CN104701554A - Preparation method of graphene-metal nanoparticle composite - Google Patents
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- CN104701554A CN104701554A CN201510021473.4A CN201510021473A CN104701554A CN 104701554 A CN104701554 A CN 104701554A CN 201510021473 A CN201510021473 A CN 201510021473A CN 104701554 A CN104701554 A CN 104701554A
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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, particularly a kind of preparation method of Graphene-metal nano particle composite material.
Background technology
The electrocatalysis oxidation reaction of alcohol is one of major domain of electrochemical research.People have carried out large quantity research to methyl alcohol direct fuel cell for a long time, and this technology has the advantages such as energy density is high, compact, fuel source abundant, clean environmental protection, is considered to one of up-and-coming clean energy resource device.The performance of fuel cell depends on the performance of used catalyst to a great extent.Platinum (Pt) is one of the most effective methanol oxidation catalyst.Although have made great progress based on the methanol fuel cell research of Pt catalyst, also have a lot of problem to need to solve and improve, improve the electrode reaction speed of methyl alcohol as needed and prevent the problem of crossover of methanol barrier film.In addition, the use amount and then the reduction catalyst cost that reduce precious metals pt are also aspects.At present, also extensively carrying out with the research that the alcohol beyond methyl alcohol does fuel cell raw material as ethanol and ethylene glycol etc.In recent years, along with developing rapidly of anion-exchange membrane development, the research of the alkaline fuel cell of alcohol electrocatalysis oxidation reaction under alkaline medium condition is utilized also more and more to be attracted attention.Compared with acid medium, a significant advantage of alkaline medium is that alcohol oxidation reaction easily carries out, and reaction speed is fast.
The research of the electrocatalytic reaction of alcohol also contributes to the electrochemistry formated of compound.Such as, in the oxidation reaction of polyalcohol, generate the compound of some high added values, by improving selectivity, some compound that can obtain wherein with good yield.Such as, the research preparing dihydroxyacetone (DHA) by acetone electrochemical oxidation process has been reported.1,2-PD is also polyalcohol, and its oxidation reaction can generate many kinds of substance, wherein has lactic acid.The production mainly biological fermentation process of current lactic acid.Therefore, the electrocatalysis oxidation reaction research of 1,2-PD also highly significant.
Finishing is the effective ways improving electrode activity.The part surface of basal electrode is modified with other metals, by the interaction between adatom and substrate atoms, can improve electrode activity and anti-poisoning capability.In conventional several surface modification methods, electrochemical reducing tool in the deposition controlling metal and sediment structure has great advantage.
Palladium (Pd) is conventional electrode material, also for the finishing to other metal materials, as the modification on Au, Pt and Ag surface to monocrystalline or polycrystalline.Although also there is the report of the metal pair Pd finishinges such as Cu, Bi, Pt and Au, this kind of report is very limited, and one of reason is that the monocrystalline of Pd is not easy preparation.Ag is also a kind of electrode material, but Ag itself is very low to the electro catalytic activity of alcohol oxidation reaction.
In recent years, Graphene (Graphene) is widely used in the research in chemistry, material science and physics field.In electrochemical research, Graphene is used as the performance that the carrier of catalyst demonstrates many excellences, and Graphene, as the carrier of all kinds of metal nanoparticle, for oxidation or the reduction reaction of many kinds of substance, obtains good effect.
When studying the electrocatalysis oxidation reaction of 1,2-PD, we are with Graphene as carrier supported palladium nano particle and Nano silver grain respectively, and to prepare after composite material as electrode for this reaction, result as shown in Figure 1.Can see, the oxidation reaction spike potential in Pd/ Graphene electrodes is-0.15V vs.SCE, and peak current density is 10mA cm
-2peak is lower, and an oxidation peak is there is at+0.31V vs.SCE during forward scan in Ag/ Graphene electrodes, a reduction peak is there is at 0V about vs.SCE during negative sense scanning, illustrate that these two peaks are the reduction peak of Ag surface oxidation peak and Ag oxide respectively, this means that Ag does not have catalytic action in studied potential areas.In research in the past, we find that Ag precipitation modifies the catalytic activity that Pd plane electrode can improve allylic alcohol reaction in alkaline medium significantly.Therefore, we modify after Pd plane electrode Ag for 1, the oxidation reaction of 2-propylene glycol, and react by the Pd plane electrode that Ag modifies within the scope of a larger Ag precipitation capacity, result shows 1, the oxidation peak difference of 2-propylene glycol is smaller, and its peak current density is also lower than the Pd electrode of unmodified, and wherein representational Ag precipitation capacity is 0.5 μ g cm
-2ag modify Pd electrode on reaction as shown in Figure 2.The oxidation reaction spike potential therefrom can seeing the 1,2-PD in the Pd plane electrode that Ag modifies is-0.16V vs.SCE, and peak current density is only 0.78mA cm
-2.This result shows, although Ag modifies Pd plane electrode can improve the catalytic activity of reacting allylic alcohol, does not have this effect to 1,2-PD oxidation reaction.
Summary of the invention
The technical problem to be solved in the present invention is: Pd/ Graphene is to the active low problem of 1,2-PD electrocatalysis oxidation reaction.
The present invention solves the technical scheme that its technical problem adopts: provide a kind of Ag to modify the Pd nano particle method of load on Graphene, namely constant potential electrochemical deposition method is adopted, Ag is deposited on the surface of graphene-supported Pd nano particle, prepare the Pd/ graphene composite material that Ag modifies, this composite material has high catalytic activity as the oxidation reaction of 1,2-PD under electrode pair alkaline media condition.
This technical scheme specifically comprises the following steps:
Prepared by a, Pd/ graphene composite material
Adopt Hummers method, liquid phase oxidation introduces the hydrophily oxy radicals such as epoxy radicals, hydroxyl and carboxyl at graphite flake basal plane and edge, and obtain graphite oxide (GO), then ultrasonic stripping graphite linings obtains GO nanometer sheet.Due to GO nanometer sheet is scattered in water can be electronegative because of ionization, precursor Pd (NO
3)
2after adding, Pd
2+gO surface is adsorbed on by electrostatic adsorption; Finally, the NaBH under normal temperature is adopted
4one stage reduction method, adds excessive NaBH
4, reduction GO and Pd simultaneously
2+, obtain Pd/ graphene composite material.
Concrete steps: get appropriate GO and redistilled water, then add required Pd (NO wherein
3)
2carry out ultrasonic oscillation after solution, obtain dark brown transparence liquid.Then excessive NaBH is added under magnetic stirring
4carry out redox reaction, generate Pd nano particle load on Graphene; After question response is complete, sample is transferred in test tube and staticly settle Pd/ Graphene; After removing most of supernatant liquor, in vitro adding ethanol in proper amount, carrying out ultrasonic disperse after making it reach certain volume, obtaining tusche shape liquid; Pipette the Al that appropriate tusche shape liquid is coated onto priority 0.3um and 0.05um
2o
3polishing powder polishing the glassy carbon electrode surface of ultrasonic cleaning in redistilled water, drying at room temperature, namely obtains Pd/ graphene composite material electrode.
Wherein, above-mentioned GO amount is 1.5 ~ 2.5mg.
The volume of above-mentioned dark brown transparence liquid is 14.15 ~ 23.58mL, Pd (NO
3)
2concentration be 0.25mM.
The above-mentioned ultrasonic oscillation time is 0.5 ~ 1h.
Above-mentioned NaBH
4addition is 0.03 ~ 0.05g.
The above-mentioned stirring reaction time is 0.5 ~ 1.5h.
It is above-mentioned that to staticly settle the time be 10 ~ 12h.
Above-mentioned add ethanol after the ultrasonic vibration time be 5 ~ 10min.
Above-mentioned tusche shape liquid volume is 0.75 ~ 1.25mL.
Above-mentioned glass-carbon electrode diameter is 4mm.
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/ graphene composite material obtained above is 20.3 μ g cm with the Pd load capacity that glass carbon substrate geometric area is benchmark
– 2.
The Ag on b, Pd/ graphene composite material surface modifies
With silver sulfate, sulfuric acid and redistilled water preparation Ag precursor solution, then with the glass-carbon electrode being coated with Pd/ graphene composite material prepared in step a for work electrode, Pt sheet is to electrode, Pt electrode is reference electrode, from Ag precursor solution precipitate reduction Ag to Pd nanoparticle surface under constant potential condition, the Pd/ graphene composite material with different Ag modification amount is obtained, with Ag by controlling the sedimentation time
(x)-Pd/ Graphene represents the Pd/ graphene composite material that Ag modifies, the Ag precipitation capacity that wherein it is benchmark with glass carbon substrate geometric electrode area that x represents, unit μ g cm
– 2.
Silver sulfate concentration in above-mentioned Ag precursor solution is 1.0mM, and sulfuric acid concentration is 0.05M.
Above-mentioned Ag sedimentation potential gets certain value within the scope 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: the method for modifying in the present invention is simple, the precipitation modification time is very short, and precipitation capacity can accurately control, although Ag itself does not have catalytic action in alkaline medium to 1,2-PD oxidation reaction, and the Ag obtained
(x)-Pd/ graphene composite material in alkaline medium to the electro catalytic activity of 1,2-PD oxidation reaction far above modify before Pd/ Graphene electrodes, modification effect is clearly; Ag modification amount is little, saves the use amount of Ag.
Accompanying drawing explanation
Fig. 1 is the cyclic voltammetry curve of Ag/ Graphene and Pd/ Graphene in the 0.5M NaOH solution containing 0.1M 1,2-PD.Sweep speed: 50mV s
– 1.
Fig. 2 is the cyclic voltammetry curve of the Pd plane electrode that in the 0.5M NaOH solution containing 0.1M 1,2-PD, Ag modifies.Sweep speed: 50mV s
– 1.
Fig. 3 is Ag
(0.9 μ g)eSEM (SEM) figure on-Pd/ graphene composite material surface.
Fig. 4 is Ag in the 0.5M NaOH solution containing 0.1M 1,2-PD
(0.5 μ g)-Pd/ Graphene, Ag
(0.9 μ g)-Pd/ Graphene and Ag
(1.8 μ g)the cyclic voltammetry curve of-Pd/ Graphene.Sweep speed: 50mV s
– 1.
Fig. 5: the Ag of preparation in embodiment 1
(0.9 μ g)-Pd/ graphene composite material, (Ag load capacity is 20.7 μ gcm with Ag/ Graphene
– 2), (Pd load capacity is 20.3 μ g cm to Pd/ Graphene
– 2), the cyclic voltammetry curve in the 0.5M NaOH solution containing 0.1M 1,2-PD.Sweep speed: 50mV s
– 1.
Embodiment
Embodiment 1:
Get 2mg GO and 16.5mL redistilled water, then add the 2mM Pd (NO of 2.35mL wherein
3)
2ultrasonic oscillation 40min after solution, obtains dark brown transparence liquid; Then 0.04g NaBH is added under magnetic stirring
4, magnetic agitation 1h, transfers to sample in test tube afterwards and staticly settles 10h and obtain Pd/ Graphene; To remove in test tube after most of supernatant liquor, add ethanol in proper amount, make the volume of in vitro solution system reach 1mL, then ultrasonic disperse 5min, obtain tusche shape liquid; Pipette wherein 5uL tusche shape liquid and be coated onto the Al of priority 0.3um and 0.05um
2o
3polishing powder polishing the glassy carbon electrode surface of ultrasonic cleaning in redistilled water, room temperature (25 DEG C) dry 20min, namely obtains Pd/ graphene composite material.
Successively get 15mL redistilled water, 5mL 2mM silver sulfate and the 53.2 μ L concentrated sulfuric acids (quality purity 98.0%) to join in the 50mL beaker of a dried and clean and prepare Ag precursor solution, in above-mentioned solution, pass into nitrogen, discharge the oxygen wherein dissolved.The glass-carbon electrode being coated with Pd/ graphene composite material of above-mentioned preparation, as work electrode, is placed in this Ag precursor solution, is to electrode with Pt sheet, Pt electrode is reference electrode, under current potential-0.2V vs.Pt, carry out constant potential precipitate reduction Ag, sedimentation time 2s, namely obtains Ag
(0.9 μ g)-Pd/ graphene composite material, Ag precipitation capacity is 0.9 μ g cm
– 2.Load capacity due to Pd is 20.3 μ g cm
– 2, the atomic ratio obtaining Ag and Pd is 1:23.See that Graphene is sheet by Fig. 3, and observe fold.Metallic load is at Graphene basal plane and edge, and what have is wrapped up completely by Graphene, but distribution uniform, particle aggregation phenomenon is fewer.
With Ag prepared above
(0.9 μ g)-Pd/ graphene composite material checks the catalytic effect to 1,2-PD oxidation reaction in sodium hydroxide solution.For this reason, successively get 20mL redistilled water, 147 μ L 1,2-propylene glycol (purity>=99.7%) and 0.4g NaOH (purity>=96.0%) join in the 50mL beaker of a dried and clean prepares alcoholic solution, and above-mentioned preparation is coated with Ag
(0.9 μ g)the electrode of-Pd/ graphene composite material with after redistilled water clean surface as work electrode, Pt electrode is to electrode, and saturated calomel electrode is reference electrode, contains 1 above-mentioned, carry out cyclic voltammetry in the sodium hydroxide solution of 2-propylene glycol, result as shown in Figure 4.Ag
(0.9 μ g)in-Pd/ Graphene electrodes, the peak point current of 1,2-PD oxidation reaction is 23.6mAcm
-2.
Pd/ Graphene electrodes in Fig. 1 is the Pd/ Graphene electrodes before Ag precipitation, and this electrode Pd load capacity is 20.3 μ gcm
– 2, the Ag load capacity of Ag/ Graphene is 20.7 μ g cm
– 2.Pd/ Graphene is identical with the molal quantity of Pd with Ag of Ag/ Graphene, and the reaction condition of Fig. 1 with Fig. 4 is also identical.
Comparison diagram 1 and Fig. 4 can see, Ag
(0.9 μ g)peak point current in-Pd/ Graphene electrodes is 2.2 times in Pd/ Graphene electrodes, and is oxidized take-off potential and spike potential is basically identical to the corresponding current potential in Pd/ Graphene electrodes.
Embodiment 2:
Experimental procedure is identical with embodiment 1, and just the Ag sedimentation time is 1s.Obtain Ag
(0.5 μ g)-Pd/ graphene combination electrode, Ag precipitation capacity is 0.5 μ g cm
– 2.
With Ag prepared above
(0.5 μ g)-Pd/ Graphene electrodes checks the catalytic effect to 1,2-PD oxidation reaction in sodium hydroxide solution.Result as shown in Figure 4.Comparison diagram 1 and Fig. 4 can see, Ag
(0.5 μ g)in-Pd/ Graphene electrodes, the peak point current of 1,2-PD oxidation reaction is 1.7 times in Pd/ Graphene electrodes, and reaction potential (oxidation take-off potential and spike potential) is basically identical with the reaction potential in Pd/ Graphene electrodes.
Embodiment 3:
Experimental procedure is identical with embodiment 1, and just the Ag sedimentation time is 5s.Obtain Ag
(1.8 μ g)-Pd/ graphene combination electrode, Ag precipitation capacity is 1.8 μ g cm
– 2.
With Ag prepared above
(1.8 μ g)-Pd/ Graphene electrodes checks the catalytic effect to 1,2-PD oxidation reaction in sodium hydroxide solution.Result as shown in Figure 4.Comparison diagram 1 and Fig. 4 can see, Ag
((1.8 μ g)in-Pd/ Graphene electrodes, the peak point current of 1,2-PD oxidation reaction is 2 times in Pd/ Graphene electrodes, and reaction potential (oxidation take-off potential and spike potential) is basically identical with the reaction potential in Pd/ Graphene electrodes.
Comparative example 1:
Electrode prepared in embodiment 1 is used for 1,3-PD oxidation reaction, compares the catalytic effect of this electrode pair 1,3-PD and 1,2-PD oxidation reaction.For this reason, preparation, containing the 0.5M sodium hydroxide solution of 0.1M 1,3-PD, then passes into nitrogen, discharges the oxygen dissolved.The Ag that embodiment 1 prepares
(0.9 μ g)-Pd/ Graphene electrodes is placed in above-mentioned solution, is to electrode with Pt sheet, and saturated calomel electrode is reference electrode, with sweep speed 50mV s
– 1carry out cyclic voltammetry.
Result shows: Ag
((0.9 μ g)in-Pd/ Graphene electrodes, the peak point current of 1,3-PD oxidation reaction is 10.4mA cm
– 2, Pd/ Graphene electrodes is 9.2mA cm
– 2.Ag
((0.9 μ g)peak point current in-Pd/ Graphene electrodes is 1.13 times of peak point current in Pd/ Graphene electrodes.Also see the increase along with Ag precipitation capacity in experiment, in the Pd/ Graphene electrodes that Ag modifies, the peak current of 1,3-PD oxidation reaction reduces gradually.This illustrates compared with Pd/ Graphene electrodes, the few of advantage of the catalytic action of Pd/ Graphene electrodes to 1,3-PD oxidation reaction that Ag modifies.
Comparative example 2:
Graphene carrier carbon black-supported in embodiment 1 is replaced, checks different carriers on the impact of catalyst effect.For this reason, by embodiment 1 step, do carrier with carbon black, prepare the Pd/ carbon black composite material with Pd/ Graphene electrodes with same molal quantity load capacity, namely palladium load capacity is 20.3 μ g cm
-2.Then, the Ag carrying out Pd/ carbon black by embodiment 1 step modifies, and obtaining Ag precipitation capacity is 0.9 μ g cm
– 2ag
(0.9 μ g)-Pd/ carbon black combination electrode.This electrode is placed in the 0.5M sodium hydroxide solution containing 0.1M 1,2-PD, and be to electrode with Pt sheet, saturated calomel electrode is reference electrode, with sweep speed 50mVs
– 1carry out cyclic voltammetry.
Result shows: Ag
((0.9 μ g)on-Pd/ carbon black electrode, the peak point current of 1,2-PD oxidation reaction is 5.4mA cm
– 2, Pd/ carbon black electrode is 6.9mA cm
– 2.Ag
((0.9 μ g)peak point current on-Pd/ carbon black electrode is lower than the peak point current on Pd/ carbon black electrode.Also see the increase along with Ag precipitation capacity in experiment, on the Pd/ carbon black electrode that Ag modifies, the peak current of 1,2-PD oxidation reaction reduces gradually.This illustrates that Ag precipitation is unfavorable for the catalytic action of Pd/ carbon black electrode pair 1,2-PD oxidation reaction.
Claims (5)
1. a Pd/ graphene composite material for Ag modification, it is characterized in that: in described composite material, Ag is deposited on the surface of graphene-supported Pd nano particle, and the atomic ratio scope of Ag and the Pd obtained is 1:41 ~ 1:11.
2. the preparation method of the Pd/ graphene composite material of Ag modification as claimed in claim 1, is characterized in that: described preparation method is,
Prepared by a, Pd/ graphene composite material
Get 1.5 ~ 2.5mg graphite oxide and redistilled water, then add Pd (NO wherein
3)
2carry out ultrasonic oscillation after solution, obtain Pd (NO
3)
2concentration is the dark brown transparence liquid 14.15 ~ 23.58mL of 0.25mM; Then under magnetic stirring, in above-mentioned dark brown transparence liquid, add the NaBH of 0.03 ~ 0.05g
4, continue stirring reaction 0.5 ~ 1.5h, generate Pd nano particle and load on Graphene; After question response is complete, reactant liquor is transferred in test tube and leave standstill 10 ~ 12h, be settled out Pd/ Graphene; In test tube, add ethanol after removing supernatant liquor, carry out ultrasonic disperse 5 ~ 10min, obtain tusche shape liquid 0.75 ~ 1.25mL; Pipette above-mentioned tusche shape liquid 5 μ L to be coated onto and to use Al
2o
3polishing powder polishing the glassy carbon electrode surface of ultrasonic cleaning in redistilled water, drying at room temperature, namely obtains Pd/ graphene composite material;
The finishing of b, Pd/ graphene composite material
Ag precursor solution is made with silver sulfate, sulfuric acid and redistilled water, then with the glass-carbon electrode being coated with Pd/ graphene composite material prepared in step a for work electrode, Pt sheet is to electrode, Pt electrode is reference electrode, under constant potential condition, from described Ag precursor solution, precipitate reduction Ag to Pd/ graphene composite material is surperficial, obtains the Pd/ graphene composite material with different Ag modification amount by controlling the sedimentation time.
3. the preparation method of the Pd/ graphene composite material of Ag modification as claimed in claim 2, it is characterized in that: in step b, in described Ag precursor solution, silver sulfate concentration is 1.0mM, and sulfuric acid concentration is 0.05M.
4. the preparation method of the Pd/ graphene composite material of Ag modification as claimed in claim 2, it is characterized in that: in step b, described constant potential condition is the arbitrary value within the scope of-0.15 ~-0.25V vs.Pt.
5. the application of the Pd/ graphene composite material that the Ag as described in any one of Claims 1-4 modifies, it is characterized in that: described is applied as, the Pd/ graphene composite material of described Ag modification amount is as electrode catalytic oxidation 1,2-PD under alkaline medium condition.
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| CN107445149A (en) * | 2016-05-31 | 2017-12-08 | 嘉泉大学校产学协力团 | Graphene metal nanoparticle complex |
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| CN106179336A (en) * | 2016-07-12 | 2016-12-07 | 陕西理工学院 | A kind of bimetallic catalyst and preparation method thereof |
| CN106319576A (en) * | 2016-09-13 | 2017-01-11 | 合肥工业大学 | Two-electrode electrochemical reduction method for preparing silver-graphene nano composite material at indoor temperature |
| 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 |
| CN107543849A (en) * | 2017-07-31 | 2018-01-05 | 常州大学 | The high activity electrode preparation method on the two kinds of step of noble metal one modification common metal nano composite material surfaces |
| CN108777311A (en) * | 2018-06-04 | 2018-11-09 | 东华大学 | A kind of Pd/MGN composite material and preparation methods and application with either high redox electro catalytic activity |
| CN109817999A (en) * | 2019-01-23 | 2019-05-28 | 西北工业大学 | Silver catalysis magnalium laminar hydroxide film formates fuel cell and preparation method |
| 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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