CN104525190B - A kind of preparation method of palladium/three-dimensional grapheme compounded microbeads - Google Patents

A kind of preparation method of palladium/three-dimensional grapheme compounded microbeads Download PDF

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CN104525190B
CN104525190B CN201510001511.XA CN201510001511A CN104525190B CN 104525190 B CN104525190 B CN 104525190B CN 201510001511 A CN201510001511 A CN 201510001511A CN 104525190 B CN104525190 B CN 104525190B
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palladium
compounded microbeads
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dimensional grapheme
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CN104525190A (en
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孙立国
曹晓俭
赵冬梅
汪成
张艳红
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Heilongjiang University
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    • YGENERAL 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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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads, relates to the preparation method of a kind of compounded microbeads.The present invention is to solve that the preparation method preparing palladium/three-dimensional grapheme catalyst at present is the most complex, be not suitable for the technical problem of industrial mass production.A kind of preparation method of the palladium/three-dimensional grapheme compounded microbeads of the present invention be sequentially include the following steps: one, mixing raw material wiring solution-forming;Two, curing molding;Three, calcining.The invention have the advantages that the method novelty of the present invention is unique, simple to operate, process safety is the most environmentally friendly, and the palladium obtained/three-dimensional grapheme compounded microbeads size is controlled, uniform particle diameter, it is one of Perfected process preparing three-dimensional grapheme microballon, is suitable for industrial mass production.

Description

A kind of preparation method of palladium/three-dimensional grapheme compounded microbeads
Technical field
The present invention relates to the preparation method of a kind of compounded microbeads.
Technical background
Graphene is the two-dimensional structure with monoatomic layer thickness, since it is by mechanically pulling off system by Geim first, by In the characteristic of its uniqueness, it is extensively studied at aspects such as catalysis, energy conversion, storage and sensors and has applied.Graphite Alkene has big theoretical specific surface area, high electronic conductivity, good chemical stability and relatively low production cost and is urging Change in reaction owing to partly conjugated structure makes it that substrate is had stronger absorbability thus is used as assisting material.Some researchs Showing, the metal nanoparticle being carried on Graphene is supported on carbon nanometer with those in electro-catalysis and direct-type fuel cell Metal nanoparticle on pipe is compared more excellent catalysis activity and broader practice prospect.In recent years, many researchs refer to Going out in the electroxidation of ethanol or formic acid, palladium catalyst shows, than platinum catalyst, the anti-CO that higher catalysis is active and higher The ability of poisoning.On the basis of first principle calculation, some researchs show, Graphene PZTrack and palladium dZBetween track Electronics hydridization ensure that the existence of abundant pi-electron on Graphene, this causes having between Graphene and palladium the strongest mutual Effect, Graphene is the most weak much with the combination on palladium surface.Obviously, palladium/graphene catalyst shows in a fuel cell Go out the electrocatalysis characteristic of excellence.At present, great majority about the researchs of palladium/graphene catalyst be by electrochemical co-deposition, Palladium is carried on two-dimensional graphene lamella by the method such as in-situ reducing, liquid-phase reduction.
Three-dimensional grapheme, as a kind of novel aggregated structure, has caused everybody great attention.By hydrothermal method, Wu etc. demonstrate Fe3O4Nanometer particle load is having the three-dimensional nitrogen-doped graphene aeroge of interconnective big hole on framework On the all-solid-state supercapacitor of upper and based on three-dimensional nitrogen boron codope monolithic graphite alkene aeroge.The preparation such as Gong Mixed architecture with three-dimensional grapheme as main chain includes MoS2/ Graphene and FeOx/ Graphene.Meng etc. have invented one Unique full Graphene core-shell structure copolymer composite fibre, its mesochite is three-dimensional class mesh structural porous Graphene skeleton shell.By hard template side Method, Choi etc. is by being prepared for three-dimensional macropore graphene film with polystyrene colloid particle as template.Huang etc. are with two Silicon oxide ball has synthesized as pore former and has had controllable grain size (30~120nm) and superelevation pore volume (-4.3cm3·g-1) nanometer many Hole grapheme foam.Being deposited by chemical gaseous phase, Singh etc. has obtained having complete foam network structure and the most controlled Microscopic porosity and the graphene sheet layer of roughness;Bi etc. use foamed nickel catalyst graphene growth to become the Graphene of three-dimensional Network.By the method for template assemblies, Vickery etc. has produced more regular three-dimensional sponge shape macropore support and hollow micron The graphene-polymer nano composite material of size spherical structure.Yin etc. report the self assembly strategy of a kind of expansion and obtain Bionical hierarchical structure, this structure is made up of the graphene sheet layer of functionalization.Xiao etc. illustrate a kind of Novel air electrode, It comprises a kind of uncommon layer functions functionalized graphene with unique double-pore structure.Lee etc. report by graphene oxide Sheet three-dimensional is self-assembled into the carbon film with mechanical tenacity pore structure.Additionally, hard as three dimensional structure surface of PS such as Fan Template, this three dimensional structure has many empty redox graphenes, ruptures, also by thermal decomposition, the reduction-oxidation graphite obtained Alkene and the how empty composite of silicon dioxide.
In in the past few years, the single dispersing microballon that microflow control technique obtains be widely used in preparing three-D photon crystal colloid pearl, Photonic crystal colorimetric sensing film, bio-carrier coding and the multiple monitoring etc. of tumor markers.
The preparation method preparing palladium/three-dimensional grapheme catalyst at present is the most complex, is not suitable for industrial mass production.
Summary of the invention
The present invention is to solve that the preparation method preparing palladium/three-dimensional grapheme catalyst at present is the most complex, be not suitable for industry The technical problem of large-scale production, and the preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads is provided.
The preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads of the present invention is to sequentially include the following steps:
One, mixing raw material wiring solution-forming: by graphene oxide solution that 5g mass fraction is 1%~1.5%, the poly-second of 0.25g Alkene pyrrolidone and 0.0714gPdCl2Uniformly mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: take the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, promote with syringe pump Syringe makes Composite Particles Disperse Phase solution fall in the bulge equipped with 50mL dimethicone, is 60 DEG C~70 DEG C in temperature It is to be incubated 12h~24h under conditions of 500rpm with rotating speed, obtains compounded microbeads;The material of described bulge is poly-third Alkene;
Three, calcining: the compounded microbeads that step 2 is obtained take out from bulge after under nitrogen protection from room temperature with 5 DEG C The heating rate of/min rises to 750 DEG C, is then to be incubated 2h under conditions of 750 DEG C and nitrogen are protected in temperature, obtain palladium/ Three-dimensional grapheme compounded microbeads.
The invention have the advantages that
One, in the polypropylene bulge that step 2 of the present invention uses, polypropylene is a kind of special hydrophobic material, and surface can be low, Composite Particles Disperse Phase solution Di Hebi of non-stick container in high-speed agitating process can be made, and spherical shape can be remained Looks;
Two, the present invention is in high-speed agitating process, uses direct-fired mode that Composite Particles Disperse Phase solution is carried out fast setting, Accelerate the evaporation of moisture in drop, it is possible to make the pattern of drop be fixed at short notice;
Three, the method novelty of the present invention is unique, and simple to operate, process safety is the most environmentally friendly, the palladium/three-dimensional obtained Graphene compounded microbeads size is controlled, uniform particle diameter, is one of Perfected process preparing three-dimensional grapheme microballon, is suitable for industry Large-scale production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of palladium/three-dimensional grapheme compounded microbeads amplification 100 times of test one preparation;
Fig. 2 is the SEM figure on the palladium/three-dimensional grapheme compounded microbeads surface of test one preparation;
Fig. 3 is the figure of the SEM within palladium/three-dimensional grapheme compounded microbeads of test one preparation;
Fig. 4 is the XRD figure of the palladium/three-dimensional grapheme compounded microbeads of test one preparation;
Fig. 5 is the song using the palladium/three-dimensional grapheme compounded microbeads of test one preparation that ethanol carries out electro-catalysis in test two Line.
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 presses Following steps are carried out:
One, mixing raw material wiring solution-forming: by graphene oxide solution that 5g mass fraction is 1%~1.5%, the poly-second of 0.25g Alkene pyrrolidone and 0.0714gPdCl2Uniformly mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: take the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, promote with syringe pump Syringe makes Composite Particles Disperse Phase solution fall in the bulge equipped with 50mL dimethicone, is 60 DEG C~70 DEG C in temperature It is to be incubated 12h~24h under conditions of 500rpm with rotating speed, obtains compounded microbeads;The material of described bulge is poly-third Alkene;
Three, calcining: the compounded microbeads that step 2 is obtained take out from bulge after under nitrogen protection from room temperature with 5 DEG C The heating rate of/min rises to 750 DEG C, is then to be incubated 2h under conditions of 750 DEG C and nitrogen are protected in temperature, obtain palladium/ Three-dimensional grapheme compounded microbeads.
Present embodiment advantage:
One, in the polypropylene bulge that present embodiment step 2 uses, polypropylene is a kind of special hydrophobic material, surface Can be low, Composite Particles Disperse Phase solution Di Hebi of non-stick container in high-speed agitating process can be made, and can remain spherical Pattern;
Two, present embodiment is in high-speed agitating process, uses direct-fired mode to carry out Composite Particles Disperse Phase solution quickly Solidification, accelerates the evaporation of moisture in drop, it is possible to make the pattern of drop be fixed at short notice;
Three, the method novelty of present embodiment is unique, and simple to operate, process safety is the most 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 suitable for Industrial mass production.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: by 5g mass fraction in step one It is graphene oxide solution, 0.25g polyvinylpyrrolidone and the 0.0714gPdCl of 1%2Uniformly mixing, obtains compound point Dephasing solution.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike one of detailed description of the invention one to two: the oxidation in step one The preparation method of Graphene is: the flaky graphite powder taking 1.2g joins in the glass there-necked flask that volume is 500mL, then Add the concentrated sulphuric acid of 50mL, glass there-necked flask is put under conditions of low whipping speed is 250r/min in ice-water bath and stir 30min, is slow added into the potassium permanganate of 10g and the sodium nitrate of 1.5g, and low whipping speed is 200r/min and ice-water bath Under the conditions of stir 2h, after glass there-necked flask is taken out from ice-water bath under conditions of room temperature and mixing speed are 250r/min Stirring 2h, is then stirring 24h under conditions of 250r/min with mixing speed in the water-bath that temperature is 35 DEG C, adds The mass fraction of 10mL~15mL be 30% hydrogen peroxide solution and the hydrochloric acid that mass fraction is 36%~38% of 10mL water-soluble Liquid, obtains thick solution, the method that the thick solution obtained uses centrifugation is isolated solution, is put into by solution In semipermeable membrane, dialysis to solution is neutral, obtains graphene oxide.Other is identical with one of detailed description of the invention one to two.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: take in step 2 The Composite Particles Disperse Phase solution that 10mL step one obtains is poured in syringe, makes composite diffusion mix with syringe pump pushing syringe Liquid falls in the bulge equipped with 50mL dimethicone, protects under conditions of temperature is 65 DEG C and rotating speed is 500rpm Temperature 20h, obtains compounded microbeads.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: take in step 2 The Composite Particles Disperse Phase solution that 10mL step one obtains is poured in syringe, makes composite diffusion mix with syringe pump pushing syringe Liquid falls in the bulge equipped with 50mL dimethicone, protects under conditions of temperature is 70 DEG C and rotating speed is 500rpm Temperature 24h, obtains compounded microbeads.Other is identical with one of detailed description of the invention one to four.
Use 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 sequentially includes the following steps:
One, mixing raw material wiring solution-forming: by graphene oxide solution that 5g mass fraction is 1%~1.5%, the poly-second of 0.25g Alkene pyrrolidone and 0.0714gPdCl2Uniformly mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: take the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, promote with syringe pump Syringe makes Composite Particles Disperse Phase solution fall in the bulge equipped with 50mL dimethicone, temperature be 65 DEG C and turn Speed is insulation 20h under conditions of 500rpm, obtains compounded microbeads;The material of described bulge is polypropylene;
Three, calcining: the compounded microbeads that step 2 is obtained take out from bulge after under nitrogen protection from room temperature with 5 DEG C The heating rate of/min rises to 750 DEG C, is then to be incubated 2h under conditions of 750 DEG C and nitrogen are protected in temperature, obtain palladium/ Three-dimensional grapheme compounded microbeads.
Test two: this test is that the palladium/three-dimensional grapheme compounded microbeads using test one preparation carries out electro-catalysis to ethanol: survey Determine in electro-catalysis ethanol process application is three-electrode system, and the electrode that palladium/three-dimensional grapheme compounded microbeads is modified is work electricity Pole, platinum electrode is to electrode, and saturated calomel electrode is reference electrode;
The concentration of alcohol used in test process is 1.0mol/L, and the electrolyte of use is the KOH solution of 1.0mol/L.
Fig. 1 is the SEM figure of palladium/three-dimensional grapheme compounded microbeads amplification 100 times of test one preparation, can from Fig. 1 Palladium/three-dimensional grapheme the compounded microbeads going out test one preparation is three-dimensional globular structure and fold pattern, and the particle diameter of ball exists About 150 μm, the uniform particle diameter of ball;
Fig. 2 is the SEM figure on the palladium/three-dimensional grapheme compounded microbeads surface of test one preparation, and bead surface is permissible in fig. 2 See substantial amounts of carbon granule, be that the polyvinylpyrrolidone as sticky object is formed after firing;
Fig. 3 is the figure of the SEM within palladium/three-dimensional grapheme compounded microbeads of test one preparation, as seen from Figure 3 at microballon Graphene sheet layer fold can be seen in inside, moreover it is possible to sees the substantial amounts of Pd nano particle of load;
Fig. 4 is the XRD figure of the palladium/three-dimensional grapheme compounded microbeads of test one preparation, as can be seen from the figure goes out at 24 ° An existing wider diffraction maximum, is the characteristic peak of Graphene;The diffraction maximum that the comparison of appearance is sharp-pointed near 40 ° is palladium (111) peak;Consistent with (200) and (220) face of palladium the most respectively 46 ° and the 68 ° little diffraction maximums occurred;
Fig. 5 is the curve that palladium/three-dimensional grapheme compounded microbeads prepared by test two employing test one carries out electro-catalysis to ethanol, The oxidation peak occurred on curve belongs to the oxidation peak of ethanol, and it is good that higher peak value embodies palladium/three-dimensional grapheme compounded microbeads Good catalysis activity, this is because the Graphene of the three dimensional structure of test one preparation has bigger specific surface area so that electrode With between electrolyte, contact area is bigger, is conducive to the carrying out of reaction.

Claims (4)

1. the preparation method of palladium/three-dimensional grapheme compounded microbeads, it is characterised in that the system of palladium/three-dimensional grapheme compounded microbeads Preparation Method is to sequentially include the following steps:
One, mixing raw material wiring solution-forming: by graphene oxide solution that 5g mass fraction is 1%~1.5%, 0.25g polyethylene Ketopyrrolidine and 0.0714gPdCl2Uniformly mixing, obtains Composite Particles Disperse Phase solution;
Two, curing molding: take the Composite Particles Disperse Phase solution that 10mL step one obtains and pour in syringe, promote with syringe pump Syringe makes Composite Particles Disperse Phase solution fall in the bulge equipped with 50mL dimethicone, temperature be 60 DEG C~70 DEG C and Rotating speed is insulation 12h~24h under conditions of 500rpm, obtains compounded microbeads;The material of described bulge is polypropylene;
Three, calcining: the compounded microbeads that step 2 is obtained take out from bulge after under nitrogen protection from room temperature with 5 DEG C The heating rate of/min rises to 750 DEG C, is then incubated 2h under conditions of temperature is 750 DEG C and nitrogen is protected, obtains palladium/tri- Dimension Graphene compounded microbeads.
The preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads the most according to claim 1, it is characterised in that step By graphene oxide solution, 0.25g polyvinylpyrrolidone and 0.0714gPdCl that 5g mass fraction is 1% in one2The most mixed Close, obtain Composite Particles Disperse Phase solution.
The preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads the most according to claim 1, it is characterised in that step Take the Composite Particles Disperse Phase solution that 10mL step one obtains in two and pour in syringe, make compound point with syringe pump pushing syringe Dephasing solution falls in the bulge equipped with 50mL dimethicone, and being 65 DEG C in temperature is the bar of 500rpm with rotating speed It is incubated 20h under part, obtains compounded microbeads.
The preparation method of a kind of palladium/three-dimensional grapheme compounded microbeads the most according to claim 1, it is characterised in that step Take the Composite Particles Disperse Phase solution that 10mL step one obtains in two and pour in syringe, make compound point with syringe pump pushing syringe Dephasing solution falls in the bulge equipped with 50mL dimethicone, and being 70 DEG C in temperature is the bar of 500rpm with rotating speed It is incubated 24h under part, obtains compounded microbeads.
CN201510001511.XA 2015-01-04 2015-01-04 A kind of preparation method of palladium/three-dimensional grapheme compounded microbeads Expired - Fee Related CN104525190B (en)

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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
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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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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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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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