CN105047952A - Dendritic nanowire catalyst carrier with metal oxide/carbon core-sheath structure and preparation method of supported catalyst - Google Patents
Dendritic nanowire catalyst carrier with metal oxide/carbon core-sheath structure and preparation method of supported catalyst Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a dendritic nanowire catalyst carrier with metal oxide/carbon core-sheath structure and a preparation method of a supported catalyst. The catalyst carrier is dendritic nanowires with the core-sheath structure; according to the core-sheath structure, the metal oxide is adopted as an inner core; and carbon is adopted as an outer sheath. The preparation method comprises the following steps: (1), preparing a uniform and transparent reactant solution; (2), carrying out solvothermal reaction; (3), centrifugally washing and drying the obtained product; and (4), coating the obtained product with a carbon sheath. The dendritic nanowire catalyst carrier with the metal oxide/carbon the core-sheath structure and the preparation method of supported metal nanoparticles disclosed by the invention are simple to operate and easy to control; a template is not needed in the preparation process; ordinary precursors such as chlorate and nitrate can be utilized; a metal organic compound required for preparation of the catalyst with a special structure is avoided; and the cost is further reduced.
Description
Technical field
The present invention relates to a kind of there is the core sheath structure of metal oxide/carbon dendroid nanowire catalyst support, preparation method and with it for carrier prepares the method for carrying metal nanoparticle catalyst.
Background technology
Polymer dielectric film fuel cell is a kind of is the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy by chemical energy, it has that energy conversion rate is high, environmental friendliness, room temperature toggle speed are fast, specific power and the outstanding feature such as specific energy is high, be acknowledged as one of electric supply installation of following main flow, but it is the key problem of limit polymerization thing dielectric film fuel cell large-scale application that a large amount of uses of noble metal catalyst cause cost to remain high.For this reason, the activity and the stability that improve catalyst is further needed, to reduce its cost.
Catalyst carrier affects its key factor that is active and stability.At present, business-purpose fuel cell catalyst mainly adopts carbon carrier.Although material with carbon element self has, specific area is large, the feature of good conductivity, and it easily at high potential place, oxide etch occurs, and causes catalyst granules to be separated with carrier, causes the decay of catalyst performance.Meanwhile, the interaction force of carbon carrier and catalyst is less, does not possess obvious co catalysis effect, affects catalyst activity.In order to improve stability and the activity of catalyst, in recent years, metal oxide shows good stability as catalyst carrier, and and metal nanoparticle between stronger interaction, thus be more and more subject to the favor of various countries researcher.But the specific area of oxide is low, the problem of poorly conductive constrains its application on a catalyst support.Little dispersiveness and the utilance that can affect catalyst of carrier surface area, the transmission of electronics in carrier conductivity missionary society impeded electrode course of reaction, all can cause catalytic activity poor.Therefore, the key issue that the surface area of oxide and conductivity become metal oxide carrier application how is improved.
In recent years, monodimension nanometer material and core-shell structured nanomaterials more and more receive publicity because of its special geometry and electronic structure.
Summary of the invention
The present invention be to solve existing fuel-cell catalyst exist catalyst performance poor, cost is high, the problem of poor stability, provide and a kind ofly have dendroid nano-wire catalyst of the core sheath structure of metal oxide/carbon and preparation method thereof, the development for fuel-cell catalyst proposes new approaches and approach.
The object of the invention is to be achieved through the following technical solutions:
Have a dendroid nanowire catalyst support for the core sheath structure of metal oxide/carbon, it is the dendroid nano wire with core sheath structure, and described core sheath structure take metal oxide as kernel, carbon is epitheca.
An above-mentioned preparation method with the dendroid nanowire catalyst support of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: oxide precursor (or mixed solution of oxide precursor and metalic contamination presoma) and acid solution are stirred 10 ~ 120min under the mixing speed of 100 ~ 1000rpm and is scattered in polyalcohol, controlling metalic contamination presoma and oxide precursor mol ratio in mixed solution is 0.001 ~ 0.3, the concentration of metal precursor is 10 ~ 100mmoL/L, and acid concentration is 0.01 ~ 1moL/L.
Two, solvent thermal reaction: mixed solution is placed in autoclave and reacts, controlling reaction temperature is 120 ~ 300 DEG C, and the reaction time is 0.5 ~ 15h, naturally cools to room temperature after question response terminates.
Three, centrifuge washing and drying: centrifugal 10 ~ 30min under the rotating speed of 2000 ~ 15000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 3 ~ 10 times to product, vacuumize 3 ~ 12h under temperature is 50 ~ 120 DEG C of conditions, namely obtains having dendritic structure oxide or metal-doped oxide nano thread.
Four, carbon coated sheath:
(1) hydro thermal method bag carbon: by the metal oxide nano-wire with dendritic structure and organic solution in mass ratio 10 ~ 30:100 mix, and under the mixing speed of 100 ~ 1000rpm, stir 10 ~ 120min obtain finely disseminated suspension-turbid liquid; Scattered suspension-turbid liquid is transferred in reactor, in 120 ~ 300 DEG C of reactions 3 ~ 10 hours; After reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours;
(2) chemical vapour deposition (CVD) bag carbon: the metal oxide nano-wire with dendritic structure is warming up to 400 ~ 900 DEG C, continue to pass into organic compound gas with the flow velocity of 0.2 ~ 10L/min, carry out chemical vapour deposition (CVD) bag carbon 10 ~ 120min, obtain the dendroid nanowire catalyst support of the core sheath structure of the coated metal oxide/carbon of chemical vapor carbon deposition.
Five, carrying metal nano particle: the metal oxide nano-wire carrier with dendritic structure is mixed 1:50 ~ 250 in mass ratio with organic solution, and 1 ~ 6h obtains finely disseminated suspension-turbid liquid under the mixing speed of 100 ~ 1000rpm; To be that 1:0.1 ~ 1.0 drip metal nanoparticle precursor solution in mass ratio in scattered suspension-turbid liquid, by NaOH, the pH of solution is transferred to 8 ~ 12, suspension-turbid liquid is placed in the microwave reactor of 800W, add thermal response 30 ~ 600s, after reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours, the catalyst that can to obtain with the dendroid nano wire of the core sheath structure of metal oxide/carbon be supported carrier metal nanoparticle.
Tool of the present invention has the following advantages:
In the dendroid nano wire carrier of one, the core sheath structure of oxide/carbon prepared by the present invention, metal-doped oxide nano thread has unique dendritic structure, and be formed by metal-doped, its doping metals enough changes the electronic structure of oxide and the catalytic activity of geometry and then effective raising catalyst;
In the dendroid shape nano wire carrier of the core sheath structure of the oxide/carbon two, prepared by the present invention, metal-doped oxide nano thread is due to the dendroid nano thread structure of its uniqueness, so have higher specific area;
Three, the dendroid shape nano wire carrier of the core sheath structure of oxide/carbon of the present invention and the preparation method of carrying metal nano particle simple to operate, be easy to control, preparation process is without the need to template, the common precursor such as available chlorate, nitrate, avoid the metallo-organic compound prepared needed for special construction catalyst, reduce costs further;
Four, in the dendroid nano wire carrier of the core sheath structure of oxide/carbon prepared of the present invention, surface coated carbon plays the effect of anchor catalyst, improves the stability of catalyst;
The dendroid nano wire carrier of the core sheath structure of the oxide/carbon five, prepared by the present invention, by solving the problem of oxide conducting difference in the method for oxide surface parcel carbon sheath.
Accompanying drawing explanation
Fig. 1 is dendritic structure Pd doped Ce O
2the TEM photo of nano wire;
Fig. 2 is that the dendroid nano wire TEM of the core sheath structure of metal oxide/carbon under low range schemes;
Fig. 3 is that the dendroid nano wire TEM of the core sheath structure of metal oxide/carbon under high magnification schemes;
Fig. 4 is the TEM photo of the nanowire supported Pd catalyst of dendroid of the core sheath structure of metal oxide/carbon;
Fig. 5 is the electron diffraction pattern of the nanowire supported Pd catalyst of dendroid of the core sheath structure of metal oxide/carbon.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: the dendroid nano wire of the core sheath structure of metal oxide/carbon that present embodiment provides is the dendroid nanowire catalyst support of the metal oxide/carbon core sheath structure with homogeneous diameter, described nanowire diameter is 3-200nm, and carbon sheath thickness is 0.5-20nm.
The dendroid nanowire catalyst support of the metal oxide described in the present embodiment/carbon core sheath structure has unique nano thread structure, this special appearance has higher active area, and nanowire diameter, carbon sheath thickness can carry out Effective Regulation, its TEM schemes as Figure 2-3.
Embodiment two: present embodiment and embodiment one unlike: described metal oxide both can be oxide also can be metal-doped type oxide, doping metals is the one or wherein several in Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and Sb, and doping ratio is 0.1 ~ 40wt.%; Metal oxide is Al
2o
3, Ga
2o
3, SiO
2, GeO
2, TiO
2, ZrO
2, V
2o
5, Cr
2o
3, MnO
2, Fe
2o
3, Fe
3o
4, Co
2o
3, NiO, CuO, ZnO, Nb
2o
5, MoO
3, RuO
2, In
2o
3, SnO
2, Sb
2o
3, Sb
2o
5, Tl
2o
3, PbO, Bi
2o
3, La
2o
3, Ta
2o
5, WO
2, WO
3, Bi
2o
3and CeO
2in one.
Embodiment three: the preparation method that present embodiments provide for the dendroid nanowire catalyst support of a kind of metal oxide/carbon core sheath structure, specifically completes according to the following steps:
One, prepare the reactant solution of transparent and homogeneous: by oxide precursor (or oxide precursor, metalic contamination presoma mixed solution) and acid solution under the mixing speed of 100 ~ 1000rpm, stir 10 ~ 120min be scattered in polyalcohol, controlling metalic contamination presoma and oxide precursor mol ratio in mixed solution is 0.001 ~ 0.3, the concentration of metal precursor is 10 ~ 100mmoL/L, and acid concentration is 0.01 ~ 1moL/L.
Two, solvent thermal reaction: mixed solution is placed in autoclave and reacts, controlling reaction temperature is 120 ~ 300 DEG C, and the reaction time is 0.5 ~ 15h, naturally cools to room temperature after question response terminates.
Three, centrifuge washing and drying: centrifugal 10 ~ 30min under the rotating speed of 2000 ~ 15000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 3 ~ 10 times to product, vacuumize 3 ~ 12h under temperature is 50 ~ 120 DEG C of conditions, namely obtains having dendritic structure oxide or metal-doped oxide nano thread.
Four, carbon coated sheath:
(1) hydro thermal method bag carbon: by the metal oxide nano-wire with dendritic structure and organic solution in mass ratio 10 ~ 30:100 mix, and under the mixing speed of 100 ~ 1000rpm, stir 10 ~ 120min obtain finely disseminated suspension-turbid liquid; Scattered suspension-turbid liquid is transferred in reactor, in 120 ~ 300 DEG C of reactions 3 ~ 10 hours; After reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours;
(2) chemical vapour deposition (CVD) bag carbon: the metal oxide nano-wire with dendritic structure is warming up to 400 ~ 900 DEG C, continue to pass into organic compound gas with the flow velocity of 0.2 ~ 10L/min, carry out chemical vapour deposition (CVD) bag carbon 10 ~ 120min, obtain the dendroid nanowire catalyst support of the core sheath structure of the coated metal oxide/carbon of chemical vapor carbon deposition.
Polyalcohol described in step one is (200 ~ 4000) with the amount of substance ratio of acid: 1.
The amount ratio of the polyalcohol described in step one and oxide precursor species is (800 ~ 1200): 1.
Ethanol described in step 3 is (1 ~ 3) with the mixed liquor volume ratio of deionized water: 1.
The dendroid nanowire catalyst support of the metal oxide described in present embodiment/carbon core sheath structure, the doping of metal wherein can change electronic structure and the geometry of oxide.
Winding nanometer wire composite oxide of metal nanocatalyst described in the present embodiment has unique composite oxide of metal and is wound around nano thread structure, this special appearance has higher active area, and nanowire diameter, carbon sheath thickness can carry out Effective Regulation.
Embodiment four: present embodiment and embodiment three unlike: the presoma of the metal oxide described in step one is the one in the nitrate of Al, Ga, Si, Ge, Ti, Zr, V, Cr, Mn, Fe, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ru, In, Sn, Sb, Sb, Tl, Pb, Bi, La, Ta, W and Ce, chloride, sulfate, acetate, acetylacetonate and ester type compound.
Embodiment five: one of present embodiment and embodiment three or four unlike: the polyalcohol described in step one is a kind of or wherein several mixture in ethylene glycol, propylene glycol, glycerol, butanediol, hexylene glycol, neopentyl glycol, isopropyl alcohol, Diethylene Glycol, dipropylene glycol, trimethylolpropane, glycerine.
Embodiment six: one of present embodiment and embodiment three to five unlike: the metal precursor aqueous solution described in step one is a kind of or wherein several mixture of sulfate solution, nitrate aqueous solution, aqueous phosphatic, acetate aqueous solution, halide solution, the metal halogen hydracid aqueous solution and the metal halate aqueous solution; In the metal precursor aqueous solution, the metal of metal precursor is the one or wherein several in Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and Sb.
Embodiment seven: one of present embodiment and embodiment three to six unlike: the acid solution described in step one is nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, a kind of or wherein several mixture of acid iodide, oxalic acid, nitrous acid, phosphoric acid, sulfurous acid.
Embodiment eight: one of present embodiment and embodiment three to seven unlike: the carbon source adopted in the hydro-thermal carbon coated sheath described in step 4 is a kind of or wherein several mixture in glucose, sucrose, starch, urea, melamine, citric acid, natrium citricum, cyclodextrin, sodium cellulose glycolate, aliphatic acid, glutamic acid, alanine.
Embodiment nine: one of present embodiment and embodiment four to eight unlike, carbon coated sheath described in step 4 is chemical vapour deposition technique, and carbon source adopts a kind of or wherein several mixture in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol, ethylenediamine, urea, aniline, melamine, thiophene, citric acid.
Embodiment ten: present embodiment and embodiment three to nine unlike: adopt microwave polyol legal system for supported catalyst: with the dendroid nanowire catalyst support of the core sheath structure of metal oxide/carbon for supported carrier metal nanoparticle, specifically to complete according to the following steps:
One, prepare the reactant solution of transparent and homogeneous: by oxide precursor (or oxide precursor, metalic contamination presoma mixed solution) and acid solution under the mixing speed of 100 ~ 1000rpm, stir 10 ~ 120min be scattered in polyalcohol, controlling metalic contamination presoma and oxide precursor mol ratio in mixed solution is 0.001 ~ 0.3, the concentration of metal precursor is 10 ~ 100mmoL/L, and acid concentration is 0.01 ~ 1moL/L.
Two, solvent thermal reaction: mixed solution is placed in autoclave and reacts, controlling reaction temperature is 120 ~ 300 DEG C, and the reaction time is 0.5 ~ 15h, naturally cools to room temperature after question response terminates.
Three, centrifuge washing and drying: centrifugal 10 ~ 30min under the rotating speed of 2000 ~ 15000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 3 ~ 10 times to product, vacuumize 3 ~ 12h under temperature is 50 ~ 120 DEG C of conditions, namely obtains having dendritic structure oxide or metal-doped oxide nano thread.
Four, carbon coated sheath:
(1) hydro thermal method bag carbon: by the metal oxide nano-wire with dendritic structure and organic solution in mass ratio 10 ~ 30:100 mix, and under the mixing speed of 100 ~ 1000rpm, stir 10 ~ 120min obtain finely disseminated suspension-turbid liquid; Scattered suspension-turbid liquid is transferred in reactor, in 120 ~ 300 DEG C of reactions 3 ~ 10 hours; After reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours;
(2) chemical vapour deposition (CVD) bag carbon: the metal oxide nano-wire with dendritic structure is warming up to 400 ~ 900 DEG C, continue to pass into organic compound gas with the flow velocity of 0.2 ~ 10L/min, carry out chemical vapour deposition (CVD) bag carbon 10 ~ 120min, obtain the dendroid nanowire catalyst support of the core sheath structure of the coated metal oxide/carbon of chemical vapor carbon deposition.
Five, carrying metal nano particle: the metal oxide nano-wire carrier with dendritic structure is mixed 1:50 ~ 250 in mass ratio with organic solution, and 1 ~ 6h obtains finely disseminated suspension-turbid liquid under the mixing speed of 100 ~ 1000rpm; To be that 1:0.1 ~ 1.0 drip metal nanoparticle precursor solution in mass ratio in scattered suspension-turbid liquid, by NaOH, the pH of solution is transferred to 8 ~ 12, suspension-turbid liquid is placed in the microwave reactor of 800W, add thermal response 30 ~ 600s, after reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours, the catalyst that can to obtain with the dendroid nano wire of the core sheath structure of metal oxide/carbon be supported carrier metal nanoparticle.
Embodiment 11: present embodiment and embodiment ten unlike: in the carried metal precursor water solution described in step 5, the metal of metal precursor is the one or wherein several in Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and Sb, and loading is 10-80wt.%.
Adopt following verification experimental verification invention effect:
Experiment one: a kind of preparation method of dendritic structure oxide nano thread, specifically completes according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: will wherein cerous nitrate (0.05mmoL) and salpeter solution (0.2mL7.5moL/L) under the mixing speed of 500rpm, continue to continue stirring 60min be scattered in ethylene glycol; Two, solvent thermal reaction: mixed solution is placed in autoclave, reaction temperature is 170 DEG C, and the reaction time is 2h, naturally cools to room temperature after question response terminates.Three, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 6000rpm, obtain solid product, utilize the mixed solution of ethanol and deionized water to carry out centrifuge washing 5 times to product, vacuumize 5h under temperature is 80 DEG C of conditions, namely obtain that there is dendritic structure CeO
2nano wire.
Experiment two: the preparation method of the metal-doped oxide nano thread of a kind of dendritic structure, specifically completes according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: will wherein cerous nitrate (0.05mmoL), palladium nitrate (0.0025mmoL) and salpeter solution (0.2mL7.5moL/L) under the mixing speed of 500rpm, continue to continue stirring 60min be scattered in ethylene glycol; Two, solvent thermal reaction: mixed solution is placed in autoclave, reaction temperature is 170 DEG C, and the reaction time is 2h, naturally cools to room temperature after question response terminates.Three, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 6000rpm, obtain solid product, utilize the mixed solution of ethanol and deionized water to carry out centrifuge washing 5 times to product, vacuumize 5h under temperature is 80 DEG C of conditions, namely obtain that there is dendritic structure Pd doped Ce O
2nano wire.
Experiment three: the preparation method of the metal-doped oxide nano thread of a kind of dendritic structure, specifically completes according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: will wherein cerous sulfate (0.05mmoL), platinum chloride (0.005mmoL) and salpeter solution (0.2mL7.5moL/L) under the mixing speed of 500rpm, continue to continue stirring 60min be scattered in ethylene glycol; Two, solvent thermal reaction: mixed solution is placed in autoclave, reaction temperature is 170 DEG C, and the reaction time is 2h, naturally cools to room temperature after question response terminates.Three, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 6000rpm, obtain solid product, utilize the mixed solution of ethanol and deionized water to carry out centrifuge washing 5 times to product, vacuumize 5h under temperature is 80 DEG C of conditions, namely obtain that there is dendritic structure Pt doped Ce O
2nano wire, its TEM photo is as shown in Figure 1;
Experiment four: the preparation method of the metal-doped oxide nano thread of a kind of dendritic structure, specifically completes according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: will wherein cerous nitrate (0.05mmoL), gold chloride (0.005mmoL) and sulfuric acid solution (0.2mL7.5moL/L) under the mixing speed of 500rpm, continue to continue stirring 60min be scattered in glycerol; Two, solvent thermal reaction: mixed solution is placed in autoclave, reaction temperature is 180 DEG C, and the reaction time is 1.5h, naturally cools to room temperature after question response terminates.Three, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 6000rpm, obtain solid product, utilize the mixed solution of ethanol and deionized water to carry out centrifuge washing 5 times to product, vacuumize 5h under temperature is 80 DEG C of conditions, namely obtain that there is dendritic structure Au doped Ce O
2nano wire.
Experiment five: the preparation method of the metal-doped oxide nano thread of a kind of dendritic structure, specifically completes according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: will wherein cobalt nitrate (0.05mmoL), palladium bichloride (0.005mmoL) and salpeter solution (0.2mL7.5moL/L) under the mixing speed of 500rpm, continue to continue stirring 60min be scattered in ethylene glycol; Two, solvent thermal reaction: mixed solution is placed in autoclave, reaction temperature is 170 DEG C, and the reaction time is 2h, naturally cools to room temperature after question response terminates.Three, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 6000rpm, obtain solid product, utilize the mixed solution of ethanol and deionized water to carry out centrifuge washing 5 times to product, vacuumize 8h under temperature is 50 DEG C of conditions, namely obtain that there is dendritic structure Pd doping CoO
2nano wire.
Experiment six: the preparation method of the dendroid nano wire of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, the nano wire 30mg being prepared into metal-doped oxide is distributed in 30mL0.045moL/L D/W; Two, hydro-thermal reaction: mixed solution is placed in autoclave, reaction temperature is 170 DEG C, reaction time 8h, and question response terminates, and naturally cools to room temperature; Three, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 8000rpm, obtain solid product, utilizes the mixed solution of ethanol and deionized water to carry out centrifuge washing 5 times to product, vacuumize 8h under temperature is 80 DEG C of conditions; Four, heat treatment: solid product is placed in 400 DEG C, tube furnace, processes 4h in Ar atmosphere, finally obtains the dendroid nano wire of the core sheath structure of oxide/carbon.
Experiment seven: the preparation method of the dendroid nano wire of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, the nano wire 30mg being prepared into metal-doped oxide is distributed in 30mL0.045moL/L aqueous sucrose solution; Two, hydro-thermal reaction: mixed solution is placed in autoclave, reaction temperature is 170 DEG C, reaction time 8h, and question response terminates, and naturally cools to room temperature; Three, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 8000rpm, obtain solid product, utilizes the mixed solution of ethanol and deionized water to carry out centrifuge washing 5 times to product, vacuumize 8h under temperature is 80 DEG C of conditions; Four, heat treatment: solid product is placed in 400 DEG C, tube furnace, processes 4h in Ar atmosphere, finally obtains the dendroid nano wire of the core sheath structure of oxide/carbon.
Experiment eight: the preparation method of the dendroid nano wire of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, the nano wire 10mg-30mg being prepared into metal-doped oxide is placed in porcelain boat; Two, heat treatment: at sample is warming up to 800-1000 DEG C under Ar protection; constant temperature 1-2h, now passes into 0.2 ~ 10L/min alcohol vapour, and constant temperature terminates rear closedown alcohol vapour; naturally cool to room temperature, finally obtain the dendroid nano wire of the core sheath structure of oxide/carbon.
Experiment nine: the preparation method of the dendroid nano wire of the core sheath structure of oxide/carbon, specifically completes according to the following steps:
One, the nano wire 10mg-30mg being prepared into metal-doped oxide is placed in porcelain boat; Two, heat treatment: at sample is warming up to 800-1000 DEG C under Ar protection; constant temperature 1-2h, now passes into 0.2 ~ 10L/min ethylenediamine steam, and constant temperature terminates rear closedown ethylenediamine steam; naturally cool to room temperature, finally obtain the dendroid nano wire of the core sheath structure of oxide/carbon
Experiment ten: the preparation method of the dendroid nano wire carrying metal nano particle of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, by the dendroid nano wire powder dispersion (V:V=1:3) in isopropyl alcohol and ethylene glycol of the core sheath structure of the 40mg oxide/carbon of preparation; Two, in suspension-turbid liquid, drip palladium nitrate solution (0.01M), and with NaOH, pH value of solution is adjusted to 10-12; Three, microwave heating: solution is placed in microwave reactor, reaction time 60s, naturally cools to room temperature; Four, HNO is adopted
3the pH of solution is adjusted to 4-5; Five, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 8000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 5 times to product, vacuumize 3h under temperature is 80 DEG C of conditions, can obtain the dendroid nano wire loading Pd nano particle of the core sheath structure of oxide/carbon.
Test 11: the preparation method of the dendroid nano wire carrying metal nano particle of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, by the dendroid nano wire powder dispersion (V:V=1:3) in isopropyl alcohol and ethylene glycol of the core sheath structure of the 40mg oxide/carbon of preparation; Two, in suspension-turbid liquid, drip platinum acid chloride solution (0.01M), and with NaOH, pH value of solution is adjusted to 10-12; Three, microwave heating: solution is placed in microwave reactor, reaction time 60s, naturally cools to room temperature; Four, adopt HNO3 that the pH of solution is adjusted to 4-5; Five, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 8000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 5 times to product, vacuumize 3h under temperature is 80 DEG C of conditions, the dendroid nano wire that can obtain the core sheath structure of oxide/carbon supports Pt nano particle, as shown in Figure 4, electron diffraction pattern as shown in Figure 5 for its TEM photo.
Test 12: the preparation method of the dendroid nano wire carrying metal nano particle of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, by the dendroid nano wire powder dispersion (V:V=1:3) in isopropyl alcohol and ethylene glycol of the core sheath structure of the 40mg oxide/carbon of preparation; Two, in suspension-turbid liquid, drip platinum acid chloride solution (0.01M) and gold chloride (0.001M), and with NaOH, pH value of solution is adjusted to 10-12; Three, microwave heating: solution is placed in microwave reactor, reaction time 60s, naturally cools to room temperature; Four, adopt HNO3 that the pH of solution is adjusted to 4-5; Five, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 8000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 5 times to product, vacuumize 3h under temperature is 80 DEG C of conditions, the dendroid nano wire that can obtain the core sheath structure of oxide/carbon supports PtAu nano particle.
Test 13: the preparation method of the dendroid nano wire carrying metal nano particle of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, by the dendroid nano wire powder dispersion (V:V=1:3) in isopropyl alcohol and ethylene glycol of the core sheath structure of the 40mg oxide/carbon of preparation; Two, in suspension-turbid liquid, drip palladium nitrate solution (0.01M) and gold chloride (0.01M), and with NaOH, pH value of solution is adjusted to 10-12; Three, microwave heating: solution is placed in microwave reactor, reaction time 60s, naturally cools to room temperature; Four, adopt HNO3 that the pH of solution is adjusted to 4-5; Five, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 8000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 5 times to product, vacuumize 3h under temperature is 80 DEG C of conditions, can obtain the dendroid nano wire loading Pd Au nano particle of the core sheath structure of oxide/carbon.
Test 14: the preparation method of the dendroid nano wire carrying metal nano particle of the core sheath structure of metal oxide/carbon, specifically completes according to the following steps:
One, by the dendroid nano wire powder dispersion (V:V=1:3) in isopropyl alcohol and ethylene glycol of the core sheath structure of the 40mg oxide/carbon of preparation; Two, in suspension-turbid liquid, drip platinum acid chloride solution (0.01M) and ruthenic chloride (0.01M), and with NaOH, pH value of solution is adjusted to 10-12; Three, microwave heating: solution is placed in microwave reactor, reaction time 60s, naturally cools to room temperature; Four, HNO is adopted
3the pH of solution is adjusted to 4-5; Five, centrifuge washing and drying: at the centrifugal 15min of the rotating speed of 8000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 5 times to product, vacuumize 3h under temperature is 80 DEG C of conditions, the dendroid nano wire that can obtain the core sheath structure of oxide/carbon supports PtRu nano particle.
Claims (10)
1. there is a dendroid nanowire catalyst support for the core sheath structure of metal oxide/carbon, it is characterized in that described catalyst carrier is the dendroid nano wire with core sheath structure, described core sheath structure take metal oxide as kernel, carbon is epitheca.
2. the dendroid nanowire catalyst support with the core sheath structure of metal oxide/carbon according to claim 1, it is characterized in that described nanowire diameter is 3-200nm, carbon sheath thickness is 0.5-20nm.
3. the dendroid nanowire catalyst support with the core sheath structure of metal oxide/carbon according to claim 1, is characterized in that described metal oxide is Al
2o
3, Ga
2o
3, SiO
2, GeO
2, TiO
2, ZrO
2, V
2o
5, Cr
2o
3, MnO
2, Fe
2o
3, Fe
3o
4, Co
2o
3, NiO, CuO, ZnO, Nb
2o
5, MoO
3, RuO
2, In
2o
3, SnO
2, Sb
2o
3, Sb
2o
5, Tl
2o
3, PbO, Bi
2o
3, La
2o
3, Ta
2o
5, WO
2, WO
3, Bi
2o
3and CeO
2in one.
4. the dendroid nanowire catalyst support with the core sheath structure of metal oxide/carbon according to claim 1, it is characterized in that described metal oxide is metal-doped type oxide, doping metals is the one or wherein several in Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and Sb, and doping ratio is 0.1 ~ 40wt.%.
5. there is described in claim 1 preparation method for the dendroid nanowire catalyst support of the core sheath structure of metal oxide/carbon, it is characterized in that what described method specifically completed according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: the acid solution of to be the oxide precursor of 10 ~ 100mmoL/L or the mixed solution of oxide precursor and metalic contamination presoma and concentration by concentration be 0.01 ~ 1moL/L stirs 10 ~ 120min and is scattered in polyalcohol under the mixing speed of 100 ~ 1000rpm, controlling metalic contamination presoma and oxide precursor mol ratio in mixed solution is 0.001 ~ 0.3, polyalcohol is (200 ~ 4000) with the amount of substance ratio of acid: 1, and the amount ratio of polyalcohol and oxide precursor species is (800 ~ 1200): 1;
Two, solvent thermal reaction: mixed solution is placed in autoclave and reacts, controlling reaction temperature is 120 ~ 300 DEG C, and the reaction time is 0.5 ~ 15h, naturally cools to room temperature after question response terminates;
Three, centrifuge washing and drying: centrifugal 10 ~ 30min under the rotating speed of 2000 ~ 15000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 3 ~ 10 times to product, vacuumize 3 ~ 12h under temperature is 50 ~ 120 DEG C of conditions, namely obtains having dendritic structure oxide or metal-doped oxide nano thread;
Four, carbon coated sheath:
By the metal oxide nano-wire with dendritic structure and organic solution in mass ratio 10 ~ 30:100 mix, and under the mixing speed of 100 ~ 1000rpm, stir 10 ~ 120min obtain finely disseminated suspension-turbid liquid; Scattered suspension-turbid liquid is transferred in reactor, in 120 ~ 300 DEG C of reactions 3 ~ 10 hours; After reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours.
6. the preparation method with the dendroid nanowire catalyst support of the core sheath structure of metal oxide/carbon according to claim 5, it is characterized in that described step 4 replaces with: the metal oxide nano-wire with dendritic structure is warming up to 400 ~ 900 DEG C, continue to pass into organic compound gas with the flow velocity of 0.2 ~ 10L/min, carry out chemical vapour deposition (CVD) bag carbon 10 ~ 120min, obtain the dendroid nanowire catalyst support of the core sheath structure of the coated metal oxide/carbon of chemical vapor carbon deposition.
7. the preparation method with the dendroid nanowire catalyst support of the core sheath structure of metal oxide/carbon according to claim 5, is characterized in that described polyalcohol is a kind of or wherein several mixture in ethylene glycol, propylene glycol, glycerol, butanediol, hexylene glycol, neopentyl glycol, isopropyl alcohol, Diethylene Glycol, dipropylene glycol, trimethylolpropane, glycerine; In the presoma of described metal oxide, metal is the one in Al, Ga, Si, Ge, Ti, Zr, V, Cr, Mn, Fe, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ru, In, Sn, Sb, Sb, Tl, Pb, Bi, La, Ta, W and Ce; In described metalic contamination presoma, metal is the one or wherein several in Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and Sb; Described acid solution is nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, a kind of or wherein several mixture of acid iodide, oxalic acid, nitrous acid, phosphoric acid, sulfurous acid; Described organic solution is a kind of or wherein several mixture in glucose, sucrose, starch, urea, melamine, citric acid, natrium citricum, cyclodextrin, sodium cellulose glycolate, aliphatic acid, glutamic acid, alanine.
8. the preparation method with the dendroid nanowire catalyst support of the core sheath structure of metal oxide/carbon according to claim 6, is characterized in that described organic compound gas is a kind of or wherein several mixture in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol, ethylenediamine, urea, aniline, melamine, thiophene, citric acid.
9. there is described in claim 1 preparation method for the dendroid nanowire catalyst support carrying metal nano particle of the core sheath structure of metal oxide/carbon, it is characterized in that what described method specifically completed according to the following steps:
One, the reactant solution of transparent and homogeneous is prepared: the acid solution of to be the oxide precursor of 10 ~ 100mmoL/L or the mixed solution of oxide precursor and metalic contamination presoma and concentration by concentration be 0.01 ~ 1moL/L stirs 10 ~ 120min and is scattered in polyalcohol under the mixing speed of 100 ~ 1000rpm, controlling metalic contamination presoma and oxide precursor mol ratio in mixed solution is 0.001 ~ 0.3, polyalcohol is (200 ~ 4000) with the amount of substance ratio of acid: 1, and the amount ratio of polyalcohol and oxide precursor species is (800 ~ 1200): 1;
Two, solvent thermal reaction: mixed solution is placed in autoclave and reacts, controlling reaction temperature is 120 ~ 300 DEG C, and the reaction time is 0.5 ~ 15h, naturally cools to room temperature after question response terminates;
Three, centrifuge washing and drying: centrifugal 10 ~ 30min under the rotating speed of 2000 ~ 15000rpm, obtain solid product, the mixed solution of ethanol and deionized water is utilized to carry out centrifuge washing 3 ~ 10 times to product, vacuumize 3 ~ 12h under temperature is 50 ~ 120 DEG C of conditions, namely obtains having dendritic structure oxide or metal-doped oxide nano thread;
Four, carbon coated sheath:
By the metal oxide nano-wire with dendritic structure and organic solution in mass ratio 10 ~ 30:100 mix, and under the mixing speed of 100 ~ 1000rpm, stir 10 ~ 120min obtain finely disseminated suspension-turbid liquid; Scattered suspension-turbid liquid is transferred in reactor, in 120 ~ 300 DEG C of reactions 3 ~ 10 hours; After reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours;
Five, carrying metal nano particle: the metal oxide nano-wire carrier with dendritic structure is mixed 1:50 ~ 250 in mass ratio with organic solution, and 1 ~ 6h obtains finely disseminated suspension-turbid liquid under the mixing speed of 100 ~ 1000rpm; To be that 1:0.1 ~ 1.0 drip metal nanoparticle precursor solution in mass ratio in scattered suspension-turbid liquid, by NaOH, the pH of solution is transferred to 8 ~ 12, suspension-turbid liquid is placed in the microwave reactor of 800W, add thermal response 30 ~ 600s, after reaction terminates, filter after material being cooled to room temperature, and priority water and alcohol flushing; By the material after washing under vacuum or inert environments, in 80 ~ 120 DEG C of dryings 3 ~ 6 hours, the catalyst that can to obtain with the dendroid nano wire of the core sheath structure of metal oxide/carbon be supported carrier metal nanoparticle.
10. the preparation method with the dendroid nanowire catalyst support carrying metal nano particle of the core sheath structure of metal oxide/carbon according to claim 9, it is characterized in that described step 4 replaces with: the metal oxide nano-wire with dendritic structure is warming up to 400 ~ 900 DEG C, continue to pass into organic compound gas with the flow velocity of 0.2 ~ 10L/min, carry out chemical vapour deposition (CVD) bag carbon 10 ~ 120min, obtain the dendroid nanowire catalyst support of the core sheath structure of the coated metal oxide/carbon of chemical vapor carbon deposition.
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