CN102969514B - Metal-coated oxide nano core-shell structure catalyst and preparation method thereof - Google Patents
Metal-coated oxide nano core-shell structure catalyst and preparation method thereof Download PDFInfo
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- CN102969514B CN102969514B CN201210508700.2A CN201210508700A CN102969514B CN 102969514 B CN102969514 B CN 102969514B CN 201210508700 A CN201210508700 A CN 201210508700A CN 102969514 B CN102969514 B CN 102969514B
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Abstract
The invention relates to a preparation method of a metal-coated oxide nano core-shell structure catalyst, and in particular relates to a preparation method of the nano fuel cell catalyst with a core-shell structure. The invention aims at solving the problems that the conventional fuel cell catalyst is not high in catalytic activity and stability as well as low in cost at the same time. According to the metal-coated oxide nano core-shell structure catalyst, metal uniformly covers a shell, and oxide nano-particles are used as an inner core. The preparation method comprises the steps of: 1, preparing uniform, transparent and stable mixed solution; 2, blending and mixing; 3, adding reducing agent into the mixture; 4, adding extraction agent into the mixture; and 5, carrying out centrifugal washing and drying to obtain the metal-coated oxide nano core-shell structure catalyst. The invention is mainly used for preparing the metal-coated oxide nano core-shell structure fuel cell catalyst.
Description
Technical field
The present invention relates to a kind of preparation method with the nanometer fuel battery catalyst of nucleocapsid structure.
Background technology
Polymer dielectric film fuel cell is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) that chemical energy is converted into electric energy, the outstanding features such as it has that energy conversion rate is high, environmental friendliness, room temperature toggle speed are fast, specific power and specific energy height, being acknowledged as one of electric supply installation of following main flow, is the key problem of limit polymerization thing dielectric film fuel cell large-scale application but a large amount of uses of noble metal catalyst cause cost high.
In recent years, have the nano material of nucleocapsid structure because its special structure has attracted extensive concern, the nuclear shell structure nano catalyst of preparation is modal is at present the bimetallic catalyst with core-casing structure of metallic cover metal.The shortcoming of this catalyst is that its kernel is still generally the noble metals such as Au, Pd, does not reach the object that reduces catalyst cost; And if kernel adopts base metal, in the long-term course of work, can there is the dissolution phenomenas such as chemistry and electrochemistry in the base metal of kernel, reduces the stability of catalyst; Therefore existing fuel-cell catalyst possesses high catalytic activity, stability and the low problem of catalyst cost while there is difference.
Summary of the invention
The present invention will solve when existing fuel-cell catalyst exists difference to possess high catalytic activity, stability and the low problem of catalyst cost, and a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure is provided.
A kind of metallic cover oxidate nano of the present invention catalyst with core-casing structure is the nano core-shell structure catalyst that the even clad metal of shell, kernel are oxide nano particles, the thickness of the described even clad metal of shell is 1nm～20nm, and the particle diameter of described oxide nano particles is 1nm～200nm.
A preparation method for metallic cover oxidate nano catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: by oxide nano particles, at power, be ultrasonic being scattered in oil phase solvent under 20W～1000W, the frequency condition that is 20kHz～80kHz, obtain the dispersion liquid that oxide nano particles concentration is 0.001mol/L～1mol/L, then add successively consisting of phase-transferring agent, mutually middle and water, and continue ultrasonic dispersion 10min～120min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain metal shell precursor water solution under the condition that low whipping speed is 100rpm～1000rpm, add rear continuation and stir 10min～60min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 100rpm～1000rpm, reducing agent is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 0 ℃～80 ℃, mixing speed is to continue stirring reaction 2h～24h under 100rpm～1000rpm condition, obtains product mixed solution; Four, add extractant: extractant is added in the product mixed solution that step 3 obtains, low whipping speed be under 100rpm～500rpm condition, stir after 3h～12h standing, get upper oil phase and with the rotating speed centrifugal treating of 3000rpm～15000rpm, obtain product; Five, centrifuge washing and dry: under the condition that is 3000rpm～15000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 3 times～15 times, in temperature, be 50 ℃～80 ℃ vacuumize 3h～12h, obtain metallic cover oxidate nano catalyst with core-casing structure; Oil phase solvent described in step 1 is 1 with the volume ratio of middle phase: (5～15); The volume ratio of the oil phase solvent described in step 1 and water is 1: (15～30); The amount of substance of the consisting of phase-transferring agent described in step 1 is (150～300) with the amount of substance of oxide nano particles ratio: 1; In metal shell precursor water solution described in step 2, the amount of substance of metal shell presoma and the amount of substance of the oxide nano particles described in step 1 are than being (0.5～50): 1; In the amount of substance of the reducing agent described in step 3 and the metal shell precursor water solution described in step 2, the amount of substance of metal shell presoma is than being (1～50): 1; The volume ratio of the water described in the extractant described in step 4 and step 1 is (1～5): 1; N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is (1～3): 1.
Advantage of the present invention: one, the prepared metallic cover oxidate nano catalyst with core-casing structure of the present invention has unique oxide kernel, its oxide kernel can change electronic structure and the geometry of outer layer metal, and then effectively improve noble metal catalyst catalytic activity and stability, carry palladium (Pd/C) catalyst with commercial carbon and compare, catalytic activity is 1.5～3 times that commercial carbon carries palladium (Pd/C) catalyst; Two, the prepared metallic cover oxidate nano catalyst with core-casing structure kernel of the present invention is oxide nano particles, the bimetallic catalyst with core-casing structure of the metallic cover metal that is noble metal with kernel is compared, greatly reduce fuel-cell catalyst noble metal dosage, effectively reduce catalyst cost; Three, the prepared metallic cover oxidate nano catalyst with core-casing structure of the present invention has the evenly feature such as controlled of good dispersion, nano particle diameter and outer casing thickness; Four, prepared metallic cover oxidate nano catalyst with core-casing structure of the present invention can be used as fuel-cell catalyst use; Five, the preparation method of metallic cover oxidate nano catalyst with core-casing structure of the present invention is simple to operate, be easy to control, can use the common presomas such as chlorate, nitrate, thereby the metallo-organic compound often using while avoiding conventional method to prepare nucleocapsid catalyst, further reduces synthetic cost.
Accompanying drawing explanation
Fig. 1 is methanol oxidation cyclic voltammetry curve figure, methanol oxidation cyclic voltammetry curve figure when zero in Fig. 1 represents that test one adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes as work electrode, methanol oxidation cyclic voltammetry curve figure when the ■ in Fig. 1 represents to test glass-carbon electrode that two employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, methanol oxidation cyclic voltammetry curve figure when the ◇ in Fig. 1 represents to test glass-carbon electrode that three employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, in Fig. 1 ● methanol oxidation cyclic voltammetry curve figure while representing that test four adopts commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode, Fig. 2 is chronoa mperometric plot figure, chronoa mperometric plot figure when the ◇ in Fig. 2 represents to test glass-carbon electrode that an employing metallic cover oxidate nano catalyst with core-casing structure makes as work electrode, chronoa mperometric plot figure when the ■ in Fig. 2 represents to test glass-carbon electrode that two employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, chronoa mperometric plot figure when the in Fig. 2 represents to test glass-carbon electrode that three employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, in Fig. 2 ● represent chronoa mperometric plot figure when test four adopts commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode.
Embodiment
Embodiment one: a kind of metallic cover oxidate nano of present embodiment catalyst with core-casing structure is the nano core-shell structure catalyst that the even clad metal of shell, kernel are oxide nano particles, the thickness of the described even clad metal of shell is 1nm～20nm, and the particle diameter of described oxide nano particles is 1nm～200nm.
Metallic cover oxidate nano catalyst with core-casing structure described in present embodiment has unique oxide kernel, its oxide kernel can change electronic structure and the geometry of outer layer metal, and then effectively improve noble metal catalyst catalytic activity and stability, carry palladium (Pd/C) catalyst with commercial carbon and compare, catalytic activity is 1.5～3 times that commercial carbon carries palladium (Pd/C) catalyst.
Metallic cover oxidate nano catalyst with core-casing structure kernel described in present embodiment is oxide nano particles, the bimetallic catalyst with core-casing structure of the metallic cover metal that is noble metal with kernel is compared, greatly reduce fuel-cell catalyst noble metal dosage, effectively reduce catalyst cost.
Metallic cover oxidate nano catalyst with core-casing structure described in present embodiment has the evenly feature such as controlled of good dispersion, nano particle diameter and outer casing thickness.
Embodiment two: present embodiment is different from embodiment one: described oxide nano particles 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 a kind of, or two or more mixture wherein, or two or more oxide solid solution being prepared from wherein.Other are identical with embodiment one.
Oxide solid solution described in present embodiment is prepared according to the following steps: 1. first two or more oxide is dissolved in acid with arbitrary proportion, through stirring, obtains mixed solution, 2. in reactor, add successively distilled water and polyvinylpyrrolidone (PVP), and adopt acid that pH value is adjusted to 4～6, obtain liquid on earth, 3. then under temperature is the water bath with thermostatic control condition of 25 ℃～80 ℃, mixed solution is added drop-wise in end liquid, and in mixed solution adition process, drip ammoniacal liquor pH value is controlled to 7～10, after solution to be mixed dropwises, and stirring reaction 10～120min, obtained oxide solid solution gel, utilize half membrane dialyzing method purifying oxide solid solution gel, purifying rear oxidation thing mischcrystal jelly obtains oxide solid solution through vacuumize.
Embodiment three: present embodiment is different from one of embodiment one or two: described metal is a kind of or wherein several in Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and Sb.Other are identical with embodiment one or two.
Embodiment four: the preparation method of a kind of metallic cover oxidate nano of present embodiment catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: by oxide nano particles, at power, be ultrasonic being scattered in oil phase solvent under 20W～1000W, the frequency condition that is 20kHz～80kHz, obtain the dispersion liquid that oxide nano particles concentration is 0.001mol/L～1mol/L, then add successively consisting of phase-transferring agent, mutually middle and water, and continue ultrasonic dispersion 10min～120min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain metal shell precursor water solution under the condition that low whipping speed is 100rpm～1000rpm, add rear continuation and stir 10min～60min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 100rpm～1000rpm, reducing agent is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 0 ℃～80 ℃, mixing speed is to continue stirring reaction 2h～24h under 100rpm～1000rpm condition, obtains product mixed solution; Four, add extractant: extractant is added in the product mixed solution that step 3 obtains, low whipping speed be under 100rpm～1000rpm condition, stir after 3h～12h standing, get upper oil phase and with the rotating speed centrifugal treating of 3000rpm～15000rpm, obtain product; Five, centrifuge washing and dry: under the condition that is 3000rpm～15000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 3 times～15 times, in temperature, be 50 ℃～80 ℃ vacuumize 3h～12h, obtain metallic cover oxidate nano catalyst with core-casing structure.
Oil phase solvent described in present embodiment step 1 is 1 with the volume ratio of middle phase: (5～15).
The volume ratio of the oil phase solvent described in present embodiment step 1 and water is 1: (15～30).
The amount of substance of the consisting of phase-transferring agent described in present embodiment step 1 is (150～300) with the amount of substance of oxide nano particles ratio: 1.
In metal shell precursor water solution described in present embodiment step 2, the amount of substance of metal shell presoma and the amount of substance of the oxide nano particles described in step 1 are than being (0.5～50): 1.
In the amount of substance of the reducing agent described in present embodiment step 3 and the metal shell precursor water solution described in step 2, the amount of substance of metal shell presoma is than being (1～50): 1.
The volume ratio of the water described in the extractant described in present embodiment step 4 and step 1 is (1～5): 1.
N-hexane/ethanolic solution described in present embodiment step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is (1～3): 1.
Metallic cover oxidate nano catalyst with core-casing structure described in present embodiment has unique oxide kernel, its oxide kernel can change electronic structure and the geometry of outer layer metal, and then effectively improve noble metal catalyst catalytic activity and stability, carry palladium (Pd/C) catalyst with commercial carbon and compare, catalytic activity is 1.5～3 times that commercial carbon carries palladium (Pd/C) catalyst.
Metallic cover oxidate nano catalyst with core-casing structure kernel described in present embodiment is oxide nano particles, the bimetallic catalyst with core-casing structure of the metallic cover metal that is noble metal with kernel is compared, greatly reduce fuel-cell catalyst noble metal dosage, effectively reduce catalyst cost.
Metallic cover oxidate nano catalyst with core-casing structure prepared by present embodiment has the evenly feature such as controlled of good dispersion, nano particle diameter and outer casing thickness.
Metallic cover oxidate nano catalyst with core-casing structure prepared by present embodiment can be used as fuel-cell catalyst and uses.
Present embodiment method is simple to operate, is easy to control, and can use the common presomas such as chlorate, nitrate, thereby the metallo-organic compound often using while avoiding conventional method to prepare nucleocapsid catalyst further reduces synthetic cost.
Embodiment five: present embodiment is different from embodiment four: the oxide nano particles described in step 1 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 a kind of, or two or more mixture wherein, or two or more oxide solid solution being prepared from wherein.Other are identical with embodiment four.
Oxide solid solution described in present embodiment is prepared according to the following steps: 1. first two or more oxide is dissolved in acid with arbitrary proportion, through stirring, obtains mixed solution, 2. in reactor, add successively distilled water and polyvinylpyrrolidone (PVP), and adopt acid that pH value is adjusted to 4～6, obtain liquid on earth, 3. then under temperature is the water bath with thermostatic control condition of 25 ℃～80 ℃, mixed solution is added drop-wise in end liquid, and in mixed solution adition process, drip ammoniacal liquor pH value is controlled to 7～10, after solution to be mixed dropwises, and stirring reaction 10～120min, obtained oxide solid solution gel, utilize half membrane dialyzing method purifying oxide solid solution gel, purifying rear oxidation thing mischcrystal jelly obtains oxide solid solution through vacuumize.
Embodiment six: present embodiment is different from one of embodiment four or five: the oil phase solvent described in step 1 is a kind of in oleic acid, linoleic acid, pentane, pentamethylene, trimethylpentane, hexane, heptane, octane, nonane, decane, dodecane and octadecylene or several mixture wherein; Consisting of phase-transferring agent described in step 1 is a kind of in enuatrol, linoleic acid sodium, neopelex, cetyl benzene sulfonic acid sodium salt, octadecyl benzene sulfonic acid sodium salt, lauryl sodium sulfate, sodium hexadecyl sulfate, sodium stearyl sulfate, dodecyl sodium sulfate, sodium cetanesulfonate, octadecyl sodium sulfonate, alkylpolyoxyethylene sodium sulphate, ceteth sodium sulphate and octadecyl polyethenoxy ether sodium sulfate or several mixture wherein; Centre described in step 1 is a kind of in ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, glycerol, butanols and amylalcohol or several mixture wherein mutually; Water described in step 1 is a kind of in deionized water and redistilled water.Other are identical with embodiment four or five.
Embodiment seven: present embodiment is different from one of embodiment four to six: the metal shell precursor water solution described in step 2 is a kind of of sulfate solution, nitrate aqueous solution, aqueous phosphatic, acetate aqueous solution, halide solution, the noble metal halogen hydracid aqueous solution and the noble metal halate aqueous solution or several mixture wherein; In metal shell precursor water solution described in step 2, the metal of metal shell presoma is a kind of or wherein several in Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and Sb.Other are identical with one of embodiment four to six.
Embodiment eight: present embodiment is different from one of embodiment four to seven: the reducing agent described in step 3 is a kind of in ascorbic acid, natrium citricum, potassium citrate, sodium borohydride, potassium borohydride, ammonium borohydride, formaldehyde and hydrazine hydrate or several mixture wherein.Other are identical with one of embodiment four to seven.
Embodiment nine: present embodiment is different from one of embodiment four to eight: the extractant described in step 4 is a kind of in toluene, dimethylbenzene, n-hexane, cyclohexane chloroform or several mixture wherein.Other are identical with one of embodiment four to eight.
Adopt following verification experimental verification invention effect:
Test one: a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: get CeO
2nano particle 0.06mmol is under 250W, the frequency condition that is 40kHz in the ultrasonic oleic acid that is scattered in 0.4mL at power, then add successively 0.4g enuatrol, 4mL ethanol and 2.5mL deionized water, and continue ultrasonic dispersion 30min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain the palladium nitrate solution of 4.5mL0.01mol/L under the condition that low whipping speed is 300rpm, add rear continuation and stir 30min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 300rpm, 1mL reducing agent ascorbic acid solution (0.04g/mL) is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 70 ℃, mixing speed is under 300rpm condition, to continue stirring reaction 24h, obtains product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is under 300rpm condition, to stir after 3h standingly, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, obtains black product; Five, centrifuge washing and dry: under the condition of rotating speed 7000rpm, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, is 80 ℃ of vacuumize 5h in temperature, obtains metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in step 5 is with CeO
2for kernel metal Pd be shell nano core-shell structure catalyst (amount of substance of Pd and CeO
2amount of substance ratio be 0.75: 1); N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1: 1.
Adopt the catalyst that this test obtains to make work electrode: 5mg catalyst is scattered in 5mL ethanol, ultrasonic 30min, obtains the dispersion liquid that catalyst concn is 1mg/mL, gets subsequently 15 μ L catalyst dispersant liquid drops and is added in glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L0.5%'s
(trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products) solution, obtains the glass-carbon electrode for three-electrode system after natural drying.
Test two: a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: get CeO
2nano particle 0.005mmol is under 250W, the frequency condition that is 40kHz in the ultrasonic oleic acid that is scattered in 0.4mL at power, then add successively 0.3g enuatrol, 4mL ethanol, 3.73mL deionized water, and continue ultrasonic dispersion 30min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain the palladium nitrate solution of 3.27mL0.01mol/L under the condition that low whipping speed is 300rpm, add rear continuation and stir 30min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 300rpm, 1ml reducing agent ascorbic acid solution (0.03g/mL) is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 70 ℃, mixing speed is under 300rpm condition, to continue stirring reaction 24h, obtains product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is under 300rpm condition, to stir after 3h standingly, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, obtains black product; Five, centrifuge washing and dry: under the condition that is 7000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, in temperature, be 80 ℃ of vacuumize 5h, obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in step 5 is with CeO
2for kernel metal Pd be shell nano core-shell structure catalyst (amount of substance of Pd and CeO
2amount of substance ratio be 6.54: 1); N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1: 1.
The catalyst that employing obtains with this test is made work electrode: 5mg catalyst is scattered in 5mL ethanol, ultrasonic 30min, obtains the dispersion liquid that catalyst concn is 1mg/mL, gets subsequently 15 μ L catalyst dispersant liquid drops and is added in glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L0.5%'s
(trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products) solution, has just obtained the glass-carbon electrode for three-electrode system after natural drying.
Test three: a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: get CeO
2nano particle 0.005mmol is under 250W, the frequency condition that is 40kHz in the ultrasonic oleic acid that is scattered in 0.4mL at power, then add successively 0.3g enuatrol, 4mL ethanol, 5mL deionized water, and continue ultrasonic dispersion 30min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain the palladium nitrate solution of 2mL0.05mol/L under the condition that low whipping speed is 300rpm, add rear continuation and stir 30min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 300rpm, 1ml reducing agent ascorbic acid solution (0.1g/mL) is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 70 ℃, mixing speed is under 300rpm condition, to continue stirring reaction 24h, obtains product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is under 300rpm condition, to stir after 3h standingly, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, obtains black product; Five, centrifuge washing and dry: under the condition that is 7000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, in temperature, be 80 ℃ of vacuumize 5h, obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in step 5 is with CeO
2for kernel metal Pd be shell nano core-shell structure catalyst (amount of substance of Pd and CeO
2amount of substance ratio be 20: 1); N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1: 1.
Adopt the catalyst that this test obtains to make work electrode: 5mg catalyst is scattered in 5mL ethanol, ultrasonic 30min, obtains the dispersion liquid that catalyst concn is 1mg/mL, gets subsequently 15 μ L catalyst dispersant liquid drops and is added in glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L0.5%'s
(trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products) solution, has just obtained the glass-carbon electrode for three-electrode system after natural drying.
Test four: adopt commercial carbon to carry palladium (Pd/C) catalyst and make work electrode, specifically complete according to the following steps:
Getting commercial carbon carries palladium (Pd/C) catalyst 5mg and is scattered in 5mL ethanol, ultrasonic 30min, obtain commercial carbon and carry the dispersion liquid that palladium (Pd/C) catalyst concn is 1mg/mL, the carbon of getting subsequently 15 μ L commercializations carries palladium (Pd/C) catalyst dispersant liquid drop and is added in glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L0.5%'s
solution (trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products), has just obtained the glass-carbon electrode for three-electrode system after natural drying.
At ambient temperature, the test three that respectively will test one adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes, test two adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make and test four to adopt commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode, the platinized platinum of 1 * 1cm is as to electrode, mercury/mercuric oxide electrode is reference electrode, at the KOH of 1mol/L and the CH of 0.5mol/L
3in OH mixed solution, carry out cyclic voltammetry scan, sweep speed is 50mV/s, scan potential range to be-0.8V is to 0.3V (vs.Hg/HgO), and as shown in Figure 1, Fig. 1 is methanol oxidation cyclic voltammetry curve figure to testing result, methanol oxidation cyclic voltammetry curve figure when zero in Fig. 1 represents that test one adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes as work electrode, methanol oxidation cyclic voltammetry curve figure when the ■ in Fig. 1 represents to test glass-carbon electrode that two employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, methanol oxidation cyclic voltammetry curve figure when the ◇ in Fig. 1 represents to test glass-carbon electrode that three employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, in Fig. 1 ● methanol oxidation cyclic voltammetry curve figure while representing that test four adopts commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode, as shown in Figure 1, the methanol oxidation peak-to-peak value electric current of metallic cover oxidate nano catalyst with core-casing structure prepared by test one to test three is all higher than common carbon-containing palladium catalyst, and a spike potential of just sweeping oxidation peak is also more negative than common carbon-containing palladium catalyst, illustrate no matter metallic cover oxidate nano catalyst with core-casing structure is the spike potential that rises at peak current density or methanol oxidation to the oxidation reaction of methyl alcohol, all more commercial carbon-containing palladium catalyst has obvious advantage, the peak current density of wherein testing the metallic cover oxidate nano catalyst with core-casing structure of three preparations is 2.5 times of commercial carbon-containing palladium catalyst, hence one can see that, metallic cover oxidate nano catalyst with core-casing structure has obvious catalytic activity advantage with respect to common carbon supported catalyst.
At ambient temperature, the test three that respectively will test one adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes, test two adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make and test four to adopt commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode, the platinized platinum of 1 * 1cm is as to electrode, mercury/mercuric oxide electrode is reference electrode, at the KOH of 1mol/L and the CH of 0.5mol/L
3constant potential current density test under carry out in OH mixed solution-0.2V current potential, the testing time is 900s, as shown in Figure 2, Fig. 2 is chronoa mperometric plot figure to testing result, chronoa mperometric plot figure when the ◇ in Fig. 2 represents to test glass-carbon electrode that an employing metallic cover oxidate nano catalyst with core-casing structure makes as work electrode, chronoa mperometric plot figure when the ■ in Fig. 2 represents to test glass-carbon electrode that two employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, chronoa mperometric plot figure when the in Fig. 2 represents to test glass-carbon electrode that three employing metallic cover oxidate nano catalyst with core-casing structure make as work electrode, in Fig. 2 ● represent chronoa mperometric plot figure when test four adopts commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode, as shown in Figure 2, metallic cover oxidate nano catalyst with core-casing structure and commercial carbon carry palladium (Pd/C) catalyst all has higher catalytic activity at the methanol oxidation initial stage, yet along with reaction continue carry out, commercial carbon carries palladium (Pd/C) catalyst because the impact of methyl alcohol intermediate product causes catalytic activity seriously to reduce, and metallic cover oxidate nano catalyst with core-casing structure interacts owing to existing between kernel and its outer layer metal, reduced and poisoned the impact of intermediate product on catalyst performance, effectively raise the antitoxin voltinism energy of catalyst, in course of reaction, show good catalytic activity and stability always, after the lasting oxidation of 900s, the catalytic activity of the metallic cover oxidate nano catalyst with core-casing structure of test three preparations is 2.7 times that commercial carbon carries palladium (Pd/C) catalyst.
Test five: a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: get CeO
2nano particle 0.005mmol is under 250W, the frequency condition that is 40kHz in the ultrasonic oleic acid that is scattered in 0.4mL at power, then add successively 0.3g enuatrol, 4mL ethanol, 3.73mL deionized water, and continue ultrasonic dispersion 30min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain the liquor argenti nitratis ophthalmicus of 3.27mL0.01mol/L under the condition that low whipping speed is 300rpm, add rear continuation and stir 30min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 300rpm, 1ml reducing agent ascorbic acid solution (0.03g/mL) is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 70 ℃, mixing speed is under 300rpm condition, to continue stirring reaction 24h, obtains product mixed solution; Four, add extractant: 10mL n-hexane is added in the product mixed solution that step 3 obtains, and low whipping speed is under 300rpm condition, to stir after 3h standingly, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, obtains black gray expandable product; Five, centrifuge washing and dry: under the condition that is 7000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, in temperature, be 80 ℃ of vacuumize 5h, obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in step 5 is to take nano core-shell structure catalyst (amount of substance of Ag and the CeO that CeO2 is shell as kernel metal A g
2amount of substance ratio be 6.54: 1); N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1: 1.
Test six: a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: get Al
2o
3nano particle 0.005mmol is under 250W, the frequency condition that is 40kHz in the ultrasonic oleic acid that is scattered in 0.4mL at power, then add successively 0.3g enuatrol, 4mL ethanol, 3.73mL deionized water, and continue ultrasonic dispersion 30min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain the palladium nitrate solution of 3.27mL0.01mol/L under the condition that low whipping speed is 300rpm, add rear continuation and stir 30min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 300rpm, 1mL reducing agent ascorbic acid solution (0.03g/mL) is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 70 ℃, mixing speed is under 300rpm condition, to continue stirring reaction 24h, obtains product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is under 300rpm condition, to stir after 3h standingly, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, obtains lark product; Five, centrifuge washing and dry: under the condition that is 7000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, in temperature, be 80 ℃ of vacuumize 5h, obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in step 5 is with Al
2o
3for kernel metal Pd be shell nano core-shell structure catalyst (amount of substance of Pd and Al
2o
3amount of substance ratio be 6.54: 1); N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1: 1.
Test seven: a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: get SnO
2nano particle 0.005mmol is under 250W, the frequency condition that is 40kHz in the ultrasonic oleic acid that is scattered in 0.4mL at power, then add successively 0.3g enuatrol, 4mL ethanol, 3.73mL deionized water, and continue ultrasonic dispersion 30min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain the ruthenic chloride solution of 3.27mL0.01mol/L under the condition that low whipping speed is 300rpm, add rear continuation and stir 30min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 300rpm, 1mL reducing agent ascorbic acid solution (0.03g/mL) is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 70 ℃, mixing speed is under 300rpm condition, to continue stirring reaction 24h, obtains product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is under 300rpm condition, to stir after 3h standingly, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, obtains black product; Five, centrifuge washing and dry: under the condition that is 7000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, in temperature, be 80 ℃ of vacuumize 5h, obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in step 5 is with SnO
2for kernel metal Ru be shell nano core-shell structure catalyst (amount of substance of Ag and SnO
2amount of substance ratio be 6.54: 1); N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1: 1.
Claims (6)
1. a preparation method for metallic cover oxidate nano catalyst with core-casing structure, is characterized in that the preparation method of metallic cover oxidate nano catalyst with core-casing structure completes according to the following steps:
One, prepare the stable mixed solution of transparent and homogeneous: by oxide nano particles, at power, be ultrasonic being scattered in oil phase solvent under 20W～1000W, the frequency condition that is 20kHz～80kHz, obtain the dispersion liquid that oxide nano particles concentration is 0.001mol/L～1mol/L, then add successively consisting of phase-transferring agent, mutually middle and water, and continue ultrasonic dispersion 10min～120min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: in the stable mixed solution of the transparent and homogeneous that dropwise adds step 1 to obtain metal shell precursor water solution under the condition that low whipping speed is 100rpm～1000rpm, add rear continuation and stir 10min～60min, obtain blend; Three, add reducing agent: under the condition that low whipping speed is 100rpm～1000rpm, reducing agent is added in the blend that step 2 obtains, after mixing, at bath temperature, be at 0 ℃～80 ℃, mixing speed is to continue stirring reaction 2h～24h under 100rpm～1000rpm condition, obtains product mixed solution; Four, add extractant: extractant is added in the product mixed solution that step 3 obtains, low whipping speed be under 100rpm～1000rpm condition, stir after 3h～12h standing, get upper oil phase and with the rotating speed centrifugal treating of 3000rpm～15000rpm, obtain product; Five, centrifuge washing and dry: under the condition that is 3000rpm～15000rpm at rotating speed, product step 4 being obtained with n-hexane/ethanolic solution carries out centrifuge washing 3 times～15 times, in temperature, be 50 ℃～80 ℃ vacuumize 3h～12h, obtain metallic cover oxidate nano catalyst with core-casing structure; Oil phase solvent described in step 1 is 1 with the volume ratio of middle phase: (5～15); The volume ratio of the oil phase solvent described in step 1 and water is 1: (15～30); The amount of substance of the consisting of phase-transferring agent described in step 1 is (150～300) with the amount of substance of oxide nano particles ratio: 1; In metal shell precursor water solution described in step 2, the amount of substance of metal shell presoma and the amount of substance of the oxide nano particles described in step 1 are than being (0.5～50): 1; In the amount of substance of the reducing agent described in step 3 and the metal shell precursor water solution described in step 2, the amount of substance of metal shell presoma is than being (1～50): 1; The volume ratio of the water described in the extractant described in step 4 and step 1 is (1～5): 1; N-hexane/ethanolic solution described in step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is (1～3): 1; Described metallic cover oxidate nano catalyst with core-casing structure is the nano core-shell structure catalyst that the even clad metal of shell, kernel are oxide nano particles, the thickness of the described even clad metal of shell is 1nm～20nm, and the particle diameter of described oxide nano particles is 1nm～200nm.
2. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 1, is characterized in that the oxide nano particles described in step 1 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 a kind of, or two or more mixture wherein, or two or more oxide solid solution being prepared from wherein.
3. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 1, is characterized in that the oil phase solvent described in step 1 is a kind of in oleic acid, linoleic acid, pentane, pentamethylene, trimethylpentane, hexane, heptane, octane, nonane, decane, dodecane and octadecylene or several mixture wherein; Consisting of phase-transferring agent described in step 1 is a kind of in enuatrol, linoleic acid sodium, neopelex, cetyl benzene sulfonic acid sodium salt, octadecyl benzene sulfonic acid sodium salt, lauryl sodium sulfate, sodium hexadecyl sulfate, sodium stearyl sulfate, dodecyl sodium sulfate, sodium cetanesulfonate, octadecyl sodium sulfonate, alkylpolyoxyethylene sodium sulphate, ceteth sodium sulphate and octadecyl polyethenoxy ether sodium sulfate or several mixture wherein; Centre described in step 1 is a kind of in ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, glycerol, butanols and amylalcohol or several mixture wherein mutually; Water described in step 1 is a kind of in deionized water or redistilled water.
4. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 1, it is characterized in that the metal shell precursor water solution described in step 2 is sulfate solution, nitrate aqueous solution, aqueous phosphatic, acetate aqueous solution, halide solution, the noble metal halogen hydracid aqueous solution and the noble metal halate aqueous solution a kind of or wherein several mixture, and in described metal shell precursor water solution, the metal of metal shell presoma is Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, a kind of or wherein several in Sn and Sb.
5. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 1, is characterized in that the reducing agent described in step 3 is a kind of in ascorbic acid, natrium citricum, potassium citrate, sodium borohydride, potassium borohydride, ammonium borohydride, formaldehyde and hydrazine hydrate or several mixture wherein.
6. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 1, is characterized in that the extractant described in step 4 is a kind of in toluene, dimethylbenzene, n-hexane, cyclohexane chloroform or several mixture wherein.
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