CN105013490A - Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof - Google Patents
Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and an electrochemical catalysis application of a metal nanoparticle-foamy carbon catalyst. The preparation method comprises the following steps: (1) a polymerizable vinyl monomer is adopted as an oil phase, a metal precursor-containing water solution is adopted as a water phase, functional polymer nanoparticles are adopted as an emulsifier, and a stable high-internal-phase Pickering emulsion is prepared; (2) the oil phase is polymerized and the internal phase is removed with a radical polymerization method, such that a polymerized high-internal-phase foam material is obtained; (3) the metal ion precursor in the polymerized high-internal-phase foam is reduced into metal nanoparticles, such that a metal nanoparticle-polymer form hybrid material is obtained; (4) high-temperature calcination is further carried out under a nitrogen atmosphere, such that a metal nanoparticle-foamy carbon hybrid material is obtained; and (5) the above material is loaded on a clean glassy carbon electrode, and electrochemical catalytic application can be carried out. The metal nanoparticle-foamy carbon catalyst preparation method has the advantages of simple process and low equipment requirement. The obtained material has good conductivity and large specific surface area. The material has a good catalytic effect in the aspect of electrochemistry.
Description
Technical field
The present invention relates to metal nanoparticle-foamy carbon Catalysts and its preparation method and purposes, belong to high performance carbon hybrid material preparations and applicatio field, be specially preparation and the electrochemical catalysis application of metal nanoparticle-foamy carbon catalyst.
Background technology
Carbon foam is a kind of is skeleton with carbon atom, mutually piles up the solid material with carbon element of lightweight of the porous network structure formed between carbon atom.Carbon foam is with its larger specific area, and the characteristics such as higher porosity and lower thermal coefficient of expansion, all have broad application prospects in fields such as battery electrode, electrochemical capacitor, heat control material, catalyst carriers.
The preparation method of current foamy carbon comprises the methods such as foaming, sol-gel process, Pocofoam method, template and inversion phase method.These methods respectively have superiority, simultaneously also Shortcomings.Such as, be raw material with pitch, the foamy carbon good heat conductivity utilizing foaming to prepare, but in order to good structure can be kept in carbonisation, must be oxidized foams before charing.This makes the technique preparing carbon foam become complicated, consuming time and expensive.
Foamy carbon, because specific area is large, good chemical stability, is usually used in catalyst carrier.Carrying metal particles on foamy carbon, the general method adopting dipping reduction.Immersion reduction method is dispersed in the solution of metal precursor by carrier foamy carbon, then excessive reducing agent is added as sodium borohydride, hydrazine hydrate etc., make metallic precursor be reduced to metal nanoparticle and be deposited on foamy carbon carrier, again after filtration, washing, the method such as dry, prepare metal nanoparticle-foamy carbon hybrid material.Immersion reduction method low consumption simple to operate, economic, environmental protection, is widely used in loaded catalyst, especially the noble metal carrier catalyst of low content.But the metal particle diameter that this method prepares is wayward, and domain size distribution is wide; In preparation process, metal loss is comparatively large, and due on carbon skeleton without the group of stable metal nano particle, easily cause catalyst to come off in using.Carbon deposition on nickel foam skeleton, is prepared grapheme foam carbon by recent researcher employing chemical vapour deposition technique.Then with the carbon foam obtained for carrier, utilize electrochemical deposition method to plate one deck Mn
3o
4, obtain metal oxide-foamy carbon composite.This material can be used for preparing the very high non-enzyme biologic sensor of sensitivity.But the instrument and equipment that this method needs price high, preparation process are loaded down with trivial details, technics comparing is complicated, the problems such as structure is wayward.
Pickering emulsion refers to the emulsion obtained as emulsifying agent using ultrafine particle.Ultra-fine solid particle can be used as oil-in-water or water-in-oil emulsifier.Which phase preferential wetting solid particle is the type of gained emulsion depend on, a phase of usual preferential wetting solid particle is foreign minister.As solid particle sometimes more easily soak by oil phase, emulsion is W/O (Water-In-Oil) type; Otherwise, as solid particle more easily soak by aqueous phase, emulsion is O/W (oil-in-water) type.Pressed powder as emulsifying agent has clay, silica, metal hydroxides, graphite, carbon black, polymer particle etc.The stability of emulsion is relevant with the concentration of solid particle, granular size, wetability etc.
Summary of the invention
The invention reside in and propose a kind ofly prepare the preparation method of metal nanoparticle-foamy carbon catalyst and be applied to electrochemical catalysis, catalyst preparing has the advantages such as equipment requirement is low, technique is simple.The present invention with vinyl monomer with di-vinyl monomers for mixing oil phase, there is the polymer nano-particle of complexation of metal ions and stable metal particle ability for emulsifying agent, the metallic precursor aqueous solution be interior phase height in phase Pickering emulsion be template, through polymerization, washing, reduction and calcination process, prepare metal nanoparticle-foamy carbon hybrid material.Then by the hybrid material modified electrode of preparation, electrochemical catalysis is applied to.
According to the first embodiment of the present invention, there is provided a kind of metal nanoparticle-foamy carbon hybrid material, it is that a kind of method by comprising following process obtains: 1) added to by emulsifying agent in the monomer mixture formed by the vinyl monomer as single functionality function monomer and the di-vinyl monomers as polyfunctionality cross-linking monomer to be formed and mix oil phase; 2) the metal precursor aqueous solution (mass fraction of metal precursor is 0.001 ~ 0.5wt%, preferred 0.005wt%) is added in above-mentioned mixing oil phase form emulsion (such as forming phase Pickering emulsion in height that internal phase volume mark is 75%-90% (preferred 75-85%)); 3) (such as by adding initator in emulsion, being preferably oil-soluble initiator) oil phase caused in emulsion carries out polymerisation, obtains perforated foams; 4) by obtained perforated foams organic solvent (as methyl alcohol or ethanol) extracting and purifying and drying to obtain dry perforated foams; 5) obtained perforated foams reducing agent is reduced in organic solvent (as oxolane), obtain metal nanoparticle-porous foam hybrid material; 6) by above step 5) in metal nanoparticle-perforated foams of obtaining carry out calcining (such as in inert atmosphere (as nitrogen or helium), in 700-1000 DEG C, more preferably calcining at 800-950 DEG C), obtain final metal nanoparticle-foamy carbon hybrid material.
According to the second embodiment of the present invention, the electrode providing a kind of hybrid material to modify or a kind of metallic nanoparticle-foamy carbon catalyst, it is obtained by following steps: by metal nanoparticle-foamy carbon hybrid material load on glass-carbon electrode, its load capacity is 70-210ug/ electrode, obtains metallic nanoparticle-foamy carbon catalyst.Such as, by obtained metal nanoparticle-foamy carbon hybrid material ultrasonic disperse in a solvent, load is on clean glass-carbon electrode, and its load capacity is 70-210ug, obtains metallic nanoparticle-foamy carbon catalyst.Wherein, reference electrode is saturated calomel electrode, and be nickel foam to electrode, electrolyte is sodium hydroxide/sodium borohydride solution, and in electrolyte, the molar concentration rate of NaOH and sodium borohydride is 10:1-120:1, preferably 20:1-60:1.
According to the third embodiment the present invention, provide a kind of method preparing metal nanoparticle-foamy carbon hybrid material, the method comprises the following steps:
1) emulsifying agent is added in the monomer mixture formed by the vinyl monomer as single functionality function monomer and the divinyl compound as polyfunctionality cross-linking monomer to be formed and mix oil phase;
2) the metal precursor aqueous solution (mass fraction of metal precursor is 0.001 ~ 0.5wt%, preferred 0.005wt%) is added in above-mentioned mixing oil phase form emulsion (such as forming phase Pickering emulsion in height that internal phase volume mark is 75%-90% (preferred 75-85%));
3) oil phase caused in emulsion carries out polymerisation (such as by adding initator in emulsion, to be preferably oil-soluble initiator), obtains perforated foams;
4) by obtained perforated foams organic solvent (as methyl alcohol or ethanol) extracting and purifying and drying to obtain dry perforated foams;
5) obtained perforated foams reducing agent is carried out reduction in organic solvent (as oxolane) and obtain metal nanoparticle-perforated foams; With
6) by above step 5) in metal nanoparticle-perforated foams of obtaining carry out calcining (such as in inert atmosphere (as nitrogen or helium), in 700-1000 DEG C, more preferably calcining at 800-950 DEG C), obtain final metal nanoparticle-foamy carbon hybrid material.
According to the 4th embodiment of the present invention, there is provided a kind of and prepare the electrode of hybrid material modification or a kind of method preparing metal nanoparticle-foamy carbon catalyst, the method comprises: 7) by the step 6 of above method) the middle metal nanoparticle-foamy carbon hybrid material load obtained is on glass-carbon electrode, and its load capacity is 70-210ug/ electrode.Such as, by obtained metal nanoparticle-foamy carbon hybrid material ultrasonic disperse in a solvent, load is on clean glass-carbon electrode, and its load capacity is 70-210ug, obtains metallic nanoparticle-foamy carbon catalyst.Wherein, reference electrode is saturated calomel electrode, and be nickel foam to electrode, electrolyte is sodium hydroxide/sodium borohydride solution, and in electrolyte, the molar concentration rate of NaOH and sodium borohydride is 10:1-120:1, preferably 20:1-60:1.
In above-mentioned first, the 3rd embodiment or in this application, preferably, in above-mentioned steps 2) in, be inside the aqueous solution containing metal precursor (or containing metal ion) mutually, the concentration of metal ion (or metal precursor) is 0.005wt%-0.03wt%, preferably 0.01wt%-0.02wt% in aqueous.
Metal precursor is transistion metal compound.Transition metal wherein in transistion metal compound is palladium, platinum, zirconium, hafnium, scandium or titanium.
Preferably, transistion metal compound is chlorine palladium acid H
2pdCl
4or ammonium chloropalladate salt (NH
4)
2pdCl
4, chloroplatinic acid H
2ptCl
6or chloroplatinic acid ammonium salt (NH
4)
2ptCl
6, the acid of chlorine hafnium or chlorine hafnium acid ammonium salt.
In step 1) in, emulsifying agent is or comprises polymer beads subtype emulsifying agent.Emulsifying agent is more preferably the polymer nano-particle of the average grain diameter with 3-80nm (more preferably 8-60nm, more preferably 12-50nm).Emulsifier is the 0.055wt%-0.22wt% of oil phase amount, preferred 0.08wt%-0.15wt%.Preferably, contain can with metal-complexing and can the construction unit of stable metal particle for polymer-type emulsifying agent.The agent of Pickering emulsion emulsifiers is polymer nano-particle.More preferably, polymer-type emulsifying agent is the copolymer of vinylpyridine or vinyl pyrrolidone, the copolymer of such as 4-vinylpridine or vinyl pyrrolidone and methyl methacrylate (MMA); Generally, it has the average grain diameter of 3-80nm (more preferably 8-60nm, more preferably 12-50nm).
Step 3 at said method) in need to add initator phase Pickering emulsion in height is transformed into polymerization high in phase Pickering emulsion.The initator added is oil-soluble initiator, and such as oil-soluble radical closes initator, as azo compound or peroxide compound.The consumption of initator is the 1%-3% (wt) of amount of monomer.
Reducing agent is, such as, and sodium borohydride, potassium borohydride, hydrazine hydrate or polyol compound.Reducing metal ions can be metallic by reducing agent.
In this application, preferably, the vinyl monomer as single functionality function monomer is styrene, substituted phenylethylene, esters of acrylic acid [such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate], acrylonitrile or their mixture.Divinyl compound (or being called di-vinyl monomers) as polyfunctionality cross-linking monomer is divinylbenzene, GDMA, ethylene glycol diacrylate, dimethyl allene acid propylene glycol ester, diacrylate propylene glycol ester, dimethacrylate tetramethylene glycol ester, diacrylate tetramethylene glycol ester, dimethacrylate pentadiol ester, diacrylate pentadiol ester, dimethacrylate hexylene glycol ester, hexanediol diacrylate.
Generally, for mixing oil phase, polyfunctionality cross-linking monomer: the mixed volume of single functionality function monomer, than being 0.2:1.8-1.8:0.2, is preferably 0.5:1.7-1.6:0.5, more preferably 0.6:1.6-1.2:0.7, more preferably 0.7:1.5-1.0:0.1.
Generally, polymer need be sintered into carbon under inert atmosphere (as nitrogen atmosphere).Suitable calcining heat is 700-1000 DEG C, more preferably 800-950 DEG C.In calcination process, heating rate is 1-5 DEG C/min, temperature retention time 90min-150min.
In this application, step 2) in aqueous phase is added drop-wise in oil phase forms emulsion under agitation, mixing speed is 1000-6000rpm.
More particularly, described method of the present invention comprises:
(1) preparation of high interior phase Pickering emulsion
A, mixed volume are than being polyfunctionality cross-linking monomer: single functionality function monomer=0.2:1.8-1.8:0.2 is mixing oil phase
B, emulsifying agent is dissolved in mixing oil phase with the 0.055%-0.22% content relative to oil phase mass fraction
C, metallic precursor is soluble in water
Metallic precursor solution slowly joins in oil phase by d, under agitation (1000rpm ~ 6000rpm), forms high interior phase Pickering emulsion (internal phase volume mark is 75%-90%)
2) preparation of, metal nanoparticle-foamy carbon catalyst
A, in phase Pickering emulsion in the height prepared, add a certain amount of initator, cause the polymerization of oil phase at a certain temperature;
B, by obtained perforated foams solvent extraction, drying under reduced pressure;
C, the metal nanoparticle-polymeric foam prepared is placed in solvent, adds reducing agent reduction, filter, washing, dry;
D, dried perforated foams is placed in tube furnace calcines under certain condition, obtain required metal nanoparticle-foamy carbon hybrid material.
E, by obtained metal nanoparticle-foamy carbon hybrid material ultrasonic disperse in a solvent, load is on clean glass-carbon electrode, and its load capacity is 70-210ug/ electrode, obtains metallic nanoparticle-foamy carbon catalyst.
In general, in above-mentioned steps d, before being calcined or before carbonization, the mean cell diameter size of dried polymer foams is 100-250 μm, and preferred 120-200 μm, as 160 μm.After calcining rear or carbonization, the mean cell diameter size of foam of polymers carbon hybrid material is 20-90 μm, and preferred 40-80 μm, as 60 μm.
In foamy carbon hybrid material, the mass fraction of metallic is 0.15 ~ 1.5wt%, preferably 0.20 ~ 1.2wt%, more preferably 0.27 ~ 0.81wt%.
The catalyst that the present invention obtains is in electrochemical applications.
Metal nanoparticle provided by the invention/foamy carbon composite has the following advantages:
Compared with the preparation of other metallics-foamy carbon catalyst, the present invention has following beneficial effect:
1. the present invention prepares that foamy carbon technique is simple, equipment requirement is low.
2. metallic presoma is incorporated in polymer foams by the interaction between polymer emulsifier particle and metallic by the present invention, introduces functional group without the need to any chemical processing process, can the single or various metals particle alloy of load.
3. Inventive polymers emulsifying agent particle through calcining after pore-forming, therefore metal nanoparticle original position can be loaded to foamed material formed micropore or mesoporous in.
4. after calcining, foamy carbon specific area is large, chemical stability good and have certain electric conductivity, and therefore catalyst material electrochemical catalysis activity is good.
Accompanying drawing explanation
Fig. 1 is the metal nanoparticle-foam hybrid material SEM photo of embodiment 1.
Fig. 2 is metal nanoparticle-foamy carbon hybrid material (calcining heat is 1000 DEG C) the SEM photo of embodiment 1.
Fig. 3 is the metal nanoparticle-foamy carbon hybrid material catalyzing N aBH of embodiment 1
4electrochemical oxidation cyclic voltammetry curve.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.
The preparation method of metal nanoparticle-foamy carbon catalyst is provided in the following embodiments, it is characterized in that with phase Pickering emulsion template method preparation in Water-In-Oil height.In high, the internal phase volume mark of phase Pickering emulsion is 75%-90%.
Be inside the aqueous solution of containing metal precursor mutually, the concentration of metal ion is 0.005%-0.02%.
Foreign minister consists of polymerisable vinyl monomer and di-vinyl monomers mixture.Vinyl monomer comprises styrene, substituted phenylethylene, methyl methacrylate, methyl acrylate, acrylonitrile or their mixture.Di-vinyl monomers can be divinylbenzene, GDMA or mixture both it.
In the emulsion formed, add radical polymerization initiator phase Pickering emulsion in height is become phase Pickering emulsion in polymerization height.The initator added is that oil-soluble radical closes initator, comprises azo compound or peroxide compound.The consumption of initator is the 1%-3% of amount of monomer.
The agent of Pickering emulsion emulsifiers is polymer particle.Require in polymer composition containing can with metallic ion coordination and can the construction unit of stable metal particle.Emulsifier is the 0.055%-0.22% of oil phase quality.
Polymer particle is preferably the particle of the copolymer of vinylpyridine or vinyl pyrrolidone.
In order to form phase Pickering emulsion in Water-In-Oil height, need to be added drop-wise in oil phase by aqueous phase under agitation to be formed, mixing speed is 1000-6000rpm.
Adopt reducing agent, as sodium borohydride, reducing metal ions is metallic by hydrazine hydrate or polyol compound.
Polymer needs high-temperature calcination under nitrogen atmosphere to become carbon.The temperature of polymer calcining is looked polymer composition and is determined.Suitable calcining heat is 700-1000 DEG C, and heating rate is 1-5 DEG C/min, temperature retention time 90min-150min.
The metal nanoparticle formed-foamy carbon catalyst, metallic is 70-210ug in the load capacity of glass-carbon electrode, reference electrode is saturated calomel electrode, be nickel foam to electrode, electrolyte is sodium hydroxide/sodium borohydride solution, and in electrolyte, the molar concentration rate of NaOH and sodium borohydride is 10:1-120:1.
Embodiment 1
Main material-the polymer nano-particle used in the present embodiment: polymethyl methacrylate-b-P4VP (PMMA
2250-b-P4VP
286, footmark represents the degree of polymerization, Mw/Mn=1.13) and be purchased from Polymer Source company.In DMF solvent, add propargyl bromide obtain through intramolecular crosslinking.Average grain diameter 12 nanometer.
The preparation process of the present embodiment metal nanoparticle/foamy carbon composite is specific as follows: polymer nano-particle raw material (the single molecular chain head-tail structure by average grain diameter being 12nm, tail is line style PMMA polymer, head is crosslinked P4VP polymer, wherein P4VP represents poly 4 vinyl pyridine), be dissolved in divinylbenzene and acrylonitrile mixed system.Divinylbenzene: acrylonitrile volume ratio is 9:1, polymer nano-particle is 0.16% relative to oil phase mass fraction.Under the condition stirring (1000rpm), the aqueous solution (mass fraction is 0.005%) of chlorine palladium acid metal precursor is slowly dropped in oil phase, formed internal phase volume mark be 75% height in phase Pickering emulsion.Add relative to oil phase mass fraction be 1.5% initiator A IBN, cause at 60 DEG C oil phase polymerization, obtain polymer foams.By obtained polymer foams as in tetrahydrofuran solvent, add 1ml hydrazine hydrate, at 50 DEG C of reaction 6h.After filtration, the extracting of product absolute methanol, then drying obtain metal nanoparticle-foam of polymers hybrid material.Obtained metal nanoparticle-foam of polymers hybrid material is placed in tube furnace and carries out carbonization treatment further at nitrogen atmosphere, tube furnace Carbonization Conditions is: heating rate is 5 DEG C/min, calcining heat 800 DEG C, temperature retention time 120min.Carbonization treatment is complete can obtain metal nanoparticle-foamy carbon hybrid material.By metal nanoparticle-foamy carbon hybrid material load at glass-carbon electrode, its load capacity is 100ug, and reference electrode is saturated calomel electrode, is nickel foam to electrode, and electrolyte is sodium hydroxide/sodium borohydride solution, and concentration ratio is 30:1, carries out electro-chemical test.
As shown in fig. 1, before being calcined or before carbonization, the mean cell diameter size of dried polymer foams is 158.94 μm.As shown in Figure 2, after carbonization, the mean cell diameter size of foam of polymers carbon hybrid material is 59.95 μm
In foamy carbon hybrid material, the mass fraction of metallic is 0.64wt%.
Fig. 3 is the metal nanoparticle-foamy carbon hybrid material catalyzing N aBH of the present embodiment 1
4electrochemical oxidation cyclic voltammetry curve.
Embodiment 2
The preparation process of the present embodiment metal nanoparticle/foamy carbon composite is specific as follows: take relative to oil phase mass fraction be 0.16% monochain polymer nano particle PMMA-b-P4VP, being dissolved in volume ratio is divinylbenzene: the mixing oil phase of acrylonitrile=1:9, is stirred to solution transparent.Preparation mass fraction is the chlorine palladium acid metal precursor aqueous solution of 0.005%.Under the condition of the stirring of 1000rpm, the aqueous solution being dissolved with chlorine palladium acid metal precursor is slowly dropped in oil phase, formed internal phase volume mark be 75% height in phase Pickering emulsion.Add relative to oil phase mass fraction be 1.5% initiator A IBN, at 60 DEG C, cause the polymerization of oil phase, formed polymeric foam.By obtained polymeric foam as in tetrahydrofuran solvent, add 1ml hydrazine hydrate, at 50 DEG C of reaction 6h, make the metallic precursor of load on foamed material be reduced to metal nanoparticle.Metal nanoparticle-foam of polymers hybrid material is obtained after extracting, drying.Obtained metal nanoparticle-foam of polymers hybrid material is placed in tube furnace and carries out carbonization treatment further, tube furnace Carbonization Conditions is: heating rate is 5 DEG C/min, calcining heat 1000 DEG C, temperature retention time 120min.Carbonization treatment is complete can obtain metal nanoparticle-foamy carbon hybrid material.By metal nanoparticle-foamy carbon hybrid material load at glass-carbon electrode, its load capacity is 100ug, and reference electrode is saturated calomel electrode, is nickel foam to electrode, and electrolyte is sodium hydroxide/sodium borohydride solution, and concentration ratio is 30:1, carries out electro-chemical test.
After calcining rear or carbonization, the mean cell diameter size of foam of polymers carbon hybrid material is 55 μm.
In foamy carbon hybrid material, the mass fraction of metallic is 0.56wt%.
Embodiment 3
The preparation process of the present embodiment metal nanoparticle/foamy carbon composite is specific as follows: take relative to oil phase mass fraction be 0.22% monochain polymer nano particle PMMA-b-P4VP, being dissolved in volume ratio is divinylbenzene: the mixing oil phase of acrylonitrile=9:1, is stirred to solution transparent.Preparation mass fraction is the chlorine palladium acid metal precursor aqueous solution of 0.005%.Under the condition of the stirring of 1000rpm, the aqueous solution being dissolved with chlorine palladium acid metal precursor is slowly dropped in oil phase, formed internal phase volume mark be 75% height in phase Pickering emulsion.Add relative to oil phase mass fraction be 1.5% initiator A IBN, at 60 DEG C, cause the polymerization of oil phase, formed polymeric foam.By obtained polymeric foam as in tetrahydrofuran solvent, add the hydrazine hydrate of 1ml, at 50 DEG C of reaction 6h, make the metallic precursor of load on foamed material be reduced to metal nanoparticle.Metal nanoparticle-foam of polymers hybrid material is obtained after extracting, drying.Obtained metal nanoparticle-foam of polymers hybrid material is placed in tube furnace and carries out carbonization treatment further, tube furnace Carbonization Conditions is: heating rate is 5 DEG C/min, calcining heat 800 DEG C, temperature retention time 120min.Carbonization treatment is complete can obtain metal nanoparticle-foamy carbon hybrid material.By metal nanoparticle-foamy carbon hybrid material load at glass-carbon electrode, its load capacity is 100ug, and reference electrode is saturated calomel electrode, is nickel foam to electrode, and electrolyte is sodium hydroxide/sodium borohydride solution, and concentration ratio is 30:1, carries out electro-chemical test.
After calcining rear or carbonization, the mean cell diameter size of foam of polymers carbon hybrid material is 43 μm.
In foamy carbon hybrid material, the mass fraction of metallic is 0.48wt%.
Claims (10)
1. metal nanoparticle-foamy carbon hybrid material, it is that a kind of method by comprising following process obtains: 1) added to by emulsifying agent in the monomer mixture formed by the vinyl monomer as single functionality function monomer and the divinyl compound as polyfunctionality cross-linking monomer to be formed and mix oil phase; 2) the metal precursor aqueous solution (mass fraction of metal precursor is 0.001 ~ 0.5wt%, preferred 0.005wt%) is added in above-mentioned mixing oil phase form emulsion (such as forming phase Pickering emulsion in height that internal phase volume mark is 75%-90% (preferred 75-85%)); 3) (such as by adding initator in emulsion, being preferably oil-soluble initiator) oil phase caused in emulsion carries out polymerisation, obtains perforated foams; 4) by obtained perforated foams organic solvent (as methyl alcohol or ethanol) extracting and purifying and drying to obtain dry perforated foams; 5) the perforated foams reducing agent of obtained carried metal presoma is reduced in organic solvent (as oxolane), obtain metal nanoparticle-porous foam hybrid material; 6) carburising step: by above step 5) in metal nanoparticle-porous foam hybrid material of obtaining carry out calcining (such as in inert atmosphere (as nitrogen or helium), in 700-1000 DEG C, more preferably calcining at 800-950 DEG C), obtain final metal nanoparticle-foamy carbon hybrid material.
2. material according to claim 1, wherein in step 6) in before carbonization, the mean cell diameter size of dried polyalcohol stephanoporate foamed material is 100-250 μm, and preferred 120-200 μm, as 160 μm; And calcining is rear or after carbonization, the mean cell diameter size of foam of polymers carbon hybrid material is 20-90 μm, preferred 40-80 μm, as 60 μm.
3. material according to claim 1 and 2, wherein, in foamy carbon hybrid material, the mass fraction of metallic is 0.15 ~ 1.5wt%, preferably 0.20 ~ 1.2wt%, more preferably 0.27 ~ 0.81wt%.
4. metallic nanoparticle-foamy carbon catalyst, it is obtained by following steps: by metal nanoparticle-foamy carbon hybrid material load of obtaining in claim 1-3 on glass-carbon electrode, its load capacity is 70-210ug/ electrode, obtains metal nanoparticle-foamy carbon catalyst; Preferably, described catalyst is obtained by following steps: by metal nanoparticle-foamy carbon hybrid material ultrasonic disperse of obtaining in claim 1-3 in a solvent, load is on clean glass-carbon electrode, its load capacity is 70-210ug, obtains metal nanoparticle-foamy carbon catalyst; Preferably, reference electrode is saturated calomel electrode, and be nickel foam to electrode, electrolyte is sodium hydroxide/sodium borohydride solution, and in electrolyte, the molar concentration rate of NaOH and sodium borohydride is 10:1-120:1, preferably 20:1-60:1).
5. prepare a method for metal nanoparticle-foamy carbon hybrid material, the method comprises the following steps:
1) emulsifying agent is added in the monomer mixture formed by the vinyl monomer as single functionality function monomer and the divinyl compound as polyfunctionality cross-linking monomer to be formed and mix oil phase;
2) the metal precursor aqueous solution (mass fraction of metal precursor is 0.001 ~ 0.5wt%, preferred 0.005wt%) is added in above-mentioned mixing oil phase form emulsion [such as forming phase Pickering emulsion in height that internal phase volume mark is 75%-90% (preferred 75-85%)];
3) oil phase caused in emulsion carries out polymerisation (such as by adding initator in emulsion, to be preferably oil-soluble initiator), obtains perforated foams;
4) by obtained perforated foams organic solvent (as methyl alcohol or ethanol) extracting and purifying and drying to obtain dry perforated foams;
5) obtained perforated foams reducing agent is reduced in organic solvent (as oxolane), obtain metal nanoparticle-perforated foams; With
6) by above step 5) in metal nanoparticle-perforated foams of obtaining carry out calcining (such as in inert atmosphere (as nitrogen or helium), in 700-1000 DEG C, more preferably calcining at 800-950 DEG C), obtain final metal nanoparticle-foamy carbon hybrid material.
6. method according to claim 5, wherein in step 1) in, emulsifying agent is or comprises polymer beads subtype emulsifying agent; Be more preferably the polymer nano-particle of the average grain diameter with 3-80nm (more preferably 8-60nm, more preferably 12-50nm); Further preferably, polymer beads subtype emulsifying agent is the copolymer of the copolymer of vinylpyridine or vinyl pyrrolidone, such as 4-vinylpridine or vinyl pyrrolidone and methyl methacrylate (MMA); Preferably, emulsifier is the 0.055wt%-0.22wt% of oil phase amount, preferred 0.08wt%-0.15wt%.
7. the method according to claim 5 or 6, wherein in above-mentioned steps 2) in, be inside the aqueous solution of metal precursor mutually, the concentration of metal ion is 0.005wt%-0.03wt%, preferably 0.01wt%-0.02wt% in aqueous;
Preferably, metal precursor is transistion metal compound, and the transition metal wherein in transistion metal compound is palladium, platinum, zirconium, hafnium, scandium or titanium; More preferably, transistion metal compound is chlorine palladium acid H
2pdCl
4or ammonium chloropalladate salt (NH
4)
2pdCl
4, chloroplatinic acid H
2ptCl
6or chloroplatinic acid ammonium salt (NH
4)
2ptCl
6, the acid of chlorine hafnium or chlorine hafnium acid ammonium salt.
8., according to the method in claim 5-7 described in any one, the vinyl monomer wherein as single functionality function monomer is styrene, substituted phenylethylene, esters of acrylic acid [such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate], acrylonitrile or their mixture; And/or,
Divinyl compound (or being called di-vinyl monomers) as polyfunctionality cross-linking monomer is divinylbenzene, GDMA, ethylene glycol diacrylate, dimethyl allene acid propylene glycol ester, diacrylate propylene glycol ester, dimethacrylate tetramethylene glycol ester, diacrylate tetramethylene glycol ester, dimethacrylate pentadiol ester, diacrylate pentadiol ester, dimethacrylate hexylene glycol ester, hexanediol diacrylate; And/or
In mixing oil phase, polyfunctionality cross-linking monomer: the mixed volume of single functionality function monomer, than being 0.2:1.8-1.8:0.2, is preferably 0.5:1.7-1.6:0.5, more preferably 0.6:1.6-1.2:0.7, more preferably 0.7:1.5-1.0:0.1.
9. according to the method in claim 5-8 described in any one, wherein in the step 3 of said method) in initator be oil-soluble radical close initator, as azo compound or peroxide compound; Preferably, the consumption of initator is the 1%-3% (wt) of amount of monomer; And/or
The reducing agent used is sodium borohydride, potassium borohydride, hydrazine hydrate or polyol compound; And/or
Step 6) in calcining heat be 700-1000 DEG C, more preferably 800-950 DEG C, and in calcination process, heating rate is 1-5 DEG C/min, temperature retention time 90min-150min.
10. prepare a method for metal nanoparticle-foamy carbon catalyst, the method comprises: the step 6 by claim 5) the middle metal nanoparticle-foamy carbon hybrid material load obtained is on glass-carbon electrode, and its load capacity is 70-210ug/ electrode; More preferably, described method comprises: the step 6 by claim 5) the middle metal nanoparticle-foamy carbon hybrid material ultrasonic disperse obtained is in a solvent, load is on clean glass-carbon electrode, and its load capacity is 70-210ug, obtains metallic nanoparticle-foamy carbon catalyst; Preferably, reference electrode is saturated calomel electrode, and be nickel foam to electrode, electrolyte is sodium hydroxide/sodium borohydride solution, and in electrolyte, the molar concentration rate of NaOH and sodium borohydride is 10:1-120:1, preferably 20:1-60:1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108470916A (en) * | 2018-02-07 | 2018-08-31 | 深圳大学 | It is a kind of using three-dimensional porous carbon material as the fuel cell oxygen reduction catalyst of raw material and preparation method |
| CN108607570A (en) * | 2016-12-12 | 2018-10-02 | 北京化工大学 | A kind of foam carbon-supported catalysts and its preparation method and application |
| CN109529770A (en) * | 2018-12-29 | 2019-03-29 | 中国科学院兰州化学物理研究所 | A method of porous carbon adsorbent material is prepared as template using the Pickering lotion that semicoke is stable |
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| CN111420676A (en) * | 2020-03-17 | 2020-07-17 | 中国石油大学(北京) | Inorganic-organic hybrid metal super-particle and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167556A (en) * | 2014-08-19 | 2014-11-26 | 刘昊 | Air electrode of lithium air battery, preparation method of air electrode and lithium air battery |
| CN104361996A (en) * | 2014-10-16 | 2015-02-18 | 大连交通大学 | Preparation method for directly generating manganese dioxide on surface of substrate |
| CN104607120A (en) * | 2014-10-16 | 2015-05-13 | 江南大学 | Particulate emulsifier based on cyclomatrix-type polyphosphazene microspheres, and preparation method thereof |
| CN104710554A (en) * | 2015-01-05 | 2015-06-17 | 泰山医学院 | Preparation method of interpenetrating network porous polymer composite material |
-
2015
- 2015-07-03 CN CN201510385895.XA patent/CN105013490B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167556A (en) * | 2014-08-19 | 2014-11-26 | 刘昊 | Air electrode of lithium air battery, preparation method of air electrode and lithium air battery |
| CN104361996A (en) * | 2014-10-16 | 2015-02-18 | 大连交通大学 | Preparation method for directly generating manganese dioxide on surface of substrate |
| CN104607120A (en) * | 2014-10-16 | 2015-05-13 | 江南大学 | Particulate emulsifier based on cyclomatrix-type polyphosphazene microspheres, and preparation method thereof |
| CN104710554A (en) * | 2015-01-05 | 2015-06-17 | 泰山医学院 | Preparation method of interpenetrating network porous polymer composite material |
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|---|---|---|---|---|
| CN108607570A (en) * | 2016-12-12 | 2018-10-02 | 北京化工大学 | A kind of foam carbon-supported catalysts and its preparation method and application |
| CN108470916A (en) * | 2018-02-07 | 2018-08-31 | 深圳大学 | It is a kind of using three-dimensional porous carbon material as the fuel cell oxygen reduction catalyst of raw material and preparation method |
| CN108470916B (en) * | 2018-02-07 | 2020-09-01 | 深圳大学 | Fuel cell oxygen reduction catalyst taking three-dimensional porous carbon material as raw material and preparation method thereof |
| CN109529770A (en) * | 2018-12-29 | 2019-03-29 | 中国科学院兰州化学物理研究所 | A method of porous carbon adsorbent material is prepared as template using the Pickering lotion that semicoke is stable |
| CN109529770B (en) * | 2018-12-29 | 2021-09-14 | 中国科学院兰州化学物理研究所 | Method for preparing porous carbon adsorbent material by taking semicoke-stable Pickering emulsion as template |
| CN111307891A (en) * | 2020-03-06 | 2020-06-19 | 山西大学 | Electrode system for electrochemical detection and application thereof |
| CN111420676A (en) * | 2020-03-17 | 2020-07-17 | 中国石油大学(北京) | Inorganic-organic hybrid metal super-particle and preparation method and application thereof |
| CN111420676B (en) * | 2020-03-17 | 2021-05-25 | 中国石油大学(北京) | Inorganic-organic hybrid metal super-particle and preparation method and application thereof |
| CN113856758A (en) * | 2021-11-05 | 2021-12-31 | 珠海复旦创新研究院 | Metal composite Janus polymer nanoparticle catalyst and preparation method and application thereof |
| CN113856758B (en) * | 2021-11-05 | 2023-05-26 | 珠海复旦创新研究院 | Metal composite Janus polymer nanoparticle catalyst and preparation method and application thereof |
| CN114230713A (en) * | 2021-12-31 | 2022-03-25 | 苏州星日化学有限公司 | Method for reducing surface fusion and surface adhesion of high internal phase emulsion in polymerization process |
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