CN104959137A - High catalytic activity graphene-Pd @ Pt core-shell structure nanoflower compound and preparation method thereof - Google Patents
High catalytic activity graphene-Pd @ Pt core-shell structure nanoflower compound and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a high catalytic activity graphene-Pd @ Pt core-shell structure nanoflower compound and a preparation method thereof. First, at room temperature, ascorbic acid is used for reducing an aqueous solution of graphene oxide and palladium chloride to obtain palladium nanoparticles with regular morphology and assemble the palladium nanoparticles in situ onto the chemically-reduced graphene, then the resulting graphene-palladium is used as a seed crystal, seed growth method is used, chloroplatinic acid is added into the reaction solution, and the microwave-assisted rapid reduction of the chloroplatinic acid is perforemed to obtain graphene supported Pd @ Pt core-shell structure nanoflower. The electrochemical data shows that under alkaline conditions, the catalytic oxidation activity of the graphene-Pd @ Pt core-shell structure nanoflower compound is much higher than that of a graphene-platinum-palladium alloy compound, and the graphene-platinum compound and a commercial platinum carbon catalyst show great potential as fuel cell electrode material. The preparation process is simple, materials are non-toxic and harmless, and Pd @ Pt core-shell structure nanoparticles monodispersed on the graphene can be obtained without adding of any additional surfactant.
Description
Technical field
The present invention relates to the preparation field of nano composite material, the Graphene-palladium@platinum nuclear shell structure nano in particular to a kind of high catalytic activity spends compound and preparation method thereof.
Background technology
Noble metal bimetal nano crystalline substance has the advantages such as higher catalytic activity and stability due to intermetallic coupling and cooperative effect, become study hotspot in recent years, platinum, palladium has a wide range of applications at catalytic field as two kinds of important noble metals, as the oxidation of CO, the micromolecular oxidation such as methyl alcohol, utilize intermetallic coupling, the palladium platinum nano-crystal with core-shell structure designing loose structure not only can improve its catalytic activity, its stability can also be strengthened, can as the catalyst of the reaction of DMFC anodic methanol oxidation using this, thus greatly reduce the commercialization cost of fuel cell.
Graphene as a kind of novel Two-dimensional Carbon nano material, only by one deck sp
2hydbridized carbon atoms arrangement forms, it is two-dimensional material the thinnest on the known world, there is excellent electric conductivity and huge specific area, therefore utilize Graphene to carry out metal supported catalyst and be considered to a kind of available strategy improving catalytic activity and reduce noble metal utilisation.
At present, the method of carried metal nano particle on Graphene reported is mainly by two step synthesis, the Graphene of the first synthetic metals nano particle of the first step and electronation, and then by adding surfactant and physical action makes metal nanoparticle be adsorbed on (S. H. Sun et al on Graphene
j. Am. Chem. Soc. 2012,134,2492).This method technique relative complex, the adhesion of nano particle and Graphene is more weak easily to come off, and surfactant add the surface-active site covering metal nanoparticle and the electric conductivity reducing Graphene.
Therefore, develop and a kind of under surfactant-free condition, prepare metal nanoparticle-graphene composite material by coreduction metal precursor and graphene oxide be significant.
Summary of the invention
Graphene-palladium@platinum nuclear shell structure nano flower compound that the object of the present invention is to provide a kind of high catalytic activity and preparation method thereof, the method agents useful for same is comparatively simple, nontoxic, and preparation method is simple, easily realizes.In alkaline electro medium, the electrode that obtained above-mentioned Graphene-palladium@platinum nuclear shell structure nano flower compound is modified and Graphene-pallas, Graphene-platinum, and the electrode that business platinum carbon is modified is compared, and has more excellent catalytic activity and stability to the oxidation of methyl alcohol.
The present invention is achieved in that the method is the palladium nano-particles first obtaining original position load on Graphene, and then induce the growth of platinum in this, as seed thus obtain Graphene-palladium platinum nuclear shell structure nano flower compound, concrete steps are as follows:
(1) preparation of graphene oxide: the red fuming nitric acid (RFNA) of to be the concentrated sulfuric acid of 95-98% and 20-100ml mass concentration by 10-100ml mass concentration be 65-68% is mixed to be incorporated in 0 DEG C of condition of ice bath lower magnetic force and to stir 5-50 minute, then add 1-200g natural flake graphite, vigorous stirring prevents from reuniting; After being uniformly dispersed, add 10-200g potassium chlorate, under finally removing ice bath room temperature, react 20-150 hour; After question response completes, product is washed, ultrasonic stripping, flocculate with NaOH and in 20-80 DEG C of dry 2-10 hour, grind, obtain graphene oxide pressed powder;
(2) preparation of Graphene-palladium compound: 5-40mg graphene oxide powder ultrasonic is scattered in 10-200ml deionized water and obtains monodispersed graphene oxide dispersion, be that the palladium chloride aqueous solution of 15 mM dropwise joins above-mentioned dispersion liquid under agitation again by 100-2000ul molar concentration, continue subsequently to stir 5-15min, subsequently 50-500mg ascorbic acid is added wherein, at room temperature stirring reaction 30-120min, obtains the palladium nano-particles of growth in situ on Graphene;
(3) preparation of Graphene-palladium platinum nuclear shell structure nano flower compound: reactant liquor obtained above is placed in microwave reactor, add the chloroplatinic acid aqueous solution that 200-2000ul molar concentration is 15 mM wherein, at 60-100 DEG C, 3-20min is reacted under the radiant power of 200-1000 W, transfer them to again in centrifuge tube after being cooled to room temperature, centrifugal 3-20 min under 4000-15000 rev/min of condition, then ethanol and water washing is used respectively, last freeze drying obtains Graphene-palladium platinum nuclear shell structure nano flower compound (i.e. Graphene-palladium@platinum nuclear shell structure nano flower compound).
Tool of the present invention has the following advantages and good effect:
1. the present invention adopts Liquid preparation methods to go out the palladium platinum nuclear shell structure nano flower of graphene-supported high degree of dispersion, because palladium platinum nano flower has three-dimensional porous structure, reactant molecule can omnibearing contact nanometer catalyst surface, therefore atom utilization ratio is substantially increased, decrease the use of noble metal, can greatly reduce its cost in this, as fuel cell electrode material.
2. synthetic method used herein implements under surfactant-free condition, thus avoid the obstruction of surfactant molecule to nanocatalyst avtive spot, make more avtive spot be exposed and participate in catalytic reaction, greatly can improve catalytic efficiency like this.
3., compared with the electrode that the Graphene utilizing this method to prepare-palladium platinum nuclear shell structure nano flower is modified and the electrode that business platinum carbon is modified, several times are improve, far above the catalyst of current bibliographical information to the catalytic oxidation performance of methyl alcohol and stability.
4. this method agents useful for same is simple, nontoxic, and technique is also comparatively simple, easily produces in enormous quantities and realizes industrialization.
Accompanying drawing explanation
Fig. 1 shows the preparation principle figure of Graphene-palladium platinum nuclear shell structure nano flower.
Fig. 2 a and b shows low power and the high power transmission electron microscope picture of Graphene-palladium compound respectively; Fig. 2 c, d, e show the Graphene-transmission electron microscope picture of palladium platinum nuclear shell structure nano flower under different multiplying; Fig. 2 f shows the line sweep distribution map of single palladium platinum nano flower.
Fig. 3 a, b show the grain size distribution of graphene-supported palladium nano-particles and palladium platinum nuclear shell structure nano flower respectively.
Fig. 4 is the transmission electron microscope picture of Graphene-pallas of the present invention.
Fig. 5 is the transmission electron microscope picture of Graphene-platinum of the present invention.
Fig. 6 is Graphene-palladium platinum nuclear shell structure nano flower, Graphene-pallas, Graphene-platinum, and the cyclic voltammetry curve (a) of the glass-carbon electrode modified of business platinum carbon catalysis methanol oxidation in the basic conditions; Time current curve (b).In figure, electric current is for benchmark with the quality of platinum.
Fig. 7 be above-mentioned four kinds of catalyst with platinum and palladium total amount for quality current density during benchmark.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.Be understandable that, this
The concrete case study on implementation that place describes is only for explaining the application, but not the restriction to the application.
embodiment 1
First, adopt the Staudenmaier legal system improved for graphene oxide.Concrete operation step is as follows: at 500ml round-bottomed flask, to add 72ml mass concentration be the concentrated sulfuric acid 36ml mass concentration of 95-98% is the red fuming nitric acid (RFNA) of 65-68%, 15 minutes are stirred at 0 DEG C of condition of ice bath lower magnetic force, then add 4g natural flake graphite, vigorous stirring prevents from reuniting; After being uniformly dispersed, add 44g potassium chlorate, react 96 hours under finally removing ice bath room temperature; After question response completes, product is washed, ultrasonic stripping, flocculate with NaOH and in 60 DEG C of dryings 24 hours, grind, obtain graphene oxide pressed powder;
Then Graphene-palladium compound is prepared, concrete steps are as follows: be scattered in 100 ml deionized waters by 10 mg graphene oxide powder ultrasonics and obtain monodispersed graphene oxide dispersion, the palladium chloride aqueous solution being 15 mM by 600 ul molar concentrations more dropwise joins above-mentioned dispersion liquid under agitation, continue subsequently to stir 15min, subsequently 250 mg ascorbic acid are added wherein, at room temperature stirring reaction 60 min, obtain the palladium nano-particles of growth in situ on Graphene, take a morsel reacted solution centrifugal, preparation TEM sample, observe its pattern, Fig. 2 a, b is respectively low power transmission electron microscope and the high power transmission electron microscope picture of Graphene-palladium nano-particles, Fig. 3 a is the grain size distribution of palladium nano-particles, as can be seen from the figure, palladium nano-particles has good monodispersity on Graphene, average grain diameter is 6.3 nm.
Finally we induce the growth of platinum using above-mentioned gained to graphene-supported palladium nano-particles as crystal seed, reaction principle figure is as Fig. 1, concrete steps are as follows: reactant liquor obtained above is placed in microwave reactor, add the chloroplatinic acid aqueous solution that 400 ul molar concentrations are 15 mM wherein, at 80 DEG C, 5 min are reacted under the radiant power of 400 W, transfer them to again in centrifuge tube after being cooled to room temperature, centrifugal 10 min under 10000 revs/min of conditions, then ethanol and water washing is used respectively, last freeze drying obtains Graphene-palladium platinum nuclear shell structure nano flower compound.Its pattern is as Fig. 2 c, shown in d, e, as can be seen from the figure, palladium@platinum core-shell nano flower is comparatively even in graphenic surface dispersion, Fig. 3 b is its grain size distribution, and average grain diameter is about 16.4 nm, and Fig. 2 f is the elemental line scan spectrogram of single palladium platinum nano flower, therefrom can find out, palladium element is mainly centered in nano flower interior zone, and platinum element is then mainly distributed in nano flower outer peripheral areas, shows that we have successfully prepared monodispersed palladium@platinum nuclear shell structure nano flower on Graphene.
As a comparison, when adding palladium bichloride and chloroplatinic acid in reaction system simultaneously, the graphene-supported pallas that adopted identical method to prepare, pattern as shown in Figure 4.Same when we do not introduce palladium bichloride in reaction system, we obtain the Pt nanoparticle of load on Graphene, and pattern as shown in Figure 5.
Graphene-palladium@platinum nuclear shell structure nano flower compound prepared by the present embodiment, as the catalyst of anode of fuel cell methanol oxidation, can significantly improve catalytic activity and stability.The performance test of methanol oxidation is carried out using this catalyst as fuel battery anode catalyst, the performance test results as shown in Figure 6,7, as can be seen from Figure 6, Graphene-palladium@platinum core-shell nano flower compound is relative to Graphene-pallas, Graphene-platinum, and business platinum carbon shows more excellent catalytic activity and stability, illustrate its great potential as fuel cell electrode material.
embodiment 2
By the preparation method of embodiment 1, just the reaction time of preparing Graphene-palladium compound stage is adjusted to 30 min by 60 min, obtains pattern as shown in Figure 2 equally.
embodiment 3
by the preparation method of embodiment 1, just the reaction time of preparing Graphene-palladium compound stage is adjusted to 90 min by 60 min, obtains result as shown in Figure 2 equally.
embodiment 4
by the preparation method of embodiment 1, just change the reaction time of preparing Graphene-palladium compound stage into 120 min by 60 min, obtain result as shown in Figure 2 equally.
embodiment 5
by the preparation method of embodiment 1, just change the quality of graphene oxide into 5 mg by 10 mg, obtain pattern as shown in Figure 2 equally.
embodiment 6
By the preparation method of embodiment 1, just change the volume of palladium chloride solution into 400 ul by 600 ul, the volume of chloroplatinic acid changes 400ul into by 600ul, obtains pattern as shown in Figure 2 equally.
embodiment 7
by the preparation method of embodiment 1, just change the microwave power in microwave reaction stage into 600W by 400W, obtain pattern as shown in Figure 2 equally.
embodiment 8
By the preparation method of embodiment 1, just change the power in microwave reaction stage into 800W by 400W, obtain pattern as shown in Figure 2 equally.
embodiment 9
by the preparation method of enforcement 1, just change the microwave reaction time into 3min by 5 min, obtain pattern as shown in Figure 2 equally.
embodiment 10
By the preparation method of embodiment 1, just change the microwave reaction time into 10min by 5 min, obtain pattern as shown in Figure 2 equally.
Above-described embodiment is illustrative principle of the present invention and effect only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art and usually know that the knowledgeable modifies or changes not departing from all that complete under disclosed spirit and technological thought, still covered by claim of the present invention.
Claims (4)
1. a preparation method for the Graphene-palladium platinum nuclear shell structure nano flower compound of high catalytic activity, is characterized in that, comprise the following steps:
(1) preparation of graphene oxide: mixed being incorporated in of red fuming nitric acid (RFNA) of to be the concentrated sulfuric acid of 95-98% and 20-100ml mass concentration by 10-100ml mass concentration be 65-68% stirs 5-50 minute at 0 DEG C of condition of ice bath lower magnetic force, then add 1-200g natural flake graphite, vigorous stirring prevents from reuniting; After being uniformly dispersed, add 10-200g potassium chlorate, under finally removing ice bath room temperature, react 20-150 hour; After question response completes, product is washed, ultrasonic stripping, flocculate with NaOH and in 20-80 DEG C of dry 2-10 hour, grind, obtain graphene oxide pressed powder;
(2) preparation of Graphene-palladium compound: 5-40mg graphene oxide powder ultrasonic is scattered in 10-200ml deionized water and obtains monodispersed graphene oxide dispersion, be that the palladium chloride aqueous solution of 15 mM dropwise joins above-mentioned dispersion liquid under agitation again by 100-2000ul molar concentration, continue subsequently to stir 5-15min, subsequently 50-500mg ascorbic acid is added wherein, at room temperature stirring reaction 30-120min, obtains the reactant liquor containing the palladium nano-particles of growth in situ on Graphene;
(3) preparation of Graphene-palladium platinum nuclear shell structure nano flower compound: the reactant liquor that above-mentioned steps (2) obtains is placed in microwave reactor, add the chloroplatinic acid aqueous solution that 200-2000ul molar concentration is 15 mM wherein, at 60-100 DEG C, 3-20min is reacted under the radiant power of 200-1000 W, transfer them to again in centrifuge tube after being cooled to room temperature, centrifugal 3-20 min under 4000-15000 rev/min of condition, then use ethanol and water washing respectively, last freeze drying obtains Graphene-palladium@platinum nuclear shell structure nano flower compound.
2. Graphene-palladium@platinum nuclear shell structure nano spends the preparation method of compound according to claim 1, it is characterized in that, in step (2), the mass ratio of graphene oxide and palladium bichloride is 0.1-10.
3. Graphene-palladium@platinum nuclear shell structure nano spends the preparation method of compound according to claim 1, it is characterized in that, in step (3), the mol ratio of chloroplatinic acid and palladium bichloride is 0.1-10.
4. by Graphene-palladium@platinum nuclear shell structure nano flower compound that method described in claim 1 is obtained.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776131A (en) * | 2016-04-21 | 2016-07-20 | 厦门大学 | Silver platinum nanocomposite loaded on graphene surface and preparation method thereof |
| CN106735298A (en) * | 2016-12-13 | 2017-05-31 | 浙江大学 | A kind of square palladium nano sheet and preparation method thereof |
| CN108630948A (en) * | 2017-03-17 | 2018-10-09 | 天津大学 | A kind of preparation method of octahedron palladium platinum catalyst with core-casing structure |
| CN108855240A (en) * | 2018-06-25 | 2018-11-23 | 厦门大学 | A method of nano-platinum particle catalytic activity is protected using glycerol |
| CN110756187A (en) * | 2019-10-28 | 2020-02-07 | 西安交通大学 | Gold-palladium/graphene catalyst growing on graphene surface in situ and preparation method thereof |
| CN111430731A (en) * | 2020-04-01 | 2020-07-17 | 安徽师范大学 | Porous carbon platinum-loaded material and preparation method and application thereof |
| CN113363507A (en) * | 2020-07-21 | 2021-09-07 | 河海大学 | Preparation method of titanium carbide supported platinum-palladium nanoflower electrode catalyst |
| CN116344839A (en) * | 2023-01-13 | 2023-06-27 | 一汽解放汽车有限公司 | High-potential catalyst and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105776131A (en) * | 2016-04-21 | 2016-07-20 | 厦门大学 | Silver platinum nanocomposite loaded on graphene surface and preparation method thereof |
| CN106735298A (en) * | 2016-12-13 | 2017-05-31 | 浙江大学 | A kind of square palladium nano sheet and preparation method thereof |
| CN106735298B (en) * | 2016-12-13 | 2018-09-18 | 浙江大学 | A kind of rectangular palladium nano sheet and preparation method thereof |
| CN108630948A (en) * | 2017-03-17 | 2018-10-09 | 天津大学 | A kind of preparation method of octahedron palladium platinum catalyst with core-casing structure |
| CN108630948B (en) * | 2017-03-17 | 2020-11-03 | 天津大学 | Preparation method of octahedral palladium-platinum core-shell structure catalyst |
| CN108855240A (en) * | 2018-06-25 | 2018-11-23 | 厦门大学 | A method of nano-platinum particle catalytic activity is protected using glycerol |
| CN110756187A (en) * | 2019-10-28 | 2020-02-07 | 西安交通大学 | Gold-palladium/graphene catalyst growing on graphene surface in situ and preparation method thereof |
| CN111430731A (en) * | 2020-04-01 | 2020-07-17 | 安徽师范大学 | Porous carbon platinum-loaded material and preparation method and application thereof |
| CN113363507A (en) * | 2020-07-21 | 2021-09-07 | 河海大学 | Preparation method of titanium carbide supported platinum-palladium nanoflower electrode catalyst |
| CN113363507B (en) * | 2020-07-21 | 2022-06-10 | 河海大学 | Preparation method of titanium carbide supported platinum-palladium nanoflower electrode catalyst |
| CN116344839A (en) * | 2023-01-13 | 2023-06-27 | 一汽解放汽车有限公司 | High-potential catalyst and preparation method and application thereof |
| CN116344839B (en) * | 2023-01-13 | 2024-05-28 | 一汽解放汽车有限公司 | High-potential catalyst and preparation method and application thereof |
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Application publication date: 20151007 |