CN102593473A - Fuel cell catalyst and preparation method thereof - Google Patents
Fuel cell catalyst and preparation method thereof Download PDFInfo
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- CN102593473A CN102593473A CN2012100329382A CN201210032938A CN102593473A CN 102593473 A CN102593473 A CN 102593473A CN 2012100329382 A CN2012100329382 A CN 2012100329382A CN 201210032938 A CN201210032938 A CN 201210032938A CN 102593473 A CN102593473 A CN 102593473A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The invention provides a fuel cell catalyst, which comprises a composite carrier and a noble metal, wherein the composite carrier is prepared by a rare earth oxide and a carbon carrier, and the noble metal is loaded on the composite carrier. The catalyst provided by the invention has excellent poisoning resisting capability. The invention also provides a preparation method of the fuel cell catalyst. The preparation method comprises the steps of: (1) mixing the carbon carrier with an acid salt solution containing rare earth element to obtain a suspension; (2) precipitating the rare earth element in the suspension with an alkaline matter to obtain a rare earth element hydroxide compounded carbon carrier; (3) sintering the rare earth element hydroxide compounded carbon carrier to obtain the composite carrier; and (4) mixing a noble metal precursor with the composite carrier, and carrying out microwave sintering to obtain the fuel cell catalyst. The preparation method provided by the invention is simple, controllable and high in production efficiency.
Description
Technical field
The present invention relates to fuel cell field, be specifically related to a kind of fuel-cell catalyst and preparation method thereof.
Background technology
Directly fuel liquid battery is the electrochemical reaction appts that a kind of direct employing liquid fuel (liquid fuels such as methyl alcohol, formic acid, ethanol) and airborne oxygen convert chemical energy to electric energy.Because its energy conversion efficiency is high, and is simple in structure, safe and reliable; Clean does not need complicated additional equipment such as reformation, heating, cooling device; Compression pump; Fans etc. are considered to most possibly at first realize commercial applications, have very wide application prospect in fields such as small portable portable power source and transducers.
At present; Directly general the employing with precious metals pt or Pd of fuel liquid battery is that main active loads on above the carbon carrier with conductivity that high specific area becomes reconciled; But because Pt or Pd catalyst in use are easy to take place intoxicating phenomenon, thereby reduced activity of such catalysts.In order to improve the anti-poisoning ability of catalyst; The researcher has proposed to reduce it and poison effect such as the binary or the multicomponent alloy of preparation Pt or Pd and other metal through Pt or Pd are modified; Seek more suitably catalyst carrier such as CNT; And utilize metal oxide to improve its activity etc. also there is the researcher to propose performance such as Chinese patent 02155255.X that different improvement preparation methods improves corresponding catalyst; 02116449.5 it is not obvious that 200710031598.0. but these methods improve the effect of anti-poisoning ability.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of fuel-cell catalyst with good anti-poisoning ability.
In order to solve above technical problem, the invention provides a kind of fuel-cell catalyst, comprise,
Complex carrier is by rare earth oxide and carbon carrier preparation;
Noble metal loads on the said complex carrier.
Preferably, said rare earth oxide is that atomic number is 15 kinds of lanthanide series of 57 to 71 and scandium and the yttrium oxide of totally ten seven kinds of elements.
Preferably, said noble metal is Pt, Pd, Au, Ir, Ru, Rh, Ag and Os one or more compositions wherein,
Preferably, said carbon carrier is CNT, active carbon, carbon fiber, Graphene or carbon gel.
The present invention also provides a kind of preparation method of fuel-cell catalyst, comprising:
A) carbon carrier is mixed with the acid salt solution that contains rare earth element, obtain suspension;
B) precipitate the rare earth element in the said suspension with alkaline matter, obtain the compound carbon carrier of hydroxide of rare earth element;
C) carbon carrier sintering that the hydroxide of said rare earth element is compound obtains complex carrier;
D) presoma with noble metal mixes with said complex carrier, and microwave sintering obtains fuel-cell catalyst.
Preferably, the acid salt of said rare earth oxide is nitrate of rare earth element, sulfate or hydrochloride.
Preferably, the presoma of said noble metal is H
4PtCl
6, PtCl
4, PtCl
2(NH
3)
2, H
4PdCl
6, PdCl
4, PdCl
2(NH
3)
2, H
4AuCl
6, AuCl
4, AuCl
2(NH
3)
2
Preferably, said carbon carrier is CNT, active carbon, carbon fiber, Graphene or carbon gel.
Preferably, step a) is specially: a1) rare earth oxide is dissolved in the red fuming nitric acid (RFNA), obtains containing the acid salt solution of rare earth element;
A2) dilute said acid salt solution with 1: 1 ethanol and secondary water;
A3) carbon carrier is mixed with said acid salt solution, obtain suspension.
Preferably, step d) is specially:
D1) with the presoma mixed and dispersed of the said noble metal of said complex carrier and noble metal in ethylene glycol, obtain glycolic suspension
D2) said glycolic suspension pH value is adjusted to 10.5～11.5;
D3) with steps d 2) the alkaline glycolic suspension that obtains carries out microwave sintering 30～180s, obtains fuel-cell catalyst after removing by filter filtrating.
Catalyst provided by the invention by the doped with rare-earth oxide carbon carrier again carried noble metal obtain; Said noble metal has very high catalytic activity; Carbon carrier has good conductivity and surface area; Because noble metal and rare earth oxide have good affinity, thus incrust after the load, can not lose activity because of long-time the use yet; Said in addition rare earth oxide itself just has very abundant outer-shell electron and oxy radical can be provided, and combining with activity of such catalysts composition noble metal to provide the electro catalytic activity of catalyst; The most important thing is that catalyst middle rare earth oxide provided by the invention can pass through electronic effect and difunctional mechanism is accelerated the decomposition and the absorption of the intermediate product of fuel cell reaction, thereby improve the anti-poisoning ability of catalyst.Catalyst provided by the invention can be used for DMFC, directly aminic acid fuel battery, the directly catalytic reaction of alcohol fuel cell.
The invention provides a kind of preparation method of fuel-cell catalyst, comprising: a) carbon carrier is mixed with the acid salt solution that contains rare earth element, obtain suspension; B) precipitate the rare earth element in the said suspension with alkaline matter, obtain the compound carbon carrier of hydroxide of rare earth element; C) carbon carrier sintering that the hydroxide of said rare earth element is compound obtains complex carrier; D) presoma with noble metal mixes with said complex carrier, and microwave sintering obtains fuel-cell catalyst.Preparation method's process simple controllable provided by the invention can make the firm combination of carbon carrier, rare earth oxide and noble metal, and the catalyst that obtains has good anti-poisoning ability.
Description of drawings
Catalyst and Eu that Fig. 1 provides for the embodiment of the invention 1
2O
3The XRD figure of/C carrier;
The PdEu that Fig. 2 provides for the embodiment of the invention 2
2O
3The EDX figure of/C;
The Pd Ce that Fig. 3 provides for the embodiment of the invention 3
2O
3/ C and Ce
2O
3The XRD figure of C carrier;
The PbYb that Fig. 4 provides for the embodiment of the invention 4
2O
3The TEM figure of/C catalyst.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The present invention provides a kind of fuel-cell catalyst.Comprise,
Complex carrier.By rare earth oxide and carbon carrier preparation;
Noble metal loads on the said complex carrier.
The present invention is in order to provide a kind of catalyst with high anti-intermediate product poisoning capability, with doped with rare-earth oxide in carbon carrier.Because rare earth oxide has abundant outer-shell electron and oxy radical can be provided, and can improve the catalytic capability of catalyst activity sexual element through electronic effect and difunctional mechanism; The existence of rare earth oxide also can accelerate to decompose the generation poison control centre in the adsorbed fuel cell reaction, thereby improves the performance of battery.
According to the present invention, it is 15 kinds of lanthanide series of 57 to 71 and scandium and the yttrium oxide of totally ten seven kinds of elements that said rare earth oxide is preferably atomic number.Said carbon carrier is preferably CNT, active carbon, carbon fiber, Graphene or carbon gel.According to the present invention, said noble metal comprises: Pt, Pd, Au, Ir, Ru, Rh, Ag, Os one or more compositions wherein, more preferably Pt, Pd, Au or PtPd, PtRu, PtIr,, PtPdAu, PtRuOs, most preferably be Pt, Pd.
The catalyst of rare earth oxide and carbon complex carrier (ReO/C) load can be used for following direct fuel liquid battery and comprises DMFC, direct aminic acid fuel battery, direct alcohol fuel cell etc.Said catalyst antianode fuel has the catalyst of catalytic activity can be as the anode catalyst of fuel cell, and the target hydrogen reduction has the catalyst of catalytic activity can be as cathod catalyst; Have the part catalyst be antianode fuel have catalytic activity again the antianode hydrogen reduction catalytic activity is arranged, therefore be that available anode catalyst also can be used as cathod catalyst.
The present invention also provides a kind of preparation method of fuel catalyst, comprising:
A) carbon carrier is mixed with the acid salt solution that contains rare earth element, obtain suspension;
B) precipitate the rare earth element in the said suspension with alkaline matter, obtain the compound carbon carrier of hydroxide of rare earth element;
C) carbon carrier sintering that the hydroxide of said rare earth element is compound obtains complex carrier;
D) presoma with noble metal mixes with said complex carrier, and microwave sintering obtains fuel-cell catalyst.
According to the present invention, at first preparation contains the acid salt solution of rare earth element,
A1) rare earth oxide is dissolved in the red fuming nitric acid (RFNA), obtains containing the acid salt solution of rare earth element;
A2) carry out said acid salt solution with 1: 1 ethanol and secondary water;
A3) carbon carrier is mixed with said acid salt solution, obtain suspension.
(ReO) is dissolved in the red fuming nitric acid (RFNA) with rare earth oxide, and the ethanol and the secondary water that adopted then 1: 1 dilute.Carbon carrier joined carry out sonicated and sufficient mechanical agitation in the above-mentioned solution, obtain suspension.
Then sodium carbonate and NaOH are joined in the above-mentioned suspension, make ReO form deposition.At last, with above-mentioned suspension filtered, washing obtains stable ReO/C complex carrier thereby solid matter transferred in the tube furnace under nitrogen protection carrying out thermal decomposition process.According to the present invention, said rare earth oxide (ReO) is 1: 1～10, more preferably 1: 2～8 with red fuming nitric acid (RFNA) in molar ratio, most preferably be 1: 4～and 6.The ethanol and the secondary water that adopted 1: 1 dilute, and being diluted in 3 times at least also is to say that 1: 1 ethanol and secondary water greater than 3 times of amounts join in the top solution.The quality of said carbon carrier accounts for the 0.1wt%～99.9wt%. of ReO/C complex carrier quality, and more preferably 10wt%～80wt% most preferably is 25wt%～60wt%.
Sonicated and sufficient mechanical agitation, promptly ultrasonic time is not less than half an hour, and mechanical agitation is no less than 1 hour.
The mass ratio of preferred said sodium carbonate and said rare earth oxide is 1: 0.1～0.3.NaOH can guarantee that pH value of solution＞9 get final product.
According to the present invention, this temperature of said sintering is preferably 450-600 ℃, more preferably 500～550 ℃.
After having prepared the ReO/C complex carrier, noble metal is loaded on the said complex carrier, the preparation method is specially:
D1) with the presoma mixed and dispersed of the said noble metal of said complex carrier and noble metal in ethylene glycol, obtain glycolic suspension
D2) said glycolic suspension pH value is adjusted to 10.5～11.5;
D3) with steps d 2) the alkaline glycolic suspension that obtains carries out microwave sintering 30～180s, obtains fuel-cell catalyst after removing by filter filtrating.
Complex carrier and noble metal precursor body are fully mixed being distributed in a certain amount of ethylene glycol under the ultrasound condition, adopt sodium hydroxide solution to regulate pH value to 10.5～11.5 then.Then should be said adjusting back pH value afterwards glycolic suspension place and carry out microwave sintering in the microwave oven; Equitemperature is reduced to room temperature; Glycolic suspension is filtered, and washing is with solid matter dry noble metal catalyst that just can obtain the ReO/C load in drying box.
According to the present invention, the quality of said noble metal precursor body accounts for 1～80wt% of complex carrier and noble metal precursor physique amount summation; Said noble metal precursor body is preferably precious metal salt, like H
4PtCl
6, PtCl
4, PtCl
2(NH
3)
2, H
4PdCl
6, PdCl
4, PdCl
2(NH
3)
2, H
4AuCl
6, AuCl
4, AuCl
2(NH
3)
2
The concentration sodium hydroxide of carried noble metal use is 1～2M, requires sodium hydroxide solution to be added drop-wise in the said glycolic suspension.
According to the present invention, the time of said microwave sintering is preferably 30～180s; If greater than 1 minute, need intermittently heating as heating 1 minute heating time, stop 10s～30s.
Below be the specific embodiment of the invention, set forth technical scheme of the present invention in detail:
Embodiment 1
ReO is with Eu
2O
3Rare earth oxide is an example, is noble metal with Pd, and wherein Pd and rare earth oxide mass content in PdEuO/C is 20% and 15% to describe.
Rare earth oxide (the Eu of weighing 20mg
2O
3) be dissolved in the red fuming nitric acid (RFNA) of 10ml, adopt 1: 1 the ethanol of 40ml and secondary water to dilute then.The 80mg activated carbon joined carry out sonicated and 2 hours mechanical agitation half an hour in the above-mentioned solution, the NaOH with the 1M of the sodium carbonate liquor of the 1M of 100ml and 10mL joins in the above-mentioned solution then, makes to form Eu
2O
3Deposition.At last, above-mentioned mixed liquor is filtered, washing is carried out thermal decomposition process at a certain temperature and is obtained stable Eu thereby solid matter transferred under nitrogen protection in the tube furnace
2O
3/ C complex carrier.With the top complex carrier 80mg that obtains and a certain amount of noble metal precursor body H
2PdCl
6(containing 20mgPd) is distributed under ultrasound condition in the ethylene glycol of 50ml and fully mixes, and adopts the sodium hydroxide solution of 1M to regulate the pH value to about 11 then.Then this mixed liquor is placed and carry out the certain hour heat treated in the microwave oven, equitemperature is reduced to room temperature, and mixed liquor is filtered, and washing just can obtain PdEu 80 ℃ of following dryings with solid matter in drying box
2O
3/ C catalyst.Fig. 1 is this catalyst and Eu
2O
3The XRD figure of/C carrier.From figure, can see at Eu
2O
3Can see Eu on the/C carrier
2O
3Diffraction maximum.At PdEu
2O
3Can see the diffraction maximum of Pd in the/C catalyst.Fig. 2 is PdEu
2O
3The EDX figure of/C can see the peak of tangible Pd, Eu and O from figure, thereby proves Pd and Eu
2O
3Existence.
ReO is with Ce
2O
3Rare earth oxide is an example, is noble metal with Pd, and its content and preparation method are the same.
Fig. 3 is Pd Ce
2O
3/ C and Ce
2O
3The XRD figure of C carrier can be seen Ce from figure
2O
3And the diffraction maximum of Pd exists.
Embodiment 3
ReO is with Yb
2O
3Rare earth oxide is an example, is noble metal with Pt, and its content and preparation method are the same.
Fig. 4 is PbYb
2O
3The TEM figure of/C catalyst is on the carbon carrier that as can be seen from the figure the Pb nano particle disperses uniformly.
More than a kind of fuel-cell catalyst provided by the invention and preparation method thereof has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and execution mode; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (10)
1. a fuel-cell catalyst is characterized in that, comprise,
Complex carrier.By rare earth oxide and carbon carrier preparation;
Noble metal loads on the said complex carrier.
2. catalyst according to claim 1 is characterized in that, said rare earth oxide is that atomic number is 15 kinds of lanthanide series of 57 to 71 and scandium and the yttrium oxide of totally ten seven kinds of elements.
3. catalyst according to claim 1 is characterized in that, said noble metal is Pt, Pd, Au, Ir, Ru, Rh, Ag and Os one or more compositions wherein,
4. catalyst according to claim 1 is characterized in that, said carbon carrier is CNT, active carbon, carbon fiber, Graphene or carbon gel.
5. the preparation method of a fuel-cell catalyst is characterized in that, comprising:
A) carbon carrier is mixed with the acid salt solution that contains rare earth element, obtain suspension;
B) precipitate the rare earth element in the said suspension with alkaline matter, obtain the compound carbon carrier of hydroxide of rare earth element;
C) carbon carrier sintering that the hydroxide of said rare earth element is compound obtains complex carrier;
D) presoma with noble metal mixes with said complex carrier, and microwave sintering obtains fuel-cell catalyst.
6. catalyst according to claim 5 is characterized in that, the acid salt of said rare earth oxide is nitrate of rare earth element, sulfate or hydrochloride.
7. catalyst according to claim 5 is characterized in that, the presoma of said noble metal is H
4PtCl
6, PtCl
4, PtCl
2(NH
3)
2, H
4PdCl
6, PdCl
4, PdCl
2(NH
3)
2, H
4AuCl
6, AuCl
4, AuCl
2(NH
3)
2
8. catalyst according to claim 5 is characterized in that, said carbon carrier is CNT, active carbon, carbon fiber, Graphene or carbon gel.
9. preparation method according to claim 5 is characterized in that step a) is specially: a1) rare earth oxide is dissolved in the red fuming nitric acid (RFNA), obtains containing the acid salt solution of rare earth element;
A2) dilute said acid salt solution with 1: 1 ethanol and secondary water;
A3) carbon carrier is mixed with said acid salt solution, obtain suspension.
10. preparation method according to claim 1 is characterized in that step d) is specially:
D1) with the presoma mixed and dispersed of the said noble metal of said complex carrier and noble metal in ethylene glycol, obtain glycolic suspension
D2) said glycolic suspension pH value is adjusted to 10.5～11.5;
D3) with steps d 2) the alkaline glycolic suspension that obtains carries out microwave sintering 30～180s, obtains fuel-cell catalyst after removing by filter filtrating.
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Family
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007935A (en) * | 2012-12-13 | 2013-04-03 | 北京化工大学常州先进材料研究院 | Preparation method of Pt/antimony-doped tin oxide-graphene catalyst |
| CN103127931A (en) * | 2013-03-01 | 2013-06-05 | 北京化工大学常州先进材料研究院 | Lithium-air battery catalyst and preparation method |
| CN103401000A (en) * | 2013-08-14 | 2013-11-20 | 西南石油大学 | Catalyst for proton exchange membrane fuel battery, preparation method for catalyst and proton exchange membrane fuel battery |
| CN103474679A (en) * | 2013-09-04 | 2013-12-25 | 中国科学院福建物质结构研究所 | Anode catalyst for direct formic acid fuel cell and preparation method of anode catalyst |
| CN104229924A (en) * | 2014-08-15 | 2014-12-24 | 扬州大学 | Method for photocatalyzing dye wastewater with double-rare-earth oxide graphene composite |
| CN105680058A (en) * | 2016-01-13 | 2016-06-15 | 山东星火科学技术研究院 | Preparation method of nano-composite cathode catalyst material for lithium-air battery |
| CN105940540A (en) * | 2014-01-09 | 2016-09-14 | 潮州三环（集团）股份有限公司 | Electrochemical energy conversion devices and cells, and positive electrode-side materials for them |
| CN106450353A (en) * | 2016-09-09 | 2017-02-22 | 西北师范大学 | Rare earth-iridium composite catalyst and preparation method thereof |
| CN106622229A (en) * | 2017-01-10 | 2017-05-10 | 湘潭大学 | Preparation method of hydrogenation catalyst and method for preparing cyclohexanone through phenol selective hydrogenation |
| CN107552061A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
| CN107799779A (en) * | 2017-10-23 | 2018-03-13 | 清华大学 | Monatomic catalyst of iridium for direct methanoic acid fuel cell and preparation method thereof |
| CN108091891A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | Alkaline anion-exchange membrane fuel cell anodic nano-catalyst and preparation and application |
| CN111151237A (en) * | 2020-01-20 | 2020-05-15 | 云南电网有限责任公司电力科学研究院 | Preparation method of noble metal catalyst |
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| CN103007935A (en) * | 2012-12-13 | 2013-04-03 | 北京化工大学常州先进材料研究院 | Preparation method of Pt/antimony-doped tin oxide-graphene catalyst |
| CN103127931A (en) * | 2013-03-01 | 2013-06-05 | 北京化工大学常州先进材料研究院 | Lithium-air battery catalyst and preparation method |
| CN103401000A (en) * | 2013-08-14 | 2013-11-20 | 西南石油大学 | Catalyst for proton exchange membrane fuel battery, preparation method for catalyst and proton exchange membrane fuel battery |
| CN103401000B (en) * | 2013-08-14 | 2015-11-18 | 西南石油大学 | Used in proton exchange membrane fuel cell catalyst, its preparation method and Proton Exchange Membrane Fuel Cells |
| CN103474679A (en) * | 2013-09-04 | 2013-12-25 | 中国科学院福建物质结构研究所 | Anode catalyst for direct formic acid fuel cell and preparation method of anode catalyst |
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| CN105940540B (en) * | 2014-01-09 | 2021-02-19 | 深圳三环电子有限公司 | Electrochemical energy conversion device, battery, and positive electrode material for same |
| CN104229924A (en) * | 2014-08-15 | 2014-12-24 | 扬州大学 | Method for photocatalyzing dye wastewater with double-rare-earth oxide graphene composite |
| CN105680058B (en) * | 2016-01-13 | 2018-03-09 | 山东星火科学技术研究院 | A kind of preparation method of lithium-air battery negative electrode nano-composite catalyst material |
| CN105680058A (en) * | 2016-01-13 | 2016-06-15 | 山东星火科学技术研究院 | Preparation method of nano-composite cathode catalyst material for lithium-air battery |
| CN107552061A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
| CN106450353A (en) * | 2016-09-09 | 2017-02-22 | 西北师范大学 | Rare earth-iridium composite catalyst and preparation method thereof |
| CN108091891A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | Alkaline anion-exchange membrane fuel cell anodic nano-catalyst and preparation and application |
| CN108091891B (en) * | 2016-11-22 | 2020-11-03 | 中国科学院大连化学物理研究所 | Anode nano catalyst of alkaline anion exchange membrane fuel cell and preparation and application thereof |
| CN106622229B (en) * | 2017-01-10 | 2019-06-28 | 湘潭大学 | The preparation method and phenol selectivity of hydrogenation catalyst add the method for hydrogen preparing cyclohexanone |
| CN106622229A (en) * | 2017-01-10 | 2017-05-10 | 湘潭大学 | Preparation method of hydrogenation catalyst and method for preparing cyclohexanone through phenol selective hydrogenation |
| CN107799779A (en) * | 2017-10-23 | 2018-03-13 | 清华大学 | Monatomic catalyst of iridium for direct methanoic acid fuel cell and preparation method thereof |
| CN107799779B (en) * | 2017-10-23 | 2021-01-12 | 清华大学 | Iridium monatomic catalyst for direct formic acid fuel cell and preparation method thereof |
| CN111151237A (en) * | 2020-01-20 | 2020-05-15 | 云南电网有限责任公司电力科学研究院 | Preparation method of noble metal catalyst |
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Application publication date: 20120718 |