대학교 산학협력단 | Graphene metal nanoparticle-composite |
| CN106179336A (en) * | 2016-07-12 | 2016-12-07 | 陕西理工学院 | A kind of bimetallic catalyst and preparation method thereof |
| CN106319576B (en) * | 2016-09-13 | 2018-08-28 | 合肥工业大学 | A kind of room temperature prepares two electrode electro Chemical reduction methods of silver-graphene nanocomposite |
| CN107543849B (en) * | 2017-07-31 | 2019-07-26 | 常州大学 | The high activity electrode preparation method on two kinds of one step of noble metal modification common metal nanocomposite surfaces |
| CN108777311B (en) * | 2018-06-04 | 2021-07-02 | 东华大学 | Pd/MGN composite material with high oxidation-reduction electrocatalytic activity and preparation method and application thereof |
| CN109817999B (en) * | 2019-01-23 | 2022-04-08 | 西北工业大学 | Silver-catalyzed magnalium layered hydroxide membrane formate fuel cell and preparation method thereof |
| CN111307896A (en) * | 2019-12-04 | 2020-06-19 | 济宁医学院 | Preparation method of composite electrode capable of improving NADH catalytic effect |
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