CN104525190A - Preparation method for palladium/three-dimensional graphene composite microspheres - Google Patents
Preparation method for palladium/three-dimensional graphene composite microspheres Download PDFInfo
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- CN104525190A CN104525190A CN201510001511.XA CN201510001511A CN104525190A CN 104525190 A CN104525190 A CN 104525190A CN 201510001511 A CN201510001511 A CN 201510001511A CN 104525190 A CN104525190 A CN 104525190A
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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
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- 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
Abstract
The invention relates to a preparation method for composite microspheres, in particular to a preparation method for palladium/three-dimensional graphene composite microspheres. The preparation method for the palladium/three-dimensional graphene composite microspheres solves the technical problems that existing preparation methods for the palladium/three-dimensional graphene composite microspheres are complicated and are not suitable for industrial large-scale production. The preparation method comprises the following steps that firstly, raw materials are mixed to prepare a solution; secondly, solidification and forming are conducted; thirdly, calcination is conducted. The preparation method for the palladium/three-dimensional graphene composite microspheres has the advantages that the method is novel and unique, operation is easy, the process is safe, reliable and environmentally friendly, the obtained palladium/three-dimensional graphene composite microspheres are controllable in size and uniform in particle size, the preparation method is one of the ideal preparation methods for the palladium/three-dimensional graphene composite microspheres, and the preparation method is suitable for industrial large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of compounded microbeads.
Technical background
Graphene is the two-dimensional structure with monoatomic layer thickness, from it first by Geim by since mechanical stripping system, due to the characteristic of its uniqueness, be extensively studied in catalysis, energy conversion, storage and sensor and applied.Graphene has large theoretical specific surface area, high electronic conductivity, good chemical stability and lower production cost and in catalytic reaction, makes it have stronger adsorption capacity to matrix due to partly conjugated structure thus be used as auxiliary material.Some researchs show, the metal nanoparticle be carried on Graphene is compared with those load metal nanoparticles on the carbon nanotubes in electro-catalysis with direct-type fuel cell more excellent catalytic activity and more wide application prospect.In recent years, much research points out that palladium catalyst shows the ability of higher catalytic activity and stronger CO tolerance catalysts than platinum catalyst in the electroxidation of ethanol or formic acid.On the basis of first principle calculation, some researchs show, Graphene P
ztrack and palladium d
zelectronics hydridization between track ensure that the existence of abundant pi-electron on Graphene, and this causes there is very strong interaction between Graphene and palladium, and the combination on Graphene and palladium surface is then weak a lot.Obviously, palladium/graphene catalyst shows excellent electrocatalysis characteristic in a fuel cell.At present, great majority are be carried on two-dimensional graphene lamella by palladium by methods such as electrochemical co-deposition, in-situ reducing, liquid-phase reductions about the research of palladium/graphene catalyst.
Three-dimensional grapheme, as the novel aggregated structure of one, has caused everybody great attention.By hydrothermal method, Wu etc. demonstrate Fe
3o
4on the all-solid-state supercapacitor of nanometer particle load on the three-dimensional nitrogen-doped graphene aeroge having interconnective large hole on framework and based on the monolithic graphite alkene aeroge of three-dimensional nitrogen boron codope.The preparation such as Gong be that the mixed architecture of main chain comprises MoS with three-dimensional grapheme
2/ Graphene and FeOx/ Graphene.Meng etc. have invented a kind of full Graphene core-shell structure copolymer composite fibre of uniqueness, and its mesochite is three-dimensional class mesh structural porous Graphene skeleton shell.By hard template method, Choi etc. by with polystyrene colloid particle as Template preparation three-dimensional macropore graphene film.Huang etc. to have synthesized as pore former with silica spheres and have had controllable grain size (30 ~ 120nm) and superelevation pore volume (-4.3cm
3g
-1) Nano-size Porous Graphite alkene foam.By chemical vapour deposition (CVD), Singh etc. obtain has complete foam network structure and the graphene sheet layer of well controlled microscopic porosity and roughness; The Graphene network that Bi etc. use foamed nickel catalyst graphene growth to become three-dimensional.By the method for template assemblies, Vickery etc. produce the graphene-polymer nano composite material of more regular three-dimensional sponge shape macropore support and hollow micron-sized spherical structure.Yin etc. report a kind of self assembly strategy of expansion to obtain bionical hierarchical structure, and this structure is made up of the graphene sheet layer of functionalization.Xiao etc. illustrate a kind of Novel air electrode, and it comprises a kind of uncommon layer functions functionalized graphene with unique double-pore structure.Lee etc. report and are self-assembled into the carbon film with mechanical tenacity pore structure by graphene oxide sheet three-dimensional.In addition, Fan etc. are with PS as the hard template on three-dimensional structure surface, and this three-dimensional structure has many empty redox graphenes, also have the how empty composite of to be broken by the thermal decomposition redox graphene that obtains and silica.
In the past few years, the single dispersing microballon that microflow control technique obtains is widely used in preparing the multiple monitoring etc. of three-D photon crystal colloid pearl, photonic crystal colorimetric sensing film, bio-carrier coding and tumor markers.
The preparation method preparing palladium/three-dimensional grapheme catalyst is at present comparatively complicated, is not suitable for industrial mass production.
Summary of the invention
The present invention will solve the preparation method's comparatively complexity preparing palladium/three-dimensional grapheme catalyst at present, is not suitable for the technical problem of industrial mass production, and provides the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads.
The preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads of the present invention carries out according to the following steps:
One, mixed material wiring solution-forming: be the graphene oxide solution of 1% ~ 1.5%, 0.25g polyvinylpyrrolidone and 0.0714gPdCl by 5g mass fraction
2homogeneous phase mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: get the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 60 DEG C ~ 70 DEG C and rotating speed is the condition of 500rpm, is incubated 12h ~ 24h, obtains compounded microbeads; The material of described bulge is polypropylene;
Three, calcine: compounded microbeads step 2 obtained rises to 750 DEG C from room temperature with the heating rate of 5 DEG C/min after taking out from bulge under nitrogen protection; then be incubated 2h under the condition of 750 DEG C and nitrogen protection in temperature, obtain palladium/three-dimensional grapheme compounded microbeads.
Advantage of the present invention:
One, in the polypropylene bulge that adopts of step 2 of the present invention, polypropylene is a kind of special hydrophobic material, and surface energy is low, can make the Di Hebi of Composite Particles Disperse Phase solution non-stick container in high-speed agitating process, and can remain spherical pattern;
Two, the present invention is in high-speed agitating process, adopts direct-fired mode to carry out rapid curing to Composite Particles Disperse Phase solution, accelerates the evaporation of moisture in drop, the pattern of drop can be made at short notice to be fixed;
Three, method of the present invention is novel unique, and simple to operate, process safety is reliably environmentally friendly, and the palladium obtained/three-dimensional grapheme compounded microbeads size is controlled, uniform particle diameter, is one of Perfected process preparing three-dimensional grapheme microballon, is applicable to industrial mass production.
Accompanying drawing explanation
Fig. 1 is the SEM figure that the palladium/three-dimensional grapheme compounded microbeads of test one preparation amplifies 100 times;
Fig. 2 is the SEM figure on palladium/three-dimensional grapheme compounded microbeads surface prepared by test one;
Fig. 3 is the SEM figure of palladium/three-dimensional grapheme compounded microbeads inside prepared by test one;
Fig. 4 is the XRD figure of palladium/three-dimensional grapheme compounded microbeads prepared by test one;
Fig. 5 is the palladium/three-dimensional grapheme compounded microbeads adopting test one to prepare in test two carries out electro-catalysis curve to ethanol.
Detailed description of the invention
Detailed description of the invention one: present embodiment is the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads, specifically carries out according to the following steps:
One, mixed material wiring solution-forming: be the graphene oxide solution of 1% ~ 1.5%, 0.25g polyvinylpyrrolidone and 0.0714gPdCl by 5g mass fraction
2homogeneous phase mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: get the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 60 DEG C ~ 70 DEG C and rotating speed is the condition of 500rpm, is incubated 12h ~ 24h, obtains compounded microbeads; The material of described bulge is polypropylene;
Three, calcine: compounded microbeads step 2 obtained rises to 750 DEG C from room temperature with the heating rate of 5 DEG C/min after taking out from bulge under nitrogen protection; then be incubated 2h under the condition of 750 DEG C and nitrogen protection in temperature, obtain palladium/three-dimensional grapheme compounded microbeads.
Present embodiment advantage:
One, present embodiment step 2 adopt polypropylene bulge in polypropylene be a kind of special hydrophobic material, surface energy is low, can make the Di Hebi of Composite Particles Disperse Phase solution non-stick container in high-speed agitating process, and can remain spherical pattern;
Two, present embodiment is in high-speed agitating process, adopts direct-fired mode to carry out rapid curing to Composite Particles Disperse Phase solution, accelerates the evaporation of moisture in drop, the pattern of drop can be made at short notice to be fixed;
Three, the method for present embodiment is novel unique, simple to operate, process safety is reliably environmentally friendly, and the palladium obtained/three-dimensional grapheme compounded microbeads size is controlled, uniform particle diameter, be one of Perfected process preparing three-dimensional grapheme microballon, be applicable to industrial mass production.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: be the graphene oxide solution of 1%, 0.25g polyvinylpyrrolidone and 0.0714gPdCl by 5g mass fraction in step one
2homogeneous phase mixing, obtains Composite Particles Disperse Phase solution.Other is identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one to two unlike: the preparation method of the graphene oxide in step one is: the flaky graphite powder getting 1.2g joins in the glass there-necked flask that volume is 500mL, add the concentrated sulfuric acid of 50mL again, glass there-necked flask being put into ice-water bath low whipping speed is stir 30min under the condition of 250r/min, slowly add the potassium permanganate of 10g and the sodium nitrate of 1.5g again, low whipping speed is stir 2h under the condition of 200r/min and ice-water bath, under room temperature and mixing speed are the condition of 250r/min, 2h is stirred after being taken out from ice-water bath by glass there-necked flask, then in temperature be in the water-bath of 35 DEG C and mixing speed be stir 24h under the condition of 250r/min, the mass fraction adding 10mL ~ 15mL is again the hydrogen peroxide solution of 30% and the mass fraction of 10mL is the aqueous hydrochloric acid solution of 36% ~ 38%, obtain thick solution, the method of centrifugation is adopted to isolate solution the thick solution obtained, solution is put into pellicle dialysis to solution for neutral, obtain graphene oxide.Other is identical with one of detailed description of the invention one to two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: get the Composite Particles Disperse Phase solution that 10mL step one obtains in step 2 and pour in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 65 DEG C and rotating speed is the condition of 500rpm, is incubated 20h, obtains compounded microbeads.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: get the Composite Particles Disperse Phase solution that 10mL step one obtains in step 2 and pour in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 70 DEG C and rotating speed is the condition of 500rpm, is incubated 24h, obtains compounded microbeads.Other is identical with one of detailed description of the invention one to four.
Adopt following verification experimental verification effect of the present invention:
Test one: this test is the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads, specifically carries out according to the following steps:
One, mixed material wiring solution-forming: be the graphene oxide solution of 1% ~ 1.5%, 0.25g polyvinylpyrrolidone and 0.0714gPdCl by 5g mass fraction
2homogeneous phase mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: get the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 65 DEG C and rotating speed is the condition of 500rpm, is incubated 20h, obtains compounded microbeads; The material of described bulge is polypropylene;
Three, calcine: compounded microbeads step 2 obtained rises to 750 DEG C from room temperature with the heating rate of 5 DEG C/min after taking out from bulge under nitrogen protection; then be incubated 2h under the condition of 750 DEG C and nitrogen protection in temperature, obtain palladium/three-dimensional grapheme compounded microbeads.
Test two: this test is that the palladium/three-dimensional grapheme compounded microbeads adopting test one to prepare carries out electro-catalysis to ethanol: what apply in mensuration electro-catalysis ethanol process is three-electrode system, the electrode that palladium/three-dimensional grapheme compounded microbeads is modified is working electrode, platinum electrode is to electrode, and saturated calomel electrode is reference electrode;
The concentration of alcohol used in test process is 1.0mol/L, the KOH solution that the electrolyte of use is 1.0mol/L.
Fig. 1 is the SEM figure that the palladium/three-dimensional grapheme compounded microbeads of test one preparation amplifies 100 times, as can be seen from Figure 1 palladium/three-dimensional grapheme the compounded microbeads testing a preparation is three-dimensional globular structure and fold pattern, the particle diameter of ball at about 150 μm, the uniform particle diameter of ball;
Fig. 2 is the SEM figure on palladium/three-dimensional grapheme compounded microbeads surface prepared by test one, and bead surface can see a large amount of carbon granules in fig. 2, is formed after firing as the polyvinylpyrrolidone of sticky object;
Fig. 3 is the SEM figure of palladium/three-dimensional grapheme compounded microbeads inside prepared by test one, can see graphene sheet layer fold as seen from Figure 3, can also see a large amount of Pd nano particle of load in microballon inside;
Fig. 4 is the XRD figure of palladium/three-dimensional grapheme compounded microbeads prepared by test one, as can be seen from the figure in the diffraction maximum that 24 ° of appearance one are wider, is the characteristic peak of Graphene; The more sharp-pointed diffraction maximum occurred near 40 ° is (111) peak of palladium; Then consistent with (200) and (220) face of palladium respectively in the little diffraction maximums of 46 ° and 68 ° appearance;
Fig. 5 is palladium/three-dimensional grapheme compounded microbeads that test two adopts test one to prepare carries out electro-catalysis curve to ethanol, the oxidation peak that curve occurs belongs to the oxidation peak of ethanol, higher peak value embodies the catalytic activity that palladium/three-dimensional grapheme compounded microbeads is good, this is because the Graphene of the three-dimensional structure of test one preparation has larger specific area, make contact area between electrode and electrolyte larger, be conducive to the carrying out reacted.
Claims (5)
1. a preparation method for palladium/three-dimensional grapheme compounded microbeads, is characterized in that the preparation method of palladium/three-dimensional grapheme compounded microbeads carries out according to the following steps:
One, mixed material wiring solution-forming: be the graphene oxide solution of 1% ~ 1.5%, 0.25g polyvinylpyrrolidone and 0.0714gPdCl by 5g mass fraction
2homogeneous phase mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: get the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 60 DEG C ~ 70 DEG C and rotating speed is the condition of 500rpm, is incubated 12h ~ 24h, obtains compounded microbeads; The material of described bulge is polypropylene;
Three, calcine: compounded microbeads step 2 obtained rises to 750 DEG C from room temperature with the heating rate of 5 DEG C/min after taking out from bulge under nitrogen protection; then be incubated 2h under the condition of 750 DEG C and nitrogen protection in temperature, obtain palladium/three-dimensional grapheme compounded microbeads.
2. the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads according to claim 1, it is characterized in that in step one by 5g mass fraction be 1% graphene oxide solution, 0.25g polyvinylpyrrolidone and 0.0714gPdCl
2homogeneous phase mixing, obtains Composite Particles Disperse Phase solution.
3. the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads according to claim 1, it is characterized in that the preparation method of the graphene oxide in step one is: the flaky graphite powder getting 1.2g joins in the glass there-necked flask that volume is 500mL, add the concentrated sulfuric acid of 50mL again, glass there-necked flask being put into ice-water bath low whipping speed is stir 30min under the condition of 250r/min, slowly add the potassium permanganate of 10g and the sodium nitrate of 1.5g again, low whipping speed is stir 2h under the condition of 200r/min and ice-water bath, under room temperature and mixing speed are the condition of 250r/min, 2h is stirred after being taken out from ice-water bath by glass there-necked flask, then in temperature be in the water-bath of 35 DEG C and mixing speed be stir 24h under the condition of 250r/min, the mass fraction adding 10mL ~ 15mL is again the hydrogen peroxide solution of 30% and the mass fraction of 10mL is the aqueous hydrochloric acid solution of 36% ~ 38%, obtain thick solution, the method of centrifugation is adopted to isolate solution the thick solution obtained, solution is put into pellicle dialysis to solution for neutral, obtain graphene oxide.
4. the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads according to claim 1, it is characterized in that getting in step 2 the Composite Particles Disperse Phase solution that 10mL step one obtains pours in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 65 DEG C and rotating speed is the condition of 500rpm, is incubated 20h, obtains compounded microbeads.
5. the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads according to claim 1, it is characterized in that getting in step 2 the Composite Particles Disperse Phase solution that 10mL step one obtains pours in syringe, Composite Particles Disperse Phase solution is made to fall into the bulge that 50mL dimethicone is housed with syringe pump pushing syringe, under temperature is 70 DEG C and rotating speed is the condition of 500rpm, is incubated 24h, obtains compounded microbeads.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106549168A (en) * | 2016-10-20 | 2017-03-29 | 哈尔滨工程大学 | The preparation method of the three-dimensional Pd Ni nano-wire array catalyst of catalyzing hydrogen peroxide electroreduction |
| CN106654300A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Method for preparing monodisperse metal atom/graphene composite material employing electrochemical dissolved graphite |
| CN109847776A (en) * | 2018-10-17 | 2019-06-07 | 黑龙江大学 | A kind of photocatalysis membrana and the method for preparing the photocatalysis membrana using vapour deposition process |
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| WO2011066288A2 (en) * | 2009-11-25 | 2011-06-03 | Massachusetts Institute Of Technology | Systems and methods for enhancing growth of carbon-based nanostructures |
| CN103203460A (en) * | 2013-03-14 | 2013-07-17 | 东南大学 | Method for preparing grapheme-Ag nano-particle composite material |
| CN103433037A (en) * | 2013-09-09 | 2013-12-11 | 东南大学 | Preparation method of graphene foam and precious metal nano-particle composite material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011066288A2 (en) * | 2009-11-25 | 2011-06-03 | Massachusetts Institute Of Technology | Systems and methods for enhancing growth of carbon-based nanostructures |
| CN103203460A (en) * | 2013-03-14 | 2013-07-17 | 东南大学 | Method for preparing grapheme-Ag nano-particle composite material |
| CN103433037A (en) * | 2013-09-09 | 2013-12-11 | 东南大学 | Preparation method of graphene foam and precious metal nano-particle composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106549168A (en) * | 2016-10-20 | 2017-03-29 | 哈尔滨工程大学 | The preparation method of the three-dimensional Pd Ni nano-wire array catalyst of catalyzing hydrogen peroxide electroreduction |
| CN106549168B (en) * | 2016-10-20 | 2018-12-11 | 哈尔滨工程大学 | The preparation method of the three-dimensional Pd-Ni nano-wire array catalyst of catalyzing hydrogen peroxide electroreduction |
| CN106654300A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Method for preparing monodisperse metal atom/graphene composite material employing electrochemical dissolved graphite |
| CN109847776A (en) * | 2018-10-17 | 2019-06-07 | 黑龙江大学 | A kind of photocatalysis membrana and the method for preparing the photocatalysis membrana using vapour deposition process |
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