CN102723503A - Direct-methanol fuel cell anode catalyst and preparation method - Google Patents
Direct-methanol fuel cell anode catalyst and preparation method Download PDFInfo
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- CN102723503A CN102723503A CN2012101403941A CN201210140394A CN102723503A CN 102723503 A CN102723503 A CN 102723503A CN 2012101403941 A CN2012101403941 A CN 2012101403941A CN 201210140394 A CN201210140394 A CN 201210140394A CN 102723503 A CN102723503 A CN 102723503A
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Abstract
The present invention discloses a direct-methanol fuel cell anode catalyst and a preparation method, which belongs to the field of the fuel cell catalyst. According to the invention, a stabilizer and a carrier of the catalyst is cucurbit [6] uril, an active substance of the catalyst is platinum nanoparticles, the regulation and control of growth of different crystal planes are realized by regulating the types of the reducing agents, so that the control of shape of the catalyst can be realized. The diameter of nanoparticles is less than 10nm, and the catalyst has the advantages of uniform diameter of nanoparticles, high energy plane enrichment, uniform distribution, high catalytic activity, excellent ability of carbon monoxide poisoning resistance and the like.
Description
Technical field
The present invention relates to utilize hexa-atomic melon ring as stabilizer and preparing carriers Pt nanoparticle method as the DMFC anode catalyst.Have high activity through the adjusting of kinetic factor effectively being regulated and control the pattern and the decentralization of Pt nanoparticle, being prepared, the DMFC anode catalyst of good anti-poisoning capability, belong to the fuel-cell catalyst field.
Background technology
Directly the methyl alcohol dye cell is directly to use liquid methanol to act as a fuel to supply with the source, belongs to a kind of in the Proton Exchange Membrane Fuel Cells.Low temperature is given birth to electricity, is given birth to simple in structure, the efficient and environmental friendliness of electricity, characteristic such as especially stores and the transportation aspect is safer and makes direct methyl alcohol dye cell become the main flow that portable electronic product is used.Directly the anode catalyst and the cathod catalyst of methyl alcohol dye cell are the catalyst based on noble metal platinum, and this becomes the bottleneck of direct methyl alcohol dye cell large-scale commercial applicationsization.In addition, the intermediate product carbon monoxide of Methanol Decomposition etc. has very strong adsorption capacity to platinum, thereby this sharply descends the catalyst activity reduction battery efficiency.So the commercialization of DMFC still is faced with problems such as activity of such catalysts, stability, life-span, anti-poisoning capability.The method that addresses these problems at present mainly is preparation based on the metal of the alloy of platinum or non-platinum as catalyst, but platinum remains the catalysis material best to the methanol catalytic oxidation reacting catalytic performance.For example having bibliographical information to have only the catalytic activity of the platinum nano-cluster of 12 pt atoms is 13 times of commercially available platinum carbon catalyst, but the stability and the useful life of such pt atom bunch are limited.Also have the alloy of bibliographical information alkali metal and platinum can strengthen catalytic performance, cause catalyst decomposes but the active component of alloy catalyst is easy to loss.So the balance between catalytic activity and stability, performance and the cost remains the key point of DMFC Catalyst Design and preparation.And improve the catalytic performance of platinum catalyst and strengthen platinum catalyst anti-carbon monoxide poisoning capability is to address the above problem the most directly and effective method.
Solve at present the method that the anode catalyst of DMFC poisons and be mostly to use metal pair platinum surfaces such as ruthenium, nickel, cobalt and tin to modify, but these metal ingredients are easy to run off and make catalysqt deactivation.In the research and development of new fuel cell catalyst, seldom use organic molecule that the metallic catalyst surface is modified at present, this mainly is because most of organic molecules can hinder the avtive spot of catalyst surface.Also just so, the organic molecule of in catalyst preparation process, introducing also often needs very numerous and diverse processing procedure to clean up, and such cleaning process often causes a large amount of losses of catalyst.The hexa-atomic melon ring of Macrocyclic compound (CB [6]) has the rigidity symmetrical structure, and thermal stability and chemical stability are all very high.Hexa-atomic melon ring utmost point indissoluble in general common solvent is separated, and keeps its electroneutral molecular structure.Research in recent years shows, the weak electrostatic interaction energy of hexa-atomic melon ring and metal surface enough well can not hinder the avtive spot of nano-material surface stable nanoparticles the time yet.In addition, hexa-atomic melon ring can also with some micromolecule effects, like carbon monoxide, carbon dioxide etc., such interaction can reduce the bond energy of carbon monoxide to a certain extent.And thereby hexa-atomic melon ring can form abundant hydrogen bond with hydrone and makes hydrone more be prone to be dissociated into the oxidation on the platinum catalyst surface such as the methanol oxidation intermediate product that helps carbon monoxide.Under hexa-atomic melon ring stabilization,, can realize having the controllable growth of the Pt nanoparticle of different-shape through the adjusting of reducing agent kind.The existence of structural characteristics of Pt nanoparticle and hexa-atomic melon ring makes these show good activity and anti-carbon monoxide poisoning capability based on the Pt nanoparticle of hexa-atomic melon ring to the catalytic oxidation of methyl alcohol.
Summary of the invention
The objective of the invention is to overcome existing technical problem in production of above-mentioned DMFC anode catalyst and the use; Provide to prepare Pt nanoparticle with hexa-atomic melon ring as stabilizer and be used for the DMFC anode catalyst, and realized the method for Pt nanoparticle pattern regulation and control through the adjusting of reducing agent kind.
The DMFC anode catalyst of the present invention's preparation, it consists of the compound of hexa-atomic melon ring and platinum, and wherein the effective active composition is a platinum.
Described Preparation of catalysts method may further comprise the steps:
(1) the hexa-atomic melon ring of preparation is as the stabilizer and the carrier of nanocatalyst;
(2) hexa-atomic melon ring and platinum presoma are joined in the deionized water, mol ratio is not less than 3, stirs to obtain mixture A;
(3) in the mixture A that step (2) is prepared, add reducing agent, obtain mixture B; Wherein reducing agent is selected from one or both in ascorbic acid, the ethylene glycol;
(4) cooling naturally after being not less than 120 ℃ of-140 ℃ of slakings of the mixture B in the step (3);
(5) product that obtains of step (4) centrifugal after, promptly get said catalyst after washing with alcohol, the drying.
The present invention utilizes hexa-atomic melon ring to prepare three kinds of particle diameters as stabilizer to be used for the DMFC anode catalyst less than the Pt nanoparticle of 10 nanometers.The shape of these three kinds of nanoparticle catalysts is respectively to have the nanoparticle catalyst that enriches twin plane, the nanoparticle catalyst and and the polypody shape nanoparticle catalyst of almost spherical.Cyclic voltammetry curve in sulfuric acid solution has explained that the parcel crystal face of three kinds of Pt nanoparticle catalyst has nothing in common with each other, and is also inequality to the performance of anodic oxidation of methanol.The present invention has realized the pattern regulation and control of Pt nanoparticle through to the adjusting of reducing agent kind, has realized the regulation and control of different crystal faces growths, also promptly realizes the play a crucial role regulation and control of factor of platinum nano catalyst catalytic performance.Compare with commercially available platinum charcoal, three kinds of prepared platinum nano catalysts of the present invention all show excellent catalytic activity and anti-carbon monoxide poisoning capability to the catalytic oxidation of methyl alcohol.Preparation technology of the present invention is simple, and is easy to operate, but industrialization production.
Description of drawings
Fig. 1. the transmission electron microscope photo of the catalyst that obtains with ascorbic acid reduction;
Fig. 2. the transmission electron microscope photo of the catalyst that the spent glycol reduction obtains;
Fig. 3. the transmission electron microscope photo of the catalyst that obtains with the common reduction of ascorbic acid and ethylene glycol;
Fig. 4. three kinds of catalyst in 0.5 mol/L sulfuric acid solution to 2 mol/L anodic oxidation of methanol;
Specific embodiments
Below in conjunction with embodiment and accompanying drawing the present invention is done further detailed second of fast returning, but do not limit the present invention.The transmission electron microscope that transmission electron microscope photo uses is: JEOL-2010, working voltage are 200 kilovolts; The instrument that electro-chemical test uses is: Epsilon EC electrochemical work station (BASi, the U.S.)
Case study on implementation 1
The hexa-atomic melon ring of (1) 0.200 mmol and the H of 0.067 mmol
2PtCl
66H
2O joins in the 15 mL deionized waters, stirs the light yellow turbid solution A that obtained mixing in hour;
(2) in the turbid solution A that step (1) obtains, add 0.30 g KBr and 0.24 g ascorbic acid, obtain mixture B;
(3) in the mixture B that step (2) obtains, drip 1 mol/L potassium hydroxide aqueous solution, regulate the pH value and equal 9, obtain mixture C;
(4) mixture C that step (3) is obtained is placed in the oil bath that is heated to 120 ℃ in advance reacted 6 hours, naturally cooled to room temperature;
(5) product that step (4) is obtained carries out centrifugal (7900 rev/mins), and twice, 50 ℃ of drying of 30 mL washing with alcohol obtained DMFC anode catalyst according to the invention in 10 hours.
The transmission electron microscope photo of the catalyst that Fig. 1 provides for case study on implementation 1 can be seen from Fig. 1 that the catalyst that is synthesized is to be rich in twin plane, particle diameter and to be about 5nm and to be evenly distributed.What insert in the high-resolution-ration transmission electric-lens photo on Fig. 1 the right is the corresponding Fourier transform in selected zone.
The preparation of the glass-carbon electrode of surface catalyst layer: get the catalyst that 1 this case study on implementation of mg is synthesized, in the ultrasonic ethanol that is dispersed in 1 mL (1 hour).Getting 5 μ L dropping is the glass-carbon electrode surface of 3 mm at diameter, air dry under the room temperature.
The mensuration of the cyclic voltammetry curve of catalyst: adopt three-electrode system to measure the chemical property of catalyst.As work electrode, platinum filament is to electrode with the glass-carbon electrode of the above-mentioned surface catalyst layer for preparing, and Ag/AgCl is a reference electrode.In the aqueous solution that contains 2mol/L methyl alcohol and 0.5 mol/L sulfuric acid, room temperature condition is measured cyclic voltammetry curve down.
(1) is the cyclic voltammetry curve of the catalyst that provides of case study on implementation 1 among Fig. 4.(1) can find out that the catalyst that is synthesized has stronger electro-chemical activity and good anti-carbon monoxide poisoning capability from Fig. 4, and the current density of forward scan is 1.67 times of negative sense sweep current density.
Case study on implementation 2
The hexa-atomic melon ring of (1) 0.200 mmol and the H of 0.067 mmol
2PtCl
66H
2O joins in the 15 mL deionized waters, stirs the light yellow turbid solution A that obtained mixing in hour;
(2) in the turbid solution A that step (1) obtains, add 0.30 g KBr and 15mL ethylene glycol, obtain mixture B;
(3) the mixture B that step (2) is obtained is placed in the oil bath that is heated to 120 ℃ in advance and reacted 6 hours, naturally cools to room temperature;
(4) product that step (3) is obtained carries out centrifugal (7900 rev/mins), and twice, 50 ℃ of drying of 30 mL washing with alcohol obtained DMFC anode catalyst according to the invention in 10 hours.
The transmission electron microscope photo of the catalyst that Fig. 2 provides for case study on implementation 2 can see that from Fig. 2 the catalyst that is synthesized is almost spherical, particle diameter and is about 5nm and is evenly distributed.What insert in the high-resolution-ration transmission electric-lens photo on Fig. 4 the right is the corresponding Fourier transform in selected zone.
The preparation of the glass-carbon electrode of surface catalyst layer: get the catalyst that 1 this case study on implementation of mg is synthesized, in the ultrasonic ethanol that is dispersed in 1 mL (1 hour).Getting 5 μ L dropping is the glass-carbon electrode surface of 3 mm at diameter, air dry under the room temperature.
The mensuration of the cyclic voltammetry curve of catalyst: adopt three-electrode system to measure the chemical property of catalyst.As work electrode, platinum filament is to electrode with the glass-carbon electrode of the above-mentioned surface catalyst layer for preparing, and Ag/AgCl is a reference electrode.In the aqueous solution that contains 2mol/L methyl alcohol and 0.5 mol/L sulfuric acid, room temperature condition is measured cyclic voltammetry curve down.
(2) are the cyclic voltammetry curves of the catalyst that provides of case study on implementation 2 among Fig. 4.(2) can find out that the catalyst that is synthesized has stronger electro-chemical activity and good anti-carbon monoxide poisoning capability from Fig. 4.
Case study on implementation 3
The hexa-atomic melon ring of (1) 0.200 mmol and the H of 0.067 mmol
2PtCl
66H
2O joins in the 15 mL deionized waters, stirs the light yellow turbid solution A that obtained mixing in hour;
(2) in the turbid solution A that step (1) obtains, add 0.30 g KBr, 0.24 g ascorbic acid and 15mL ethylene glycol, obtain mixture B;
(3) the mixture B that step (2) is obtained is placed in the oil bath that is heated to 120 ℃ in advance and reacted 6 hours, naturally cools to room temperature;
(4) product that step (3) is obtained carries out centrifugal (7900 rev/mins), and twice, 50 ℃ of drying of 30 mL washing with alcohol obtained DMFC anode catalyst according to the invention in 10 hours.
The transmission electron microscope photo of the catalyst that Fig. 3 provides for case study on implementation 2 can see that from Fig. 3 the catalyst that is synthesized is polypody shape, particle diameter and is about 5nm and is evenly distributed.What insert in the high-resolution-ration transmission electric-lens photo on Fig. 5 the right is the corresponding Fourier transform in selected zone.
The preparation of the glass-carbon electrode of surface catalyst layer: get the catalyst that 1 this case study on implementation of mg is synthesized, in the ultrasonic ethanol that is dispersed in 1 mL (1 hour).Getting 5 μ L dropping is the glass-carbon electrode surface of 3 mm at diameter, air dry under the room temperature.
The mensuration of the cyclic voltammetry curve of catalyst: adopt three-electrode system to measure the chemical property of catalyst.As work electrode, platinum filament is to electrode with the glass-carbon electrode of the above-mentioned surface catalyst layer for preparing, and Ag/AgCl is a reference electrode.In the aqueous solution that contains 2mol/L methyl alcohol and 0.5 mol/L sulfuric acid, room temperature condition is measured cyclic voltammetry curve down.
(3) are the cyclic voltammetry curves of the catalyst that provides of case study on implementation 3 among Fig. 4.(3) can find out that the catalyst that is synthesized has stronger electro-chemical activity and good anti-carbon monoxide poisoning capability from Fig. 4.
The above content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. DMFC anode catalyst, it consists of the compound of hexa-atomic melon ring and platinum, and wherein the effective active composition is a platinum.
2. described Preparation of catalysts method of claim 1 may further comprise the steps:
(1) the hexa-atomic melon ring of preparation is as the stabilizer and the carrier of nanocatalyst;
(2) hexa-atomic melon ring and platinum presoma are joined in the deionized water, mol ratio is not less than 3, stirs to obtain mixture A;
(3) in the mixture A that step (2) is prepared, add reducing agent, obtain mixture B; Wherein reducing agent is selected from one or both in ascorbic acid, the ethylene glycol;
(4) cooling naturally after being not less than 120 ℃ of-140 ℃ of slakings of the mixture B in the step (3);
(5) product that obtains of step (4) centrifugal after, promptly get said catalyst after washing with alcohol, the drying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351409A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Hexahydric cucurbit urils based polar porous material and synthetic method thereof |
| CN103594718A (en) * | 2013-11-25 | 2014-02-19 | 中国科学院福建物质结构研究所 | Preparation and usage of nanoribbon-shaped Cucurbit[6]uril carried cubic palladium nanoparticles |
| CN104368389A (en) * | 2014-12-07 | 2015-02-25 | 中国科学院福建物质结构研究所 | Supermolecule crystal material based platinum nano-catalyst and preparation and application thereof |
| CN105797768A (en) * | 2016-03-23 | 2016-07-27 | 中国科学院福建物质结构研究所 | Iridium nano-catalyst carried by six-membered cucurbituril and preparation and application thereof |
| CN111326749A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院福建物质结构研究所 | Co-supported carbon nano catalytic material with tungsten carbide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205242A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Method for preparing dispersed palladium nanoparticle catalyst with controllable appearance by using cucurbit[6]uril (CB[6]) |
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2012
- 2012-05-09 CN CN2012101403941A patent/CN102723503A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205242A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Method for preparing dispersed palladium nanoparticle catalyst with controllable appearance by using cucurbit[6]uril (CB[6]) |
Non-Patent Citations (2)
| Title |
|---|
| A. CORMA, H. GARCIA, P. MONTES-NAVAJAS ET AL: "Gold Nanoparticles in Organic Capsules: A Supramolecular Assembly of Gold Nanoparticles and Cucurbituril", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
| 曹敏纳: "《中国科学技术大学博士学位论文》", 20 September 2011 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351409A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Hexahydric cucurbit urils based polar porous material and synthetic method thereof |
| CN103351409B (en) * | 2013-07-30 | 2016-05-18 | 贵州大学 | A kind of hexa-atomic melon cyclic group polarity porous material and synthetic method thereof |
| CN103594718A (en) * | 2013-11-25 | 2014-02-19 | 中国科学院福建物质结构研究所 | Preparation and usage of nanoribbon-shaped Cucurbit[6]uril carried cubic palladium nanoparticles |
| CN103594718B (en) * | 2013-11-25 | 2019-07-30 | 中国科学院福建物质结构研究所 | The preparation and use of cube palladium nano-particles of the hexa-atomic melon ring load of nano strip |
| CN104368389A (en) * | 2014-12-07 | 2015-02-25 | 中国科学院福建物质结构研究所 | Supermolecule crystal material based platinum nano-catalyst and preparation and application thereof |
| CN105797768A (en) * | 2016-03-23 | 2016-07-27 | 中国科学院福建物质结构研究所 | Iridium nano-catalyst carried by six-membered cucurbituril and preparation and application thereof |
| CN105797768B (en) * | 2016-03-23 | 2019-05-28 | 中国科学院福建物质结构研究所 | The iridium nanocatalyst and its preparation and use of hexa-atomic melon ring load |
| CN111326749A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院福建物质结构研究所 | Co-supported carbon nano catalytic material with tungsten carbide |
| CN111326749B (en) * | 2018-12-14 | 2021-06-18 | 中国科学院福建物质结构研究所 | Co-supported carbon nano catalytic material with tungsten carbide |
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Application publication date: 20121010 |