CN103474674A - Compounding method for palladium/graphene structural carbon material combined electrode catalyst - Google Patents
Compounding method for palladium/graphene structural carbon material combined electrode catalyst Download PDFInfo
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- CN103474674A CN103474674A CN2012101879962A CN201210187996A CN103474674A CN 103474674 A CN103474674 A CN 103474674A CN 2012101879962 A CN2012101879962 A CN 2012101879962A CN 201210187996 A CN201210187996 A CN 201210187996A CN 103474674 A CN103474674 A CN 103474674A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a compounding method of palladium and a graphene structural carbon material (selected from one of graphene, carbon nanotube or fullerene), and helps to prepare a palladium/graphene structural carbon material combined electrode catalyst. The compounding method comprises the following steps: putting a graphene structural carbon material in 1-methyl-2-pyrrolidone and performing ultrasonic dispersion; respectively adding glycol and a palladium nitrate solution and mixing uniformly, then transferring the mixed system in a hydro-thermal kettle for a reaction, after the reaction is finished, centrifugally separating to obtain a solid product, performing washing and drying to obtain the palladium/graphene structural carbon material combined electrode catalyst. According to the compounding method, the graphene structural carbon material is taken as a substrate; and by employing the hydro-thermal synthetic method, the prepared palladium/graphene structural carbon material combined electrode catalyst has better application prospect and economical benefit in the field of direct methanol fuel cells.
Description
Technical field
The present invention a kind ofly be take the graphene-structured material with carbon element as substrate, and, in the combination electrode catalyst preparation technology of its surface deposition crystal palladium nano-particles, belongs to field of material preparation.
The complex method of the palladium of low degree of imperfection, high stability and high catalytic activity-graphene-structured material with carbon element combination electrode catalyst particularly.
Background technology
In the face of increasingly serious energy crisis and problem of environmental pollution, environmental protection and energy-saving and emission-reduction become the only way of social development, and the mode of production and the consumption pattern that change the energy will have broad prospects in future.Wherein, fuel cell is exactly a kind of important, developable energy conversion system.Direct methanoic acid fuel cell has efficiently, safety, the advantage such as green clean and get most of the attention.Therefore, seek excellent properties and relatively inexpensive, the clean new fuel cell catalyst such as existing high catalytic activity, high mithridatism, long circulation life, economic development and enhancement of environment are significant.
In research process in the past, Metal Palladium is better to the electro catalytic activity of Oxidation of Formic Acid, but its electro-catalysis less stable and easy catalytic decomposition formic acid, thereby has restricted to a great extent development and the application of direct methanoic acid fuel cell.Adopt material with carbon element as basis material, the Combined electrode catalyst prepared in its area load Metal Palladium can improve the electro-catalysis stability of palladium catalyst to Oxidation of Formic Acid, can effectively reduce again the speed that palladium decomposes formic acid simultaneously.Therefore in various material with carbon elements, the graphene-structured material with carbon element has the advantages such as bigger serface, high conductivity, electrochemical stability, and the composite material of graphene-structured material with carbon element and Metal Palladium becomes the focus of direct methanoic acid fuel cell area research in recent years.Up to the present; people realize compound (the An effective strategy for small-sized and highly-dispersed palladium nanoparticles supported on graphene with excellent performance for formic acid oxidation. Journal of Materials Chemistry 2011 of Metal Palladium nano particle and graphene-structured material with carbon element by the graphene-structured material with carbon element being carried out to surface oxidation treatment or organically-modified mode; 21,3384-3390; Highly dispersed Pd nanoparticles supported on 1,10-phenanthroline-functionalized multi-walled carbon nanotubes for electrooxidation of formic acid. Journal of Power Sources 2011,196,6232-6237).The graphene-structured material with carbon element is carried out to surface oxidation treatment can stay a large amount of defects at carbon material surface, makes its excellent properties of losing many scripts, thereby impact finally makes electro-chemical activity and the stability of catalyst; The graphene-structured material with carbon element is carried out organically-modified also can reaching the purpose of supported palladium nano particle, yet because this process matrix combines by physical action often with particle, Pd nano particle easily comes off at carbon material surface, so the electrochemical stability of catalyst is poor.
Summary of the invention
The object of the present invention is to provide the complex method of the palladium of a kind of low degree of imperfection, high stability and high catalytic activity-graphene-structured material with carbon element combination electrode catalyst.
The complex method of the palladium of low degree of imperfection, high stability and high catalytic activity-graphene-structured material with carbon element comprises the following steps:
The first step, be placed in the ultrasonic dispersion of 1-Methyl-2-Pyrrolidone by the graphene-structured material with carbon element;
Second step adds respectively ethylene glycol and palladium nitrate solution and stirs in the system of the first step;
The 3rd step, be transferred to the system of second step in water heating kettle and react;
The 4th step, go out solid product by the reaction system centrifugation of the 3rd step, washing, the dry rear palladium-graphene-structured material with carbon element combination electrode catalyst that obtains.
Ultrasonic time described in the first step is 1-3 hour, and temperature is 20-30 ℃, and described graphene-structured material with carbon element is selected from Graphene, carbon nano-tube or fullerene a kind of, and the concentration of described dispersion liquid is 0.01 g/L-1.00 g/L.
The mass ratio of the Metal Palladium described in second step and graphene-structured material with carbon element is 1:10-10:1, and the volume ratio of described 1-Methyl-2-Pyrrolidone and ethylene glycol is 1:5-5:1.
Reaction temperature described in the 3rd step is 20-200 ℃, and the described reaction time is 2-36 hour.
Compared with prior art, its advantage is in the present invention: (1) palladium-low, the anti-poisoning capability of graphene-structured material with carbon element combination electrode catalyst defect is strong, catalytic activity is high, good stability; (2) adopt softening method, avoided the use of strong acid oxidant in building-up process, green safety, environmentally friendly; (3) palladium that prepared by application the present invention-graphene-structured material with carbon element combination electrode catalyst has good application prospect and economic benefit in the direct methanoic acid fuel cell field.
The accompanying drawing explanation
Fig. 1 is the complex method schematic flow sheet of palladium of the present invention-graphene-structured material with carbon element combination electrode catalyst.
Fig. 2 is the Raman spectrogram of palladium-graphen catalyst of preparing of the invention process example 1.
Fig. 3 is the cyclic voltammetry figure of palladium-graphen catalyst of preparing of the invention process example 1.
Embodiment
As shown in Figure 1, the complex method of palladium of the present invention-graphene-structured material with carbon element combination electrode catalyst comprises the following steps preparation:
The first step, be placed in the ultrasonic dispersion of 1-Methyl-2-Pyrrolidone by the graphene-structured material with carbon element;
Second step adds respectively ethylene glycol and palladium nitrate solution and stirs in the system of the first step;
The 3rd step, be transferred to the reaction system of second step in water heating kettle and react;
The 4th step, go out solid product by the reaction system centrifugation of the 3rd step, with the deionized water washing, and the dry rear palladium-graphene-structured material with carbon element combination electrode catalyst that obtains.
embodiment 1:(quality is than palladium: Graphene=1:1) for palladium-graphene combination electrode catalyst
The first step, join the 0.10g native graphite in the 1000mL1-N-methyl-2-2-pyrrolidone N-, standing after ultrasonic 2 hours under 20 ℃, obtains the dispersion soln of Graphene;
Second step, measure the dispersion soln of 120mL Graphene, adds respectively wherein the 0.94mol/L palladium nitrate solution of 40mL ethylene glycol and 0.012mL, stirs;
The 3rd step, be transferred to the reaction system of second step in water heating kettle and react, 120 ℃ of reactions 12 hours;
The 4th step, go out solid product by the reaction system centrifugation of the 3rd step, with the deionized water washing, and the dry rear palladium-graphene combination electrode catalyst that obtains.
The Raman spectrogram that Fig. 2 is palladium-graphen catalyst of adopting embodiment 1 to prepare.As can be seen from the figure, in catalyst, the D peak intensity of Graphene is very low, illustrates in this sample and only contains a small amount of defect.
The cyclic voltammetry figure that Fig. 3 is palladium-graphen catalyst of adopting embodiment 1 to prepare.As calculated, the electro-chemical activity surface area of final catalyst can reach 81.2m
2/ g, demonstrate excellent electro-chemical activity.
embodiment 2:(quality is than palladium: carbon nano-tube=10:1) for palladium-carbon nano-tube combination electrode catalyst
The first step, join the 0.01g carbon nano-tube in the 1000mL1-N-methyl-2-2-pyrrolidone N-, standing after ultrasonic 1 hour under 25 ℃;
Second step, measure the dispersion soln of 120mL multi-walled carbon nano-tubes, adds respectively the 0.94mol/L palladium nitrate solution of 600mL ethylene glycol and 0.122mL, stirs;
The 3rd step, be transferred to the reaction system of second step in water heating kettle and react, 200 ℃ of reactions 2 hours;
The 4th step, go out solid product by the reaction system centrifugation of the 3rd step, with the deionized water washing, and the dry rear palladium-carbon nano-tube combination electrode catalyst that obtains.
embodiment 3:(quality is than palladium: fullerene=1:10) for palladium-fullerene combination electrode catalyst
The first step, join the 1.00g fullerene in the 1000mL1-N-methyl-2-2-pyrrolidone N-, standing after ultrasonic 3 hours under 30 ℃;
Second step, measure the dispersion soln of 120mL fullerene, adds respectively the 0.94mol/L palladium nitrate solution of 24mL ethylene glycol and 0.122mL, stirs;
The 3rd step, be transferred to the reaction system of second step in water heating kettle and react, 20 ℃ of reactions 36 hours;
The 4th step, go out solid product by the reaction system centrifugation of the 3rd step, with the deionized water washing, and the dry rear palladium-fullerene combination electrode catalyst that obtains.
Claims (4)
1. the complex method of a palladium and graphene-structured material with carbon element combination electrode catalyst is characterized in that described complex method comprises the following steps:
The first step, be placed in the ultrasonic dispersion of 1-Methyl-2-Pyrrolidone by the graphene-structured material with carbon element;
Second step adds respectively ethylene glycol and palladium nitrate solution and stirs in the system of the first step;
The 3rd step, be transferred to the system of second step in water heating kettle and react;
The 4th step, go out solid product by the reaction system centrifugation of the 3rd step, washing, the dry rear palladium-graphene-structured material with carbon element combination electrode catalyst that obtains.
2. the complex method of palladium according to claim 1 and graphene-structured material with carbon element combination electrode catalyst, it is characterized in that the ultrasonic time described in the first step is 1-3 hour, temperature is 20-30 ℃, described graphene-structured material with carbon element is selected from Graphene, carbon nano-tube or fullerene a kind of, and the concentration of described dispersion liquid is 0.01 g/L-1.00 g/L.
3. the complex method of palladium according to claim 1 and graphene-structured material with carbon element combination electrode catalyst, the mass ratio that it is characterized in that the Metal Palladium described in second step and graphene-structured material with carbon element is 1:10-10:1, and the volume ratio of described 1-Methyl-2-Pyrrolidone and ethylene glycol is 1:5-5:1.
4. the complex method of palladium according to claim 1 and graphene-structured material with carbon element combination electrode catalyst, is characterized in that the reaction temperature described in the 3rd step is 20-200 ℃, and the described reaction time is 2-36 hour.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894189A (en) * | 2014-04-23 | 2014-07-02 | 西南大学 | Preparation method of high-performance palladium/graphene methanoic acid oxidation catalyst |
| CN104907066A (en) * | 2015-05-18 | 2015-09-16 | 昆明理工大学 | Method for preparing carbon-supported Pd nano catalyst by utilization of NH4F modified processed carbon nano-material |
| CN105905993A (en) * | 2016-06-14 | 2016-08-31 | 北京工业大学 | Method for preparing supported palladium catalyst electrode on basis of graphene-doped Nafion film modification |
| CN107195918A (en) * | 2017-06-02 | 2017-09-22 | 东华大学 | A kind of fuel-cell catalyst and its preparation and application using graphene fullerene three-dimensional composite material as carrier |
| CN114006001A (en) * | 2021-11-11 | 2022-02-01 | 四川烯都科技有限公司 | Preparation method of high-dispersity graphene nano palladium crystal particles |
| CN115043463A (en) * | 2022-06-20 | 2022-09-13 | 南通科顺建筑新材料有限公司 | Bimetal-graphene composite electrode, preparation method and water treatment device |
-
2012
- 2012-06-08 CN CN2012101879962A patent/CN103474674A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894189A (en) * | 2014-04-23 | 2014-07-02 | 西南大学 | Preparation method of high-performance palladium/graphene methanoic acid oxidation catalyst |
| CN104907066A (en) * | 2015-05-18 | 2015-09-16 | 昆明理工大学 | Method for preparing carbon-supported Pd nano catalyst by utilization of NH4F modified processed carbon nano-material |
| CN105905993A (en) * | 2016-06-14 | 2016-08-31 | 北京工业大学 | Method for preparing supported palladium catalyst electrode on basis of graphene-doped Nafion film modification |
| CN107195918A (en) * | 2017-06-02 | 2017-09-22 | 东华大学 | A kind of fuel-cell catalyst and its preparation and application using graphene fullerene three-dimensional composite material as carrier |
| CN107195918B (en) * | 2017-06-02 | 2019-07-23 | 东华大学 | It is a kind of using graphene-fullerene three-dimensional composite material as the fuel-cell catalyst of carrier and its preparation and application |
| CN114006001A (en) * | 2021-11-11 | 2022-02-01 | 四川烯都科技有限公司 | Preparation method of high-dispersity graphene nano palladium crystal particles |
| CN115043463A (en) * | 2022-06-20 | 2022-09-13 | 南通科顺建筑新材料有限公司 | Bimetal-graphene composite electrode, preparation method and water treatment device |
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Application publication date: 20131225 |