CN104148097A - Preparation method of carbon-carried non-crystal alloy catalyst - Google Patents
Preparation method of carbon-carried non-crystal alloy catalyst Download PDFInfo
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- CN104148097A CN104148097A CN201410134489.1A CN201410134489A CN104148097A CN 104148097 A CN104148097 A CN 104148097A CN 201410134489 A CN201410134489 A CN 201410134489A CN 104148097 A CN104148097 A CN 104148097A
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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
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Abstract
The invention provides a preparation method of a non-crystal alloy catalyst used for an oxygen reduction reaction. The preparation method comprises the following steps: metal salt and sodium hypophosphite are dissolved in water, sodium citrate is added, and pH is adjusted to be 7.0-8.0 by using ammonia water; chloroplatinic acid and carbon powder are added, the mixture is stirred to be uniform and then is subjected to ultrasound treatment for 0.5-0.6h; after pH is adjusted to be 8-9 by using ammonia water, sodium borohydride is added, and the mixture is stirred for reaction for 15-16h; reaction liquid is washed to be neutral by distilled water, absolute ethyl alcohol is used for washing, and then the catalyst is obtained. The non-crystal catalyst prepared by utilizing the method takes carbon powder as a carrier and takes PtMP (M refers to Co, Ni, Fe and the like) non-crystal materials as active components, so that in comparison with a corresponding crystal catalyst, the non-crystal catalyst has larger activity surface area and better catalytic activity for the oxygen reduction reaction, and can work for a long time under a fuel cell actual-running environment.
Description
Technical field
The present invention and a kind of carbon carry the preparation method of amorphous alloy catalyst, are mainly used in the oxygen reduction reaction of fuel cell.
Background technology
Amorphous alloy is that a class has that long-range is unordered, the material of shot-range ordered structure feature.Because amorphous alloy has unique structure, electricity and magnetic performance, mechanical property and anti-wear performance, on the power equipments such as catalytic field, controller switching equipment, motor, electromagnetic sensor, be widely used.Amorphous alloy is used as catalyst and is applied in fuel cell oxygen reduction catalytic reaction owing to having following characteristics: (1) amorphous alloy can form by modulation in very wide scope, this is conducive to their electronic structure of modulation, by its electronic property of continuous adjusting, can obtain suitable catalytic active center; (2) amorphous alloy has isotropic nature, does not have the defects such as crystal boundary, stacking fault and segregation that exist in crystal alloy, and its catalytic active center is distributed in uniform chemical environment equably with single form; (3) surface atom coordination is highly unsaturated, makes its catalytic activity and is selectively generally better than corresponding crystalline-state catalyst.These features make amorphous alloy in heterogeneous catalysis, have very large attraction, are the high-efficiency cleaning new catalytic materials with very large potential use.Therefore, how to adopt new technology of preparing, make the amorphous alloy catalyst with special the Nomenclature Composition and Structure of Complexes, low price, high-performance, high stability, become the study hotspot of catalyst field.
Summary of the invention
The object of this invention is to provide the preparation method that a kind of carbon carries amorphous alloy catalyst, be mainly used in fuel cell oxygen reduction reaction.
The present invention prepares the method that carbon carries amorphous alloy eelctro-catalyst, is by slaine and sodium hypophosphite (NaH
2pO
2) soluble in water, adding natrium citricum, the ammoniacal liquor that is 2.5～3mol/L by concentration regulates pH to 7.0～8.0; Add chloroplatinic acid and carbon dust, ultrasonic 0.5～6h after stirring; With ammoniacal liquor, regulate behind pH to 8～9, add sodium borohydride (NaBH
4), stirring reaction 15～16h; Reactant liquor is washed with distilled water to neutrality, and absolute ethanol washing obtains amorphous alloy catalyst.
Described slaine is chloride or the nitrate of Co, Ni, Fe.
The mass ratio of slaine and sodium hypophosphite is 1:1～3:1.
The addition of natrium citricum is 2～3 times of slaine quality.
The addition of chloroplatinic acid is 0.2～0.5 times of slaine quality.
The addition of carbon dust is 0.5～0.6 times of slaine quality.
The addition of sodium borohydride is 0.4～0.6 times of slaine quality.
Carbon dust carries out pretreatment before use: carbon dust is scattered in acetone, at 50～60 ℃, stirs 5～6h, to remove the organic impurities in carbon dust, then water and acetone washing are to neutral, dry, stand-by.
The amorphous state PtCoP/C catalyst of take is below example, and structure and performance that carbon prepared by the present invention carries amorphous alloy catalyst are analyzed and tested.
1, XRD analysis
Fig. 1 is the XRD figure of the amorphous state PtCoP/C catalyst (and making comparisons with crystalline state PtCoP/C catalyst) prepared of the present invention.As can be seen from Figure 1, amorphous state PtCoP/C catalyst is that 42 °, 49 °, 72 ° and 87 ° are except not occurring Pt(111 at 2 θ), Pt(200), Pt(220) and the Pt(311) characteristic diffraction peak of crystal face, but be that a diffuse peaks has appearred in 45 ° of left and right at 2 θ, this is an amorphous characteristic peak, shows that this catalyst Pt CoP/C is amorphous structure.
2, catalytic performance analysis
Fig. 2 is that the amorphous state PtCoP/C catalyst (and making comparisons with crystalline state PtCoP/C catalyst) prepared of the present invention is at 0.1mol/LHClO
4cyclic voltammetry curve in solution.As shown in Figure 3, amorphous state PtCoP/C catalyst is analysed the large 15.26m of dehydrogenation area than crystalline state PtCoP/C catalyst
2/ g, illustrates that amorphous catalyst is larger than the active surface area of crystalline-state catalyst, is showing better catalytic performance aspect the electro-catalysis of fuel cell.
Fig. 3 is that the amorphous state PtCoP/C catalyst (and making comparisons with crystalline state PtCoP/C catalyst) prepared of the present invention is at 0.1MHClO
4hydrogen reduction curve map in solution.As shown in Figure 3, amorphous state PtCoP/C catalyst has improved respectively 70mV and 48mV than the half way up the mountain current potential of crystalline state PtCoP/C catalyst and take-off potential, illustrates that amorphous catalyst shows better hydrogen reduction performance than crystalline-state catalyst.
Indulge the above, amorphous catalyst prepared by the present invention be take carbon dust as carrier, take PtMP(M=Co, Ni, Fe etc.) amorphous state is active component, more corresponding crystalline-state catalyst has larger active surface area, oxygen reduction reaction is had to better catalytic activity, under fuel cell actual motion environment, can work long hours.
Accompanying drawing explanation
Fig. 1 is the XRD figure of amorphous state PtCoP/C catalyst and crystalline state PtCoP/C catalyst.
Fig. 2 is the cyclic voltammogram of amorphous state PtCoP/C catalyst and crystalline state PtCoP/C catalyst.
Fig. 3 is the hydrogen reduction curve map of amorphous state PtCoP/C catalyst and crystalline state PtCoP/C catalyst.
The specific embodiment
Preparation and the catalytic activity of carbon of the present invention being carried to amorphous alloy catalyst below by embodiment are described further.
Embodiment 1, PtCoP/C(Pt 15%) preparation of catalyst
The pretreatment of carbon dust: Vulcan XC-72 (Carbot Corp. BET:237 m
2/ g, is abbreviated as C) carbon dust is as catalyst carrier, carries out before use pretreatment, first carbon dust stirs 6h with acetone 60 ℃ of oil baths in oil bath pan, and to remove the organic impurities in carbon dust, then water and acetone wash back and forth until filtrate is extremely neutral, dry, standby.
The preparation of amorphous alloy catalyst: by 200 mg Co (NO
3)
26H
2o and 100 mg NaH
2pO
2be dissolved in 20mL distilled water, add 100mg natrium citricum; With the pH=7.5 of 3mol/L ammoniacal liquor regulator solution, add 3.3mL chloroplatinic acid and 100mg carbon dust, ultrasonic 0.5h after stirring; And then regulate pH=8～9 with 3mol/L ammoniacal liquor, dropwise add 80mgNaBH
4with the distilled water mixed liquor of 10mL, stir reduction 15～16h; Reactant liquor is washed into neutral with distillation, with absolute ethyl alcohol, wash 2～3 times, obtains amorphous alloy, is kept in absolute ethyl alcohol.In PtCoP/C catalyst, the quality percentage composition of Pt, Co, C: Pt:15%, Co:5%, C:80%.
After measured, amorphous state PtCoP/C catalyst, compared with crystalline state PtCoP/C catalyst, is analysed the large 15.26m of dehydrogenation area
2/ g, half way up the mountain current potential and take-off potential have improved respectively 70mV and 48mV.
Embodiment 2, PtCoP/C(Pt 12%) preparation of catalyst
The pretreatment of carbon dust and embodiment 1 are same.
The preparation of amorphous alloy catalyst: by 250 mg Co (NO
3)
26H
2o and 100 mg NaH
2pO
2be dissolved in 20mL distilled water, add 100mg natrium citricum; With the pH=7.5 of 3mol/L ammoniacal liquor regulator solution, add 3.1mL chloroplatinic acid and 100mg carbon dust, ultrasonic 0.5h after stirring; With 3mol/L ammoniacal liquor, regulate pH=8～9 again, dropwise add 80mgNaBH
4with the distilled water mixed liquor of 10mL, stir reduction 15～16h; Reactant liquor is washed into neutral with distillation, with absolute ethyl alcohol, wash 2～3 times, obtains amorphous alloy, is kept in absolute ethyl alcohol.In PtCoP/C catalyst, the quality percentage composition of Pt, Co, C: Pt:12%, Co:8%, C:80%.
After measured, amorphous state PtCoP/C catalyst, compared with crystalline state PtCoP/C catalyst, is analysed the large 16.72m of dehydrogenation area
2/ g, half way up the mountain current potential and take-off potential have improved respectively 63mV and 32mV.
Embodiment 3:PtNiP/C(Pt 15%) preparation of catalyst
The pretreatment of carbon dust and embodiment 1 are same.
The preparation of amorphous alloy catalyst: first by 190 mg NiCl
2with 100 mg NaH
2pO
2be dissolved in 20mL distilled water, add 100mg natrium citricum; With the pH=7.5 of 3mol/L ammoniacal liquor regulator solution, add 3.3mL chloroplatinic acid and 100mg carbon dust, ultrasonic 0.5h after stirring; With 3mol/L ammoniacal liquor, regulate pH=8～9 again, dropwise add 80mgNaBH
4with the distilled water mixed liquor of 10mL, stir reduction 15～16h; Reactant liquor is washed into neutral with distillation, with absolute ethyl alcohol, wash 2～3 times, obtains amorphous alloy catalyst, is kept in absolute ethyl alcohol.In PtNiP/C catalyst, the quality percentage composition of Pt, Ni, C: Pt:15%, Ni:5%, C:80%.
After measured, amorphous state PtNiP/C(Pt 15%) catalyst is compared with crystalline state PtNiP/C catalyst, analyses the large 16.83m of dehydrogenation area
2/ g, half way up the mountain current potential and take-off potential have improved respectively 72mV and 45mV.
Embodiment 4:PtFeP/C(Pt 15%) preparation of catalyst
The pretreatment of carbon dust and embodiment 1 are same.
The preparation of amorphous alloy catalyst: by 320mg FeCl
3with 100 mg NaH
2pO
2be dissolved in 20mL distilled water, add 100mg natrium citricum; With the pH=7.5 of 3mol/L ammoniacal liquor regulator solution, add 3.3mL chloroplatinic acid and 100mg carbon dust, ultrasonic 0.5h after stirring; With 3mol/L ammoniacal liquor, regulate pH=8～9 again, dropwise add 80mgNaBH
4with the distilled water mixed liquor of 10mL, stir reduction 15～16h; Reactant liquor is washed into neutral with distillation, with absolute ethyl alcohol, wash 2～3 times, obtains amorphous alloy catalyst, is kept in absolute ethyl alcohol.In PtFeP/C catalyst, the quality percentage composition of Pt, Fe, C: Pt:15%, Fe:5%, C:80%.
After measured, amorphous state PtFeP/C(Pt 15%) catalyst is compared with crystalline state PtFeP/C(Pt 15%) catalyst, analyse the large 18.54m of dehydrogenation area
2/ g, half way up the mountain current potential and take-off potential have improved respectively 78mV and 52mV.
Claims (9)
1. carbon carries a preparation method for amorphous alloy eelctro-catalyst, is that slaine and sodium hypophosphite is soluble in water, adds natrium citricum, with ammoniacal liquor, regulates pH to 7.0～8.0; Add chloroplatinic acid and carbon dust, ultrasonic 0.5～0.6h after stirring; With ammoniacal liquor, regulate behind pH to 8～9, add sodium borohydride, stirring reaction 15～16h; Reactant liquor is washed with distilled water to neutrality, and absolute ethanol washing obtains amorphous alloy catalyst.
2. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: described slaine is chloride or the nitrate of Co, Ni, Fe.
3. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: the mass ratio of slaine and sodium hypophosphite is 1:1～3:1.
4. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: the addition of natrium citricum is 2～3 times of slaine quality.
5. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: the addition of chloroplatinic acid is 0.2～0.5 times of slaine quality.
6. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: the addition of carbon dust is 0.5～0.6 times of slaine quality.
7. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: the addition of sodium borohydride is 0.4～0.6 times of slaine quality.
8. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: described ammonia concn is 2.5～3mol/L.
9. carbon carries the preparation method of amorphous alloy eelctro-catalyst as claimed in claim 1, it is characterized in that: described carbon dust carries out pretreatment before use: carbon dust is scattered in acetone, at 50～60 ℃, stir 5～6h, to remove the organic impurities in carbon dust, then water and acetone washing are to neutral, dry, stand-by.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489907A (en) * | 2015-11-30 | 2016-04-13 | 北京化工大学 | Carbon-nanotube-loaded platinum-iron superlattice alloy nanoparticles and preparation method therefor |
| CN113373345A (en) * | 2021-06-07 | 2021-09-10 | 中氢新能(北京)新能源技术研究院有限公司 | Supported superfine PtCoP ternary alloy nanoparticle for electrocatalytic methanol oxidation and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN102764648A (en) * | 2011-05-06 | 2012-11-07 | 北京林业大学 | Preparation method of palladium catalyst, |
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2014
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102764648A (en) * | 2011-05-06 | 2012-11-07 | 北京林业大学 | Preparation method of palladium catalyst, |
Non-Patent Citations (3)
| Title |
|---|
| YANJIAO MA等: "Ultrafine amorphous PtNiP nanoparticles supported on carbon as efficiency electrocatalyst for oxygen reduction reaction", 《JOURNAL OF POWER SOURCES》 * |
| 王星砾 等: "Pt修饰的Ni/C催化剂电催化氧化乙醇性能", 《催化学报》 * |
| 高诚辉: "《非晶态合金镀及其镀层性能》", 30 April 2004, 北京：科学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489907A (en) * | 2015-11-30 | 2016-04-13 | 北京化工大学 | Carbon-nanotube-loaded platinum-iron superlattice alloy nanoparticles and preparation method therefor |
| CN105489907B (en) * | 2015-11-30 | 2018-02-13 | 北京化工大学 | A kind of carbon nanotube loaded platinum iron superlattices alloy nano particle and preparation method thereof |
| CN113373345A (en) * | 2021-06-07 | 2021-09-10 | 中氢新能(北京)新能源技术研究院有限公司 | Supported superfine PtCoP ternary alloy nanoparticle for electrocatalytic methanol oxidation and preparation method thereof |
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Application publication date: 20141119 |