CN103752328B - A kind of preparation method of the hollow core-shell catalyst for fuel cell - Google Patents
A kind of preparation method of the hollow core-shell catalyst for fuel cell Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the hollow core-shell catalyst for fuel cell, comprise: under (1) room temperature, one or both in cobalt chloride, nickel chloride and natrium citricum are mixed with the aqueous solution, with sodium borohydride reduction under sonic oscillation condition, obtain nanometer core; (2) above-mentioned nanometer core sonic oscillation is loaded on functionalized multi-wall carbonnanotubes, after adding sodium borohydride solution, then drip chloroplatinic acid or palladium chloride aqueous solution sonic oscillation 30 ~ 60min obtains nanoshell, finally wash, be drying to obtain hollow core-shell catalyst.The present invention tests the performance of prepared catalyst Oxidation of Methanol by electrochemical cyclic voltammetry, finds that hollow core-shell structure catalyst is significantly increased compared with the performance of alloy catalyst; The present invention is simple and quick, and the catalyst cost of preparation is low, mithridatism is high, catalytic performance good, has the potential application foreground in DMFC.
Description
Technical field
The invention belongs to the preparation field of catalyst material, particularly a kind of preparation method of the hollow core-shell catalyst for fuel cell.
Background technology
Fuel cell is a kind of TRT chemical energy of fuel directly being changed into electric energy.Due in its conversion process without the need to through fuel combustion, the therefore generation of the pollutant such as nitrogenfree oxide or sulfide, and its theoretical conversion efficiency is 100%.Only have 15% ~ 40% compared to transformation efficiency and with serious pollution thermoelectricity and the larger nuclear power of nuclear pollution risk, fuel cell also has the plurality of advantages such as clean and safe, load responding is fast, running quality is high.Obvious fuel cell, to the solution energy and this two hang-up of environment, all has great significance, was once chosen as 21 century to one of large new and high technology of the mankind the most influential ten by U.S.'s Time-Life News.
Proton Exchange Membrane Fuel Cells (PEMFC) occupies the larger types of fuel cells of the market share in recent years, wherein DMFC (DMFC) is easy to get because it is with low cost, can be used as the power supply of portable electric appts such as mobile phone, notebook computer etc., become one of Main way of current fuel cell development.The research of DMFC has achieved much important technological break-through, but is reduced costs remained problem demanding prompt solution (QiaoY, etal, J.Mater.Chem., 2011,21,4027-4036) by development high performance catalyst.The Pt that the DMFC catalyst of current synthesis is mainly used in acid medium is catalyst based and catalyst based for the Pd in alkaline medium.For improving its mithridatism, particularly Pt is catalyst based, often through doping other metal, such as Ru and Sn etc., and synthesis bianry alloy catalyst Pt-M and nucleocapsid catalyst PtM or MPt (Ru, Mo, W, Sn, Pd, Ni etc.).For reducing catalyst cost, by synthesizing hollow Pt base and Pd base nano ball shell.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the hollow core-shell catalyst for fuel cell, the method is containing transition metal Co and Ni in Pt and Pd, and make hollow core-shell structure, both improve catalytic performance, and the consumption reducing noble metal reduces cost; Operating process is simple and quick, has potential application foreground in a fuel cell.
The preparation method of a kind of hollow core-shell catalyst for fuel cell of the present invention, comprising:
(1) under room temperature, one or both in cobalt chloride, nickel chloride and natrium citricum are mixed with the aqueous solution, with sodium borohydride reduction under sonic oscillation condition, obtain nanometer core;
(2) above-mentioned nanometer core sonic oscillation is loaded on functionalized multi-wall carbonnanotubes (CNTs), after adding sodium borohydride solution, drip chloroplatinic acid again or palladium chloride aqueous solution sonic oscillation 30 ~ 60min obtains nanoshell, finally wash, be drying to obtain novel hollow nucleocapsid catalyst h-MPt/CNTs or h-MPd/CNTs(h and represent hollow type, M represents single transition metal or its alloy core).
(3) above-mentioned institute controlling catalyst is placed in glassy carbon electrode surface, by the performance of electrochemical cyclic voltammetry detecting catalyst catalytic oxidation methyl alcohol.
The proportioning of the amount of substance of one or both sums in described step (1) in cobalt chloride, nickel chloride and natrium citricum, sodium borohydride is 4:5:6.
In described step (1), the time of sonic oscillation is 10 ~ 20min.
In described step (2), the concentration of functionalized multi-wall carbonnanotubes CNTs is 0.1mg/mL.
In described step (2), nanometer core is loaded on CNTs by sonic oscillation 30 ~ 60min.
In described step (2), nanoshell is platinum-shell structural, and wherein the amount proportioning of nucleocapsid metallics is 4:1.
In described step (2), nanoshell is palladium shell structure, and wherein the amount proportioning of nucleocapsid metallics is 1:1.
Washing is for first to use ultra-pure water sonic oscillation centrifuge washing 3 times in described step (2), then to vibrate centrifuge washing 3 times with EtOH Sonicate.
Drying is drying 6 ~ 10h at 40 ~ 50 DEG C in vacuum drying chamber in described step (2).
Working electrode in described step (3) is glass-carbon electrode, is platinum electrode to electrode, and reference electrode is saturated calomel electrode (SCE).
Electrolyte in described step (3) is N
2saturated 2.0MCH
3oH+1.0MH
2sO
4solution or N
2saturated 1.0MCH
3oH+0.5MNaOH solution.
In described step (3), electrolyte temperature is 22 ~ 28 DEG C, and potential scanning speed is 0.05V/s, and electric potential scanning scope is-0.2 ~ 1.0V or-1.0V ~ 0.4V.
The hollow core-shell catalyst that described step (2) obtains is for the preparation of methanol fuel cell.
The oscillator device that the present invention adopts is KQ-3200 type ultrasonic cleaner; Drying equipment is DZF-6051 vacuum drying chamber; Centrifugation apparatus is 80-2 electric centrifuge; Electro-chemical test equipment is CHI660D electrochemical workstation.
Alloying is effectively combined with hollow core-shell structure by the present invention, and develop novel MPt and the MPd catalyst of a class hollow type nucleocapsid structure, the performance of its more corresponding alloy catalyst is significantly increased, and has the application prospect in DMFC.
Beneficial effect:
(1) preparation method of the present invention catalyst performance that is simple and quick, preparation is good, overcomes general catalyst synthesis complexity, mithridatism is low, catalytic performance is poor, high in cost of production shortcoming;
(2) present invention incorporates that Alloy Anti toxicity is high, nucleocapsid structure catalytic performance is good, low cost and other advantages, prepared novel hollow catalyst with core-casing structure;
(3) the present invention has prepared carbon nanotube loaded CoNiPt and CoNiPd catalyst by introducing cheap transition metal Co and Ni, both improves catalytic performance, and additionally reduces noble metal dosage;
(4) the novel hollow nucleocapsid catalyst that prepared by the present invention has higher catalytic activity compared with alloy catalyst prepared by conventional method, in DMFC, have potential application foreground.
Accompanying drawing explanation
Fig. 1 is the TEM figure of prepared hollow core-shell structure catalyst h-CoNiPt/CNTs.
Fig. 2 be prepared hollow core-shell catalyst h-CoPt/CNTs, h-NiPt/CNTs, h-CoNiPt/CNTs and alloy catalyst CoNiPt/CNTs in acid medium to anodic oxidation of methanol cyclic voltammetry curve.
Fig. 3 be prepared hollow core-shell catalyst h-CoPd/CNTs, h-NiPd/CNTs, h-CoNiPd/CNTs and alloy catalyst CoNiPd/CNTs in alkaline medium to anodic oxidation of methanol cyclic voltammetry curve.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
The preparation of hollow core-shell catalyst h-CoPt/CNTs.
Pipette cobalt chloride solution (0.1ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), pour into rapidly and newly join sodium borohydride solution (2.4mg/ml, 10ml), after sonic oscillation 10 ~ 20min, dropwise join the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, then sonic oscillation dispersion 30 ~ 60min; Drip successively and newly join sodium borohydride solution (2.4mg/ml, 10ml), chloroplatinic acid aqueous solution (0.001M, 10ml), newly join sodium borohydride solution (2.4mg/ml, 10ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained h-CoPt/CNTs catalyst.
Embodiment 2
The preparation of hollow core-shell catalyst h-NiPt/CNTs:
Pipette nickel chloride aqueous solution (0.1ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), pour rapidly the sodium borohydride solution (2.4mg/ml newly joined into, 10ml), after sonic oscillation 10 ~ 20min, dropwise join the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, after sonic oscillation dispersion 30 ~ 60min, drip the sodium borohydride solution (2.4mg/ml newly joined successively, 10ml), chloroplatinic acid aqueous solution (0.001M, 10ml), sodium borohydride solution (the 2.4mg/ml newly joined, 10ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained NiPt-CNTs catalyst.
Embodiment 3
The preparation of hollow core-shell catalyst h-CoNiPt/CNTs:
Pipette cobalt chloride solution (0.05ml, 0.4M), nickel chloride aqueous solution (0.05ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), pour rapidly the sodium borohydride solution (2.4mg/ml newly joined into, 10ml), after sonic oscillation 10 ~ 20min, dropwise join the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, after sonic oscillation dispersion 30 ~ 60min, drip the sodium borohydride solution (2.4mg/ml newly joined successively, 10ml), chloroplatinic acid aqueous solution (0.001M, 10ml), sodium borohydride solution (the 2.4mg/ml newly joined, 10ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained h-CoNiPt/CNTs catalyst.As shown in TEM figure (Fig. 1), the catalyst of synthesis is hollow core-shell structure.
Embodiment 4
The preparation of hollow core-shell catalyst h-CoPd/CNTs:
Pipette cobalt chloride solution (0.1ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), pour into rapidly and newly join sodium borohydride solution (2.4mg/ml, 10ml), after sonic oscillation 10 ~ 20min, dropwise join the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, then sonic oscillation dispersion 30 ~ 60min; Drip successively and newly join sodium borohydride solution (2.4mg/ml, 10ml), palladium chloride aqueous solution (4ml, 0.01M), newly join sodium borohydride solution (2.4mg/ml, 10ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained h-CoPd/CNTs catalyst.
Embodiment 5
The preparation of hollow core-shell catalyst h-NiPd/CNTs:
Pipette nickel chloride aqueous solution (0.1ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), pour rapidly the sodium borohydride solution (2.4mg/ml newly joined into, 10ml), after sonic oscillation 10 ~ 20min, dropwise join the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, after sonic oscillation dispersion 30 ~ 60min, drip the sodium borohydride solution (2.4mg/ml newly joined successively, 10ml), palladium chloride aqueous solution (4ml, 0.01M), sodium borohydride solution (the 2.4mg/ml newly joined, 10ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained NiPd-CNTs catalyst.
Embodiment 6
The preparation of hollow core-shell catalyst h-CoNiPd/CNTs:
Pipette cobalt chloride solution (0.05ml, 0.4M), nickel chloride aqueous solution (0.05ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), pour rapidly the sodium borohydride solution (2.4mg/ml newly joined into, 10ml), after sonic oscillation 10 ~ 20min, dropwise join the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, after sonic oscillation dispersion 30 ~ 60min, drip the sodium borohydride solution (2.4mg/ml newly joined successively, 10ml), palladium chloride aqueous solution (40ml, 0.001M), sodium borohydride solution (the 2.4mg/ml newly joined, 10ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained CoNiPd/CNTs catalyst.
Embodiment 7
The electrocatalysis characteristic test that in acid medium, Pt is catalyst based:
Institute controlling catalyst 1mg is dispersed in 1ml ultra-pure water, after sonic oscillation 30 ~ 60min, pipettes 10 microlitres and drop in diameter 3mm glassy carbon electrode surface, dry with infrared lamp; Again by 6 microlitre Nafion(0.5wt%) solution drips and covers on a catalyst, dry obtained working electrode immediately, and insert N under infrared lamp
2saturated 2.0MCH
3oH+1.0MH
2sO
4in solution, the cyclic voltammetry curve of test anodic oxidation of methanol, potential scanning speed is 0.05V/s, and electric potential scanning scope is-0.2 ~ 1.0V, and electrolyte temperature is 22 ~ 28 DEG C.Result shows that the hollow core-shell catalyst synthesized by the present invention has good catalytic activity (in Fig. 2 1#, 2#, 3# curve) to methanol oxidation.The ternary alloy catalyst same method of synthesis in comparative example 1 is modified at glassy carbon electrode surface preparation work electrode, carry out electro-chemical test, and with the performance comparison of above-mentioned hollow core-shell catalyst, find all hollow core-shell catalyst catalysis methanol oxidation currents (1# in Fig. 2,2#, 3# curve) all higher than ternary metal alloy catalyst (in Fig. 2 0# curve), show that the catalytic performance of the more corresponding ternary alloy catalyst of hollow core-shell catalyst is all significantly increased.
Embodiment 8
The electrocatalysis characteristic test that in alkaline medium, Pd is catalyst based:
Institute controlling catalyst 1mg is dispersed in 1ml ultra-pure water, after sonic oscillation 30 ~ 60min, pipettes 10 microlitres and drop in diameter 3mm glassy carbon electrode surface, dry with infrared lamp; Again by 6 microlitre Nafion(0.5wt%) solution drips and covers on a catalyst, dry obtained working electrode immediately, and insert N under infrared lamp
2saturated 1.0MCH
3in OH+0.5MNaOH solution, the cyclic voltammetry curve of test anodic oxidation of methanol, potential scanning speed is 0.05V/s, and electric potential scanning scope is-1.0V ~ 0.4V, and electrolyte temperature is 22 ~ 28 DEG C.Result shows that the hollow core-shell catalyst synthesized by the present invention has good catalytic activity (in Fig. 3 1#, 2#, 3# curve) to methanol oxidation.The ternary alloy catalyst same method of synthesis in comparative example 2 is modified at glassy carbon electrode surface preparation work electrode, carry out electro-chemical test, and with the performance comparison of above-mentioned hollow core-shell catalyst, find all hollow core-shell catalyst catalysis methanol oxidation currents (1# in Fig. 3,2#, 3# curve) all higher than ternary metal alloy catalyst (in Fig. 3 0# curve), show that the catalytic performance of the more corresponding ternary alloy catalyst of hollow core-shell catalyst is all significantly increased.
Comparative example 1
The preparation of alloy catalyst CoNiPt/CNTs:
Pipette chloroplatinic acid aqueous solution (1ml, 0.01M), nickel chloride aqueous solution (0.05ml, 0.4M), cobalt chloride solution (0.05ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), dropwise add the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, after sonic oscillation dispersion 10 ~ 20min, pour rapidly the sodium borohydride solution (2.4mg/ml newly joined into, 30ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained CoNiPt/CNTs alloy catalyst.
Comparative example 2
The preparation of alloy catalyst CoNiPd/CNTs:
Pipette palladium chloride aqueous solution (4ml, 0.01M), nickel chloride aqueous solution (0.05ml, 0.4M), cobalt chloride solution (0.05ml, 0.4M) with sodium citrate aqueous solution (0.5ml, 0.1M) add dilution in ultra-pure water (10ml), dropwise add the CNTs(0.1mg/ml in sonic oscillation, 50ml) in solution, after sonic oscillation dispersion 30 ~ 60min, pour rapidly the sodium borohydride solution (2.4mg/ml newly joined into, 30ml), after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained CoNiPd/CNTs alloy catalyst.
Claims (1)
1., for a preparation method for the hollow core-shell catalyst of fuel cell, comprising:
Pipette 0.4M cobalt chloride solution 0.05mL, 0.4M nickel chloride aqueous solution 0.05mL and 0.1M sodium citrate aqueous solution 0.5mL adds the ultrapure dilution with water of 10mL, pour into rapidly in the 10mL2.4mg/mL sodium borohydride solution of newly joining, after sonic oscillation 10 ~ 20min, dropwise join in the 50mL0.1mg/mLCNTs solution in sonic oscillation, after sonic oscillation dispersion 30 ~ 60min, drip the 10mL2.4mg/mL sodium borohydride solution of newly joining successively, 10mL0.001M chloroplatinic acid aqueous solution, the 10mL2.4mg/mL sodium borohydride solution of newly joining, after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained h-CoNiPt/CNTs catalyst,
Or, pipette 0.4M cobalt chloride solution 0.05mL, 0.4M nickel chloride aqueous solution 0.05mL and 0.1M sodium citrate aqueous solution 0.5mL adds the ultrapure dilution with water of 10mL, pour into rapidly in the 10mL2.4mg/mL sodium borohydride solution of newly joining, after sonic oscillation 10 ~ 20min, dropwise join in the 50mL0.1mg/mLCNTs solution in sonic oscillation, after sonic oscillation dispersion 30 ~ 60min, drip the 10mL2.4mg/mL sodium borohydride solution of newly joining successively, 40mL0.001M palladium chloride aqueous solution, the 10mL2.4mg/mL sodium borohydride solution of newly joining, after sonic oscillation 30 ~ 60min, centrifugal segregation clear liquid, water and ethanol respectively wash 3 ~ 5 times, with liquor argenti nitratis ophthalmicus inspection extremely without chlorion, vacuum drying 6 ~ 10h at 40 ~ 50 DEG C, i.e. obtained CoNiPd/CNTs catalyst.
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| CN104307535B (en) * | 2014-09-12 | 2016-12-07 | 西北师范大学 | The preparation of armorphous nano oxide-noble metal heterojunction structure catalyst |
| CN104259476A (en) * | 2014-09-26 | 2015-01-07 | 中国科学院深圳先进技术研究院 | Palladium nano-particle and preparation method thereof |
| CN105680054A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell |
| CN104646026B (en) * | 2015-02-11 | 2016-03-30 | 青岛大学 | The three-dimensional composite catalyst of a kind of hollow core-shell PtNi/ Graphene and preparation method |
| CN104689852B (en) * | 2015-03-04 | 2017-04-12 | 西北师范大学 | Preparation of benzotriazole modified and carbon carrier loaded palladium-based catalyst |
| CN109841856B (en) * | 2017-11-28 | 2021-04-09 | 中国科学院大连化学物理研究所 | Preparation method of monodisperse core-shell nano catalyst for fuel cell |
| CN108745350B (en) * | 2018-06-21 | 2021-03-16 | 广东工业大学 | Preparation method and application of bimetallic core-shell catalyst |
| CN110518257B (en) * | 2019-09-03 | 2022-07-22 | 上海电气集团股份有限公司 | Preparation method of carbon-supported transition metal @ Pt core-shell structure catalyst |
| CN110890558B (en) * | 2019-11-05 | 2021-05-04 | 中新国际联合研究院 | Supported platinum-based core-shell catalyst and preparation method thereof |
| CN112499641B (en) * | 2020-12-09 | 2022-03-11 | 浙江帕瓦新能源股份有限公司 | Boron-doped precursor material with core-shell structure, positive electrode material and preparation method |
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