CN102969514A - 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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Abstract
The invention relates to a metal-coated oxide nano core-shell structure catalyst and a preparation method thereof, and in particular relates to a nano fuel cell catalyst with a core-shell structure, and a preparation method of the nano fuel cell catalyst. 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 nanometer fuel battery Catalysts and its preparation method with 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 height, 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 at present is the bimetallic catalyst with core-casing structure of metallic cover metal.The shortcoming of this catalyst is that its kernel generally still is the noble metals such as Au, Pd, does not reach the purpose that reduces the catalyst cost; And if kernel adopts base metal, in the long-term course of work, the dissolution phenomenas such as chemistry and electrochemistry can occur in the base metal of kernel, reduce the stability of catalyst; Therefore existing fuel-cell catalyst existence does not possess high catalytic activity, stability and the low problem of catalyst cost simultaneously.
Summary of the invention
The present invention will solve existing fuel-cell catalyst existence not possess simultaneously high catalytic activity, stability and the low problem of catalyst cost, and a kind of metallic cover oxidate nano catalyst with core-casing structure and preparation method thereof is provided.
A kind of metallic cover oxidate nano of the present invention catalyst with core-casing structure is that the even clad metal of shell, kernel are the nano core-shell structure catalyst of oxide nano particles, the thickness of the even clad metal of described shell is 1nm ~ 20nm, and the particle diameter of described oxide nano particles is 1nm ~ 200nm.
A kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically finish according to the following steps:
One, preparation transparent and homogeneous stable mixed solution: be that 20W ~ 1000W, frequency are ultrasonic being scattered in the oil phase solvent under the condition of 20kHz ~ 80kHz at power with oxide nano particles, obtain the dispersion liquid that oxide nano particles concentration is 0.001mol/L ~ 1mol/L, then add successively consisting of phase-transferring agent, centre and reach mutually water, and continue ultrasonic dispersion 10min ~ 120min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: low whipping speed is under the condition of 100rpm ~ 1000rpm the metal shell precursor water solution dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 10min ~ 60min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 100rpm ~ 1000rpm reducing agent to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 0 ℃ ~ 80 ℃, mixing speed is to continue stirring reaction 2h ~ 24h under 100rpm ~ 1000rpm condition, obtains the product mixed solution; Four, add extractant: extractant is added in the product mixed solution that step 3 obtains, low whipping speed is to leave standstill after stirring 3h ~ 12h under 100rpm ~ 500rpm condition, get upper oil phase and with the rotating speed centrifugal treating of 3000rpm ~ 15000rpm, namely obtain product; Five, centrifuge washing and drying: be under the condition of 3000rpm ~ 15000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 3 times ~ 15 times, be 50 ℃ ~ 80 ℃ vacuumize 3h ~ 12h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure; Oil phase solvent described in the step 1 is 1:(5 ~ 15 with the volume ratio of middle phase); The volume ratio of the oil phase solvent described in the step 1 and water is 1:(15 ~ 30); The amount of substance of the consisting of phase-transferring agent described in the step 1 and the molar ratio of oxide nano particles are (150 ~ 300): 1; The molar ratio of the amount of substance of metal shell presoma and the oxide nano particles described in the step 1 is (0.5 ~ 50) in the metal shell precursor water solution described in the step 2: 1; The molar ratio of metal shell presoma is (1 ~ 50) in the amount of substance of the reducing agent described in the step 3 and the metal shell precursor water solution described in the step 2: 1; The volume ratio of the water described in the extractant described in the step 4 and the step 1 is (1 ~ 5): 1; N-hexane/ethanolic solution described in the 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 Effective Raise noble metal catalyst catalytic activity and stability, carry palladium (Pd/C) catalyst with the carbon of commercialization and compare, catalytic activity is carried 1.5 ~ 3 times of palladium (Pd/C) catalyst for commercial carbon; Two, the prepared metallic cover oxidate nano catalyst with core-casing structure kernel of the present invention is oxide nano particles, be that the bimetallic catalyst with core-casing structure of the metallic cover metal of noble metal is compared with kernel, greatly reduce the fuel-cell catalyst noble metal dosage, effectively reduce the catalyst cost; Three, the prepared metallic cover oxidate nano catalyst with core-casing structure of the present invention has the evenly characteristics 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 the 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 that often uses when avoiding conventional method to prepare nucleocapsid catalyst further reduces synthetic cost.
Description of drawings
Fig. 1 is methanol oxidation cyclic voltammetry curve figure, methanol oxidation cyclic voltammetry curve figure when the expression test of zero among Fig. 1 one adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes as work electrode, ■ among Fig. 1 represents to test two cyclic voltammetry curve of methanol oxidation when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode figure, ◇ among Fig. 1 represents to test three cyclic voltammetry curve of methanol oxidation when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode figure, among Fig. 1 ● methanol oxidation cyclic voltammetry curve figure when expression 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, ◇ among Fig. 2 represents to test a chronoa mperometric plot figure when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes as work electrode, ■ among Fig. 2 represents to test two chronoa mperometric plot figure when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode, among Fig. 2 represents to test three chronoa mperometric plot figure when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode, among Fig. 2 ● the chronoa mperometric plot figure when expression 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 that the even clad metal of shell, kernel are the nano core-shell structure catalyst of oxide nano particles, the thickness of the even clad metal of described shell is 1nm ~ 20nm, and the particle diameter of described oxide nano particles is 1nm ~ 200nm.
The described metallic cover oxidate nano of present embodiment catalyst with core-casing structure has unique oxide kernel, its oxide kernel can change electronic structure and the geometry of outer layer metal, and then Effective Raise noble metal catalyst catalytic activity and stability, carry palladium (Pd/C) catalyst with the carbon of commercialization and compare, catalytic activity is carried 1.5 ~ 3 times of palladium (Pd/C) catalyst for commercial carbon.
The described metallic cover oxidate nano of present embodiment catalyst with core-casing structure kernel is oxide nano particles, be that the bimetallic catalyst with core-casing structure of the metallic cover metal of noble metal is compared with kernel, greatly reduce the fuel-cell catalyst noble metal dosage, effectively reduce the catalyst cost.
The described metallic cover oxidate nano of present embodiment catalyst with core-casing structure has the evenly characteristics such as controlled of good dispersion, nano particle diameter and outer casing thickness.
Embodiment two: what present embodiment and embodiment one were different is: 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, perhaps two or more mixture wherein, perhaps two or more oxide solid solution that is prepared from wherein.Other are identical with embodiment one.
The described oxide solid solution of present embodiment prepares according to the following steps: 1. at first two or more oxide is dissolved in the acid with arbitrary proportion, namely obtains mixed solution through stirring; 2. in reactor, add successively distilled water and polyvinylpyrrolidone (PVP), and adopt acid that the pH value is adjusted to 4 ~ 6, namely get on earth liquid, 3. then under temperature is 25 ℃ ~ 80 ℃ water bath with thermostatic control condition, mixed solution is added drop-wise in the end liquid, and in the mixed solution adition process, drip ammoniacal liquor the pH value is controlled at 7 ~ 10, after solution to be mixed dropwises, and stirring reaction 10 ~ 120min, namely obtained the oxide solid solution gel, utilize half membrane dialyzing method purifying oxide solid solution gel, purifying rear oxidation thing mischcrystal jelly namely obtains oxide solid solution through vacuumize.
Embodiment three: what present embodiment was different from one of embodiment one or two is: described metal is a kind of or wherein several among Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and the 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 finish according to the following steps:
One, preparation transparent and homogeneous stable mixed solution: be that 20W ~ 1000W, frequency are ultrasonic being scattered in the oil phase solvent under the condition of 20kHz ~ 80kHz at power with oxide nano particles, obtain the dispersion liquid that oxide nano particles concentration is 0.001mol/L ~ 1mol/L, then add successively consisting of phase-transferring agent, centre and reach mutually water, and continue ultrasonic dispersion 10min ~ 120min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: low whipping speed is under the condition of 100rpm ~ 1000rpm the metal shell precursor water solution dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 10min ~ 60min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 100rpm ~ 1000rpm reducing agent to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 0 ℃ ~ 80 ℃, mixing speed is to continue stirring reaction 2h ~ 24h under 100rpm ~ 1000rpm condition, obtains the product mixed solution; Four, add extractant: extractant is added in the product mixed solution that step 3 obtains, low whipping speed is to leave standstill after stirring 3h ~ 12h under 100rpm ~ 1000rpm condition, get upper oil phase and with the rotating speed centrifugal treating of 3000rpm ~ 15000rpm, namely obtain product; Five, centrifuge washing and drying: be under the condition of 3000rpm ~ 15000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 3 times ~ 15 times, be 50 ℃ ~ 80 ℃ vacuumize 3h ~ 12h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure.
Oil phase solvent described in the present embodiment step 1 is 1:(5 ~ 15 with the volume ratio of middle phase).
The volume ratio of the oil phase solvent described in the present embodiment step 1 and water is 1:(15 ~ 30).
The amount of substance of the consisting of phase-transferring agent described in the present embodiment step 1 and the molar ratio of oxide nano particles are (150 ~ 300): 1.
The molar ratio of the amount of substance of metal shell presoma and the oxide nano particles described in the step 1 is (0.5 ~ 50) in the metal shell precursor water solution described in the present embodiment step 2: 1.
The molar ratio of metal shell presoma is (1 ~ 50) in the amount of substance of the reducing agent described in the present embodiment step 3 and the metal shell precursor water solution described in the step 2: 1.
The volume ratio of the water described in the extractant described in the present embodiment step 4 and the step 1 is (1 ~ 5): 1.
N-hexane/ethanolic solution described in the present embodiment step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is (1 ~ 3): 1.
The described metallic cover oxidate nano of present embodiment catalyst with core-casing structure has unique oxide kernel, its oxide kernel can change electronic structure and the geometry of outer layer metal, and then Effective Raise noble metal catalyst catalytic activity and stability, carry palladium (Pd/C) catalyst with the carbon of commercialization and compare, catalytic activity is carried 1.5 ~ 3 times of palladium (Pd/C) catalyst for commercial carbon.
The described metallic cover oxidate nano of present embodiment catalyst with core-casing structure kernel is oxide nano particles, be that the bimetallic catalyst with core-casing structure of the metallic cover metal of noble metal is compared with kernel, greatly reduce the fuel-cell catalyst noble metal dosage, effectively reduce the catalyst cost.
The metallic cover oxidate nano catalyst with core-casing structure of present embodiment preparation has the evenly characteristics such as controlled of good dispersion, nano particle diameter and outer casing thickness.
The metallic cover oxidate nano catalyst with core-casing structure of present embodiment preparation can be used as fuel-cell catalyst and uses.
The present embodiment method is simple to operate, is easy to control, can use the common presomas such as chlorate, nitrate, thereby the metallo-organic compound that often uses when avoiding conventional method to prepare nucleocapsid catalyst further reduces synthetic cost.
Embodiment five: what present embodiment and embodiment four were different is: the oxide nano particles described in the 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, perhaps two or more mixture wherein, perhaps two or more oxide solid solution that is prepared from wherein.Other are identical with embodiment four.
The described oxide solid solution of present embodiment prepares according to the following steps: 1. at first two or more oxide is dissolved in the acid with arbitrary proportion, namely obtains mixed solution through stirring; 2. in reactor, add successively distilled water and polyvinylpyrrolidone (PVP), and adopt acid that the pH value is adjusted to 4 ~ 6, namely get on earth liquid, 3. then under temperature is 25 ℃ ~ 80 ℃ water bath with thermostatic control condition, mixed solution is added drop-wise in the end liquid, and in the mixed solution adition process, drip ammoniacal liquor the pH value is controlled at 7 ~ 10, after solution to be mixed dropwises, and stirring reaction 10 ~ 120min, namely obtained the oxide solid solution gel, utilize half membrane dialyzing method purifying oxide solid solution gel, purifying rear oxidation thing mischcrystal jelly namely obtains oxide solid solution through vacuumize.
Embodiment six: what present embodiment was different from one of embodiment four or five is: the oil phase solvent described in the step 1 is a kind of in oleic acid, linoleic acid, pentane, pentamethylene, trimethylpentane, hexane, heptane, octane, nonane, decane, dodecane and the octadecylene or several mixture wherein; Consisting of phase-transferring agent described in the 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 the octadecyl polyethenoxy ether sodium sulfate or several mixture wherein; Centre described in the step 1 is a kind of in ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, glycerol, butanols and the amylalcohol or several mixture wherein mutually; Water described in the step 1 is a kind of in deionized water and the redistilled water.Other are identical with embodiment four or five.
Embodiment seven: what present embodiment was different from one of embodiment four to six is: the metal shell precursor water solution described in the 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; The metal of metal shell presoma is a kind of or wherein several among Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and the Sb in the metal shell precursor water solution described in the step 2.Other are identical with one of embodiment four to six.
Embodiment eight: what present embodiment was different from one of embodiment four to seven is: the reducing agent described in the step 3 is a kind of in ascorbic acid, natrium citricum, potassium citrate, sodium borohydride, potassium borohydride, ammonium borohydride, formaldehyde and the hydrazine hydrate or several mixture wherein.Other are identical with one of embodiment four to seven.
Embodiment nine: what present embodiment was different from one of embodiment four to eight is: the extractant described in the step 4 is a kind of in toluene, dimethylbenzene, n-hexane, the 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 finish according to the following steps:
One, the stable mixed solution of preparation transparent and homogeneous: get CeO
2Nano particle 0.06mmol is that 250W, frequency are under the condition of 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: low whipping speed is under the condition of 300rpm the palladium nitrate solution of 4.5mL 0.01mol/L dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 30min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 300rpm 1mL reducing agent ascorbic acid solution (0.04g/mL) to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 70 ℃, mixing speed is to continue stirring reaction 24h under the 300rpm condition, obtains the product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is to leave standstill after stirring 3h under the 300rpm condition, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, namely obtains the black product; Five, centrifuge washing and drying: under the condition of rotating speed 7000rpm, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, is 80 ℃ of vacuumize 5h in temperature, namely obtains metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in the step 5 is with CeO
2Be nano core-shell structure catalyst (amount of substance of Pd and the CeO of shell for the kernel metal Pd
2Molar ratio be 0.75:1); N-hexane/ethanolic solution described in the step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1:1.
The catalyst that adopts this test to obtain is made work electrode: the 5mg catalyst is scattered in the 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 the glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L's 0.5%
(trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products) solution namely 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 finish according to the following steps:
One, the stable mixed solution of preparation transparent and homogeneous: get CeO
2Nano particle 0.005mmol is that 250W, frequency are under the condition of 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: low whipping speed is under the condition of 300rpm the palladium nitrate solution of 3.27mL 0.01mol/L dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 30min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 300rpm 1ml reducing agent ascorbic acid solution (0.03g/mL) to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 70 ℃, mixing speed is to continue stirring reaction 24h under the 300rpm condition, obtains the product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is to leave standstill after stirring 3h under the 300rpm condition, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, namely obtains the black product; Five, centrifuge washing and drying: be under the condition of 7000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, be 80 ℃ of vacuumize 5h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in the step 5 is with CeO
2Be nano core-shell structure catalyst (amount of substance of Pd and the CeO of shell for the kernel metal Pd
2Molar ratio be 6.54:1); N-hexane/ethanolic solution described in the step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1:1.
Employing is made work electrode with the catalyst that this test obtains: the 5mg catalyst is scattered in the 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 the glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L's 0.5%
(trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products) solution has just obtained being used for the glass-carbon electrode of three-electrode system after natural drying.
Test three: a kind of preparation method of metallic cover oxidate nano catalyst with core-casing structure, specifically finish according to the following steps:
One, the stable mixed solution of preparation transparent and homogeneous: get CeO
2Nano particle 0.005mmol is that 250W, frequency are under the condition of 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: low whipping speed is under the condition of 300rpm the palladium nitrate solution of 2mL 0.05mol/L dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 30min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 300rpm 1ml reducing agent ascorbic acid solution (0.1g/mL) to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 70 ℃, mixing speed is to continue stirring reaction 24h under the 300rpm condition, obtains the product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is to leave standstill after stirring 3h under the 300rpm condition, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, namely obtains the black product; Five, centrifuge washing and drying: be under the condition of 7000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, be 80 ℃ of vacuumize 5h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in the step 5 is with CeO
2Be nano core-shell structure catalyst (amount of substance of Pd and the CeO of shell for the kernel metal Pd
2Molar ratio be 20:1); N-hexane/ethanolic solution described in the step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1:1.
The catalyst that adopts this test to obtain is made work electrode: the 5mg catalyst is scattered in the 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 the glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L's 0.5%
(trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products) solution has just obtained being used for the glass-carbon electrode of three-electrode system after natural drying.
Test four: adopt commercial carbon to carry palladium (Pd/C) catalyst and make work electrode, specifically finish according to the following steps:
The carbon of getting commercialization carries palladium (Pd/C) catalyst 5mg and is scattered in the 5mL ethanol, ultrasonic 30min, obtaining commercial carbon, to carry palladium (Pd/C) catalyst concn be the dispersion liquid of 1mg/mL, the carbon of getting subsequently 15 μ L commercializations carries palladium (Pd/C) catalyst dispersant liquid drop and is added in the glass-carbon electrode surface, after ethanol is natural drying, drip 5 μ L's 0.5%
Solution (trade name of E.I.Du Pont Company registration, a kind of perfluorinated sulfonic acid series products) has just obtained being used for the glass-carbon electrode of three-electrode system after natural drying.
At ambient temperature, to test respectively glass-carbon electrode, test three that glass-carbon electrode, a test two of adopting metallic cover oxidate nano catalyst with core-casing structure to make adopt metallic cover oxidate nano catalyst with core-casing structure to make adopts the glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make and tests four and adopt commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode, the platinized platinum conduct of 1 * 1cm is to electrode, mercury/mercuric oxide electrode is reference electrode, at the KOH of 1mol/L and the CH of 0.5mol/L
3Carry out cyclic voltammetry scan in the OH mixed solution, sweep speed is 50mV/s, and the scanning potential range is-0.8V is to 0.3V (vs.Hg/HgO), testing result as shown in Figure 1, Fig. 1 is methanol oxidation cyclic voltammetry curve figure; Methanol oxidation cyclic voltammetry curve figure when the expression test of zero among Fig. 1 one adopts glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes as work electrode; ■ among Fig. 1 represents to test two cyclic voltammetry curve of methanol oxidation when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode figure; ◇ among Fig. 1 represents to test three cyclic voltammetry curve of methanol oxidation when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode figure; Among Fig. 1 ● methanol oxidation cyclic voltammetry curve figure when expression test four adopts commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode; As shown in Figure 1, test one to the methanol oxidation peak-to-peak value electric current of the metallic cover oxidate nano catalyst with core-casing structure of test three preparations all is 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 that 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 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, and metallic cover oxidate nano catalyst with core-casing structure has obvious catalytic activity advantage with respect to common carbon supported catalyst.
At ambient temperature, to test respectively glass-carbon electrode, test three that glass-carbon electrode, a test two of adopting metallic cover oxidate nano catalyst with core-casing structure to make adopt metallic cover oxidate nano catalyst with core-casing structure to make adopts the glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make and tests four and adopt commercial carbon to carry glass-carbon electrode that palladium (Pd/C) catalyst makes as work electrode, the platinized platinum conduct of 1 * 1cm is to electrode, mercury/mercuric oxide electrode is reference electrode, at the KOH of 1mol/L and the CH of 0.5mol/L
3Carry out in the OH mixed solution-constant potential current density test under the 0.2V current potential, the testing time is 900s, testing result as shown in Figure 2, Fig. 2 is chronoa mperometric plot figure; ◇ among Fig. 2 represents to test a chronoa mperometric plot figure when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure makes as work electrode; ■ among Fig. 2 represents to test two chronoa mperometric plot figure when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode; among Fig. 2 represents to test three chronoa mperometric plot figure when adopting glass-carbon electrode that metallic cover oxidate nano catalyst with core-casing structure make as work electrode; Among Fig. 2 ● the chronoa mperometric plot figure when expression 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 the 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 is owing to exist interaction between kernel and its outer layer metal, reduced and poisoned intermediate product to the impact of catalyst performance, effectively raise the antitoxin voltinism energy of catalyst, in course of reaction, show good catalytic activity and stability always, through 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 finish according to the following steps:
One, the stable mixed solution of preparation transparent and homogeneous: get CeO
2Nano particle 0.005mmol is that 250W, frequency are under the condition of 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: low whipping speed is under the condition of 300rpm the liquor argenti nitratis ophthalmicus of 3.27mL 0.01mol/L dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 30min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 300rpm 1ml reducing agent ascorbic acid solution (0.03g/mL) to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 70 ℃, mixing speed is to continue stirring reaction 24h under the 300rpm condition, obtains the product mixed solution; Four, add extractant: the 10mL n-hexane is added in the product mixed solution that step 3 obtains, and low whipping speed is to leave standstill after stirring 3h under the 300rpm condition, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, namely obtains the black gray expandable product; Five, centrifuge washing and drying: be under the condition of 7000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, be 80 ℃ of vacuumize 5h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in the step 5 is take nano core-shell structure catalyst (amount of substance of Ag and the CeO of CeO2 as kernel metal A g as shell
2Molar ratio be 6.54:1); N-hexane/ethanolic solution described in the 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 finish according to the following steps:
One, the stable mixed solution of preparation transparent and homogeneous: get Al
2O
3Nano particle 0.005mmol is that 250W, frequency are under the condition of 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: low whipping speed is under the condition of 300rpm the palladium nitrate solution of 3.27mL 0.01mol/L dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 30min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 300rpm 1mL reducing agent ascorbic acid solution (0.03g/mL) to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 70 ℃, mixing speed is to continue stirring reaction 24h under the 300rpm condition, obtains the product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is to leave standstill after stirring 3h under the 300rpm condition, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, namely obtains the lark product; Five, centrifuge washing and drying: be under the condition of 7000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, be 80 ℃ of vacuumize 5h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in the step 5 is with Al
2O
3Be nano core-shell structure catalyst (amount of substance of Pd and the Al of shell for the kernel metal Pd
2O
3Molar ratio be 6.54:1); N-hexane/ethanolic solution described in the 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 finish according to the following steps:
One, the stable mixed solution of preparation transparent and homogeneous: get SnO
2Nano particle 0.005mmol is that 250W, frequency are under the condition of 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: low whipping speed is under the condition of 300rpm the ruthenic chloride solution of 3.27mL 0.01mol/L dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 30min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 300rpm 1mL reducing agent ascorbic acid solution (0.03g/mL) to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 70 ℃, mixing speed is to continue stirring reaction 24h under the 300rpm condition, obtains the product mixed solution; Four, add extractant: 10mL toluene is added in the product mixed solution that step 3 obtains, and low whipping speed is to leave standstill after stirring 3h under the 300rpm condition, gets upper oil phase and with the rotating speed centrifugal treating of 7000rpm, namely obtains the black product; Five, centrifuge washing and drying: be under the condition of 7000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 5 times, be 80 ℃ of vacuumize 5h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure; Metallic cover oxidate nano catalyst with core-casing structure described in the step 5 is with SnO
2Be nano core-shell structure catalyst (amount of substance of Ag and the SnO of shell for kernel metal Ru
2Molar ratio be 6.54:1); N-hexane/ethanolic solution described in the step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is 1:1.
Claims (9)
1. metallic cover oxidate nano catalyst with core-casing structure, it is characterized in that metallic cover oxidate nano catalyst with core-casing structure is that the even clad metal of shell, kernel are the nano core-shell structure catalyst of oxide nano particles, the thickness of the even clad metal of described shell is 1nm ~ 20nm, and the particle diameter of described oxide nano particles is 1nm ~ 200nm.
2. a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 1 is characterized in that 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, perhaps two or more mixture wherein, perhaps two or more oxide solid solution that is prepared from wherein.
3. a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 1 is characterized in that described metal is a kind of or wherein several among Pt, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn and the Sb.
4. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure as claimed in claim 1 is characterized in that the preparation method of metallic cover oxidate nano catalyst with core-casing structure finishes according to the following steps:
One, preparation transparent and homogeneous stable mixed solution: be that 20W ~ 1000W, frequency are ultrasonic being scattered in the oil phase solvent under the condition of 20kHz ~ 80kHz at power with oxide nano particles, obtain the dispersion liquid that oxide nano particles concentration is 0.001mol/L ~ 1mol/L, then add successively consisting of phase-transferring agent, centre and reach mutually water, and continue ultrasonic dispersion 10min ~ 120min, obtain the stable mixed solution of transparent and homogeneous; Two, blending and stirring: low whipping speed is under the condition of 100rpm ~ 1000rpm the metal shell precursor water solution dropwise to be added in the stable mixed solution of transparent and homogeneous that step 1 obtains, adds rear continuation and stirs 10min ~ 60min, obtains blend; Three, add reducing agent: low whipping speed is under the condition of 100rpm～1000rpm reducing agent to be added in the blend that step 2 obtains, behind the mixing at bath temperature be under 0 ℃ ~ 80 ℃, mixing speed is to continue stirring reaction 2h ~ 24h under 100rpm ~ 1000rpm condition, obtains the product mixed solution; Four, add extractant: extractant is added in the product mixed solution that step 3 obtains, low whipping speed is to leave standstill after stirring 3h～12h under 100rpm ~ 1000rpm condition, get upper oil phase and with the rotating speed centrifugal treating of 3000rpm～15000rpm, namely obtain product; Five, centrifuge washing and drying: be under the condition of 3000rpm～15000rpm at rotating speed, the product that step 4 is obtained with n-hexane/ethanolic solution carries out centrifuge washing 3 times ~ 15 times, be 50 ℃ ~ 80 ℃ vacuumize 3h ~ 12h in temperature, namely obtain metallic cover oxidate nano catalyst with core-casing structure; Oil phase solvent described in the step 1 is 1:(5 ~ 15 with the volume ratio of middle phase); The volume ratio of the oil phase solvent described in the step 1 and water is 1:(15 ~ 30); The amount of substance of the consisting of phase-transferring agent described in the step 1 and the molar ratio of oxide nano particles are (150 ~ 300): 1; The molar ratio of the amount of substance of metal shell presoma and the oxide nano particles described in the step 1 is (0.5 ~ 50) in the metal shell precursor water solution described in the step 2: 1; The molar ratio of metal shell presoma is (1 ~ 50) in the amount of substance of the reducing agent described in the step 3 and the metal shell precursor water solution described in the step 2: 1; The volume ratio of the water described in the extractant described in the step 4 and the step 1 is (1 ~ 5): 1; N-hexane/ethanolic solution described in the step 5 is mixed by n-hexane and ethanol, and the volume ratio of n-hexane and ethanol is (1 ~ 3): 1.
5. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 4 is characterized in that the oxide nano particles described in the 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, perhaps two or more mixture wherein, perhaps two or more oxide solid solution that is prepared from wherein.
6. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 4 is characterized in that the oil phase solvent described in the step 1 is a kind of in oleic acid, linoleic acid, pentane, pentamethylene, trimethylpentane, hexane, heptane, octane, nonane, decane, dodecane and the octadecylene or several mixture wherein; Consisting of phase-transferring agent described in the 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 the octadecyl polyethenoxy ether sodium sulfate or several mixture wherein; Centre described in the step 1 is a kind of in ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, glycerol, butanols and the amylalcohol or several mixture wherein mutually; Water described in the step 1 is a kind of in deionized water or the redistilled water.
7. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 4, it is characterized in that the metal shell precursor water solution described in the 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 several mixture wherein, and the metal of metal shell presoma is Pt in the described metal shell precursor water solution, Pd, Ru, Os, Rh, Ir, Ag, Au, Re, Cr, Fe, Mn, Co, Ni, Cu, Zn, In, Sn, a kind of or wherein several with among the Sb.
8. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 4 is characterized in that the reducing agent described in the step 3 is a kind of in ascorbic acid, natrium citricum, potassium citrate, sodium borohydride, potassium borohydride, ammonium borohydride, formaldehyde and the hydrazine hydrate or several mixture wherein.
9. the preparation method of a kind of metallic cover oxidate nano catalyst with core-casing structure according to claim 4 is characterized in that the extractant described in the step 4 is a kind of in toluene, dimethylbenzene, n-hexane, the cyclohexane chloroform or several mixture wherein.
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