CN100512956C - Method for producing direct methanol fuel cell positive pole catalysts - Google Patents

Method for producing direct methanol fuel cell positive pole catalysts Download PDF

Info

Publication number
CN100512956C
CN100512956C CNB2007100306479A CN200710030647A CN100512956C CN 100512956 C CN100512956 C CN 100512956C CN B2007100306479 A CNB2007100306479 A CN B2007100306479A CN 200710030647 A CN200710030647 A CN 200710030647A CN 100512956 C CN100512956 C CN 100512956C
Authority
CN
China
Prior art keywords
cnt
ruthenium
catalyst
mass ratio
ruo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2007100306479A
Other languages
Chinese (zh)
Other versions
CN101130164A (en
Inventor
王红娟
余皓
彭峰
傅小波
周春梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CNB2007100306479A priority Critical patent/CN100512956C/en
Publication of CN101130164A publication Critical patent/CN101130164A/en
Application granted granted Critical
Publication of CN100512956C publication Critical patent/CN100512956C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 making method of anode catalyst for direct carbinol fuel battery, which comprises the following steps: adding carbon nanometer pipe in the solution of ruthenium trichloride to do ultrasonic vibration; using trace quantity of sampling pump to drip hydrogen dioxide solution slowly under indoor temperature; heating; refluxing to react; filtering; washing; drying; obtaining the hydrated ruthenium trichloride loaded by carbon nanometer pipe; dispersing the hydrated ruthenium trichloride loaded by carbon nanometer pipe into ethandiol; adding platinochloric acid solution to adjust pH value; heating; refluxing; filtering; washing; drying to obtain n-RuO2.xH2O/CNTs catalyst. The invention simplifies the technique with mild operating condition and cheap cost, which has superior CO toxicity resistance.

Description

The preparation method of DMFC anode catalyst
Technical field
The present invention relates to catalyst preparation technology, specifically is a kind of DMFC anode catalyst Pt-RuO 2XH 2The preparation method of O/CNTs.
Background technology
Fuel cell has been subjected to the great attention of countries in the world as the power technology of a kind of cleaning, efficient and stable performance.Wherein the research of Proton Exchange Membrane Fuel Cells (PEMFC) and DMFC (DMFC) more attracts people's attention.They can be used for electrical source of power, are used as the power supply of mobile phone and kneetop computer, also have the potentiality for terminal use's use of appointment in the future.But Proton Exchange Membrane Fuel Cells and use for methanol fuel cells anode catalyst all exist electro catalytic activity low, and a small amount of CO of reformation gas or the directly generation in the anodic oxidation of methanol can make catalyst poisoning, thereby the performance of battery is descended significantly.Therefore, improve the electro catalytic activity of catalyst, the anti-poisoning capability that solves catalyst has become the key issue that fuel cell studies is badly in need of solution.
Chinese invention patent notification number CN 1171671C discloses " CNT carries the preparation method of the anti-CO electrode catalyst of platinum ruthenium series ", it adopts CNT is carrier, utilization in-situ chemical reduction homogeneous deposition method, at first Pt, Ru, Sn plasma are made the cooperation ion respectively, two or three cooperation ion mixes and makes the metastable state colloid then, adopt cheap reducing agent formaldehyde or sodium borohydride etc. again, metastable state colloid reduce deposition is made on CNT.This method needs preparation earlier to cooperate steps such as ion, preparation metastable state colloid, and in last reduction step, Pt and Ru, Sn plasma all are reduced to the atom valence state.And up-to-date result of study shows: in Pt, Ru bimetallic catalyst, and Pt, hydration RuO 2The alloy catalyst that the electrocatalysis characteristic of methyl alcohol is better than PtRu atom valence state; And in PtRu atom valence state alloy catalyst, the performance of Ru effect also is by progressively changing RuO into 2Finish.The present invention then with Ru directly with hydration RuO 2Form and the compound formation catalyst of Pt, saved that Ru is converted into RuO in the course of reaction 2Step; Simultaneously, hydration RuO 2Can be used as the nuclearing centre of Pt, make the Pt particle carry out load, thereby further improve the electrocatalysis characteristic of this catalyst with higher, more uniform dispersed.
Chinese invention patent notification number CN 1221050C discloses " DMFC methanol oxidation electrode preparation method ", Chinese invention patent notification number CN1123080C discloses " preparation method of fuel cell anode catalysts ", Chinese invention patent publication number CN1601788 discloses " preparation method of DMFC anode electrocatalyst ", Chinese invention patent publication number CN1827211 discloses " supported on carbon surface hollow nanometer platinum ruthenium alloy particle eelctro-catalyst and preparation method thereof ", this several patents all relates to the preparation of fuel battery anode catalyst, but prepared Pt, Ru or the composite catalyst that constitutes with other ion or oxide, Ru all exists with metallic state, therefore, all need in course of reaction, to be converted into RuO 2Play a role, Chinese invention patent notification number CN1630122 discloses " DMFC with anode catalyst and preparation method thereof " and has not related to Ru or RuO 2Adding, in addition, the carrier of above-mentioned several patents catalyst system therefor does not all relate to the CNT with special performance, and the present invention had both adopted CNT as carrier, in preparation process Ru directly was prepared into hydration RuO again 2, the conduction of carrier and the high dispersive performance of catalyst and excellent electrocatalysis characteristic are combined, give full play to its electrocatalytic oxidation property to methyl alcohol.
Summary of the invention
The objective of the invention is to overcome above-mentioned technological deficiency, propose a kind of DMFC anode catalyst Pt/RuO 2XH 2The preparation method of O/CNTs.
The present invention adopts following technical scheme to realize this purpose, preparation DMFC anode catalyst Pt-RuO 2XH 2The method of O/CNTs comprises the steps:
(1) with in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.02～0.15, ultrasonic time is 0.5～3 hour, hydrogen peroxide with 30% is added drop-wise in this system with the drop rate of 9～20ml/h, and making the hydrogen peroxide and the volume mass ratio of ruthenium is 1.0～2.0ml:1mg, and this mixture refluxed 3.5～4.5 hours down at 75～85 ℃, filter then, wash, 80～150 ℃ of dryings obtain the CNT of hydration ruthenic oxide load, i.e. RuO 2XH 2O/CNTs;
(2) ultrasonic being scattered in the ethylene glycol of CNT of the hydration ruthenic oxide load that step (1) is made, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:0.5～2:200～300, regulating the pH value is 6.5～7.5,125～135 ℃ were refluxed 1.5～2.5 hours, and filtered then, wash, 65～75 ℃ of vacuum drying, make the DMFC anode catalyst, i.e. Pt-RuO 2XH 2O/CNTs.
In the step (1), CNT: the mass ratio of ruthenium is preferably 1:0.04～0.12; Ultrasonic time is preferably 1～2.5 hour, and baking temperature is preferably 90～130 ℃; In the step (2), ruthenium: the mass ratio of platinum is preferably 1:1～1.8.
The present invention compared with prior art has following advantage and effect:
(1) the present invention adopts hydrogen peroxide that Ru is carried out oxidation, does not need high temperature, mild condition.
(2) the present invention adopts the method for step load, at first with Ru with hydration RuO 2Form be carried on the CNT, and then add weak reductant ethylene glycol (the double solvent of doing), the Pt ion in the solution is reduced to Pt, and is carried on the CNT, so both guaranteed the RuO of first load 2Be not reduced, simultaneously, hydration RuO 2Can be Pt again nuclearing centre is provided, make the dispersion of Pt particle more even.
(3) the prepared Pt-RuO of the present invention 2XH 2The O/CNTs catalyst because the height of Pt particle evenly disperses, makes its electroactive area improve greatly, thereby has improved its electro catalytic activity to methyl alcohol; Simultaneously, Ru is with hydration RuO 2Form exist, make its poisonous species in centre that fast and effeciently produce in the oxidation methanol oxidation process, thereby improve its anti-poisoning capability.Prepared catalyst of the present invention to the electrocatalytic oxidation galvanic current of methyl alcohol up to 513A/g Pt, the initial oxidation current potential of CO is low to moderate 0.28V (vs.Ag/AgCl), carry out 1000 circle cyclic voltammetrics continuously and still can keep 66% electro catalytic activity.
Description of drawings
The Pt-RuO that Fig. 1 makes for embodiment 1 2XH 2The transmission electron microscope photo of O/CNTs catalyst.
The Pt-RuO that Fig. 2 makes for embodiment 2 2XH 2The electroactive area resolution chart of O/CNTs catalyst.
The Pt-RuO that Fig. 3 makes for embodiment 3 2XH 2The O/CNTs catalyst is to the electrocatalytic oxidation property figure of methyl alcohol.
The Pt-RuO that Fig. 4 makes for embodiment 4 2XH 2The O/CNTs catalyst is to the oxidation susceptibility of CO.
The Pt-RuO that Fig. 5 makes for embodiment 5 2XH 2The O/CNTs catalyst is to the catalytic oxidation stability diagram of methyl alcohol.
The specific embodiment
The present invention is described further below in conjunction with drawings and Examples, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
(1) with in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.02, and ultrasonic time is 0.5 hour, with the drop rate of 9ml/h, 1ml/mg RuAmount 30% hydrogen peroxide is added drop-wise in this system, this mixture refluxed 3.5 hours down at 75 ℃, filtered then, washed, 80 ℃ of dryings, obtained the CNT of hydration ruthenic oxide load;
(2) CNT of the hydration ruthenic oxide load that step (1) is made is scattered in the ethylene glycol, ultrasonic dispersion, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:0.5:200, regulating the pH value is 6.5, this mixture refluxed 1.5 hours at 125 ℃, filtered then, washed, 65 ℃ of vacuum drying, made efficient direct methyl alcohol fuel battery anode catalyst Pt/RuO 2XH 2O/CNTs.
The Pt-RuO that makes 2XH 2The transmission electron microscope photo of O/CNTs catalyst is seen Fig. 1.The prepared supported catalyst uniform load on CNTs of present embodiment as seen from the figure, average grain diameter is 3nm.
Embodiment 2
(1) in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.04, and ultrasonic time is 1 hour, with the drop rate of 10ml/h, 1.5ml/mg RuAmount 30% hydrogen peroxide is added drop-wise in this system, this mixture refluxed 4 hours down at 80 ℃, filtered then, washed, 90 ℃ of dryings, obtained the CNT of hydration ruthenic oxide load;
(2) CNT of the hydration ruthenic oxide load that step (1) is made is scattered in the ethylene glycol, ultrasonic dispersion, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:1:250, regulating the pH value is 7,130 ℃ were refluxed 2 hours, filtered then, washed, 70 ℃ of vacuum drying, made efficient direct methyl alcohol fuel battery anode catalyst Pt/RuO 2XH 2O/CNTs.
The Pt-RuO that makes 2XH 2The electroactive area test result of O/CNTs catalyst is seen Fig. 2.The prepared Pt-RuO of present embodiment as seen from Figure 2 2XH 2The O/CNTs catalyst has higher electroactive area (88m 2/ g Pt), and Pt/CNTs is 40m 2/ g Pt
Embodiment 3
(1) in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.1, and ultrasonic time is 2 hours, with the drop rate of 15ml/h, 1.7ml/mg RuAmount 30% hydrogen peroxide is added drop-wise in this system, this mixture refluxed 4.2 hours down at 78 ℃, filtered then, washed, 110 ℃ of dryings, obtained the CNT of hydration ruthenic oxide load;
(2) CNT of the hydration ruthenic oxide load that step (1) is made is scattered in the ethylene glycol, ultrasonic dispersion, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:1.5:280, regulating the pH value is 6.8,132 ℃ were refluxed 2.2 hours, filtered then, washed, 68 ℃ of vacuum drying, made efficient direct methyl alcohol fuel battery anode catalyst Pt/RuO 2XH 2O/CNTs.
The Pt-RuO that makes 2XH 2The O/CNTs catalyst is seen Fig. 3 to the electrocatalytic oxidation property testing result of methyl alcohol.The prepared Pt-RuO of present embodiment as seen from Figure 3 2XH 2The O/CNTs catalyst reduces (being 0.2V (vsAg/AgCl)) to the anodic oxidation of methanol take-off potential, and the forward oxidation peak current obviously improves (513A/g Pt), have very high electro catalytic activity, and the Pt/CNTs catalyst being 0.35V (vs Ag/AgCl) to the anodic oxidation of methanol take-off potential, the forward oxidation peak current is 182A/g Pt
Embodiment 4
(1) in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.12, and ultrasonic time is 2.5 hours, with the drop rate of 10ml/h, 1.5ml/mg RuAmount 30% hydrogen peroxide is added drop-wise in this system, this mixture refluxed 4 hours down at 80 ℃, filtered then, washed, 130 ℃ of dryings, obtained the CNT of hydration ruthenic oxide load;
(2) CNT of the hydration ruthenic oxide load that step (2) is made is scattered in the ethylene glycol, ultrasonic dispersion, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:1.8:250, regulating the pH value is 7,130 ℃ were refluxed 2 hours, filtered then, washed, 70 ℃ of vacuum drying, made efficient direct methyl alcohol fuel battery anode catalyst Pt/RuO 2XH 2O/CNTs.
The Pt-RuO that makes 2XH 2The O/CNTs catalyst is seen Fig. 4 to the oxidation susceptibility test result of CO.The prepared Pt-RuO of present embodiment as seen from Figure 4 2XH 2The O/CNTs catalyst obviously reduces (for 0.25V (vsAg/AgCl)) to the initial oxidation current potential of CO, and it (is 150C/g that CO oxidation electric weight increases Pt), and Pt/CNTs is 0.55V (vs Ag/AgCl) to the initial oxidation current potential of CO, CO oxidation electric weight 78C/g Pt, the prepared Pt-RuO of this embodiment is described 2XH 2The O/CNTs catalyst has good anti-CO poisoning capability.
Embodiment 5
(1) in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.08, and ultrasonic time is 1 hour, with the drop rate of 18ml/h, 1.9ml/mg RuAmount 30% hydrogen peroxide is added drop-wise in this system, this mixture refluxed 4.5 hours down at 83 ℃, filtered then, washed, 100 ℃ of dryings, obtained the CNT of hydration ruthenic oxide load;
(2) CNT of the hydration ruthenic oxide load that step (1) is made is scattered in the ethylene glycol, ultrasonic dispersion, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:1.2:300, regulating the pH value is 7.2,135 ℃ were refluxed 2.5 hours, filtered then, washed, 72 ℃ of vacuum drying, made efficient direct methyl alcohol fuel battery anode catalyst Pt/RuO 2XH 2O/CNTs.
Fig. 5 is the Pt-RuO that makes 2XH 2The O/CNTs catalyst is to the catalytic oxidation stability diagram of methyl alcohol.The prepared Pt-RuO of present embodiment as can be seen from Figure 2XH 2The O/CNTs catalyst is to the electro catalytic activity height of methyl alcohol, and good stability carries out 1000 circle cyclic voltammetrics continuously and still can keep 66% electro catalytic activity.
Embodiment 6
(1) in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.15, and ultrasonic time is 3 hours, with the drop rate of 20ml/h, 2ml/mg RuAmount 30% hydrogen peroxide is added drop-wise in this system, this mixture refluxed 4.5 hours down at 85 ℃, filtered then, washed, 150 ℃ of dryings, obtained the CNT of hydration ruthenic oxide load;
(2) CNT of the hydration ruthenic oxide load that step (1) is made is scattered in the ethylene glycol, ultrasonic dispersion, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:2:300, regulating the pH value is 7.5,135 ℃ were refluxed 2.5 hours, filtered then, washed, 75 ℃ of vacuum drying, made efficient direct methyl alcohol fuel battery anode catalyst Pt/RuO 2XH 2O/CNTs.

Claims (4)

1, a kind of preparation method of DMFC anode catalyst is characterized in that comprising the steps:
(1) with in the ultrasonic aqueous solution that is scattered in ruthenium trichloride of CNT, CNT wherein: the mass ratio of ruthenium is 1:0.02～0.15, ultrasonic time is 0.5～3 hour, hydrogen peroxide with 30% is added drop-wise in this system with the drop rate of 9～20ml/h, making the volume of hydrogen peroxide and the mass ratio of ruthenium is 1.0～2.0ml:1mg, and this mixture refluxed 3.5～4.5 hours down at 75～85 ℃, filtered then, washed, 80～150 ℃ of dryings obtain the CNT of hydration ruthenic oxide load;
(2) ultrasonic being scattered in the ethylene glycol of CNT of the hydration ruthenic oxide load that step (1) is made, add chloroplatinic acid, ruthenium wherein: platinum: the mass ratio of ethylene glycol is 1:0.5～2:200～300, regulating the pH value is 6.5～7.5,125～135 ℃ were refluxed 1.5～2.5 hours, filter then, wash, 65～75 ℃ of vacuum drying make the DMFC anode catalyst.
2, preparation method according to claim 1, it is characterized in that in the step (1) CNT: the mass ratio of ruthenium is 1:0.04～0.12.
3, preparation method according to claim 1 is characterized in that in the step (1), ultrasonic time is 1～2.5 hour, and baking temperature is 90～130 ℃.
4, preparation method according to claim 1, it is characterized in that in the step (2) ruthenium: the mass ratio of platinum is 1:1～1.8.
CNB2007100306479A 2007-09-29 2007-09-29 Method for producing direct methanol fuel cell positive pole catalysts Expired - Fee Related CN100512956C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2007100306479A CN100512956C (en) 2007-09-29 2007-09-29 Method for producing direct methanol fuel cell positive pole catalysts

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2007100306479A CN100512956C (en) 2007-09-29 2007-09-29 Method for producing direct methanol fuel cell positive pole catalysts

Publications (2)

Publication Number Publication Date
CN101130164A CN101130164A (en) 2008-02-27
CN100512956C true CN100512956C (en) 2009-07-15

Family

ID=39127662

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2007100306479A Expired - Fee Related CN100512956C (en) 2007-09-29 2007-09-29 Method for producing direct methanol fuel cell positive pole catalysts

Country Status (1)

Country Link
CN (1) CN100512956C (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580225B (en) * 2009-06-25 2012-05-09 上海电力学院 Method for preparing low platinum modified carbon-loaded ruthenium nano particles and application thereof
CN101964423A (en) * 2010-09-11 2011-02-02 华南理工大学 Direct methanol fuel cell anode catalyst Pt/ MnO2-RuO2/ CNTs and preparation method thereof
CN104716341B (en) * 2013-12-13 2017-11-03 中国科学院大连化学物理研究所 One kind improves the anti-SO of fuel-cell catalyst2The auxiliary agent and adding method of poisoning performance
CN105514451B (en) * 2015-12-30 2019-04-16 中国科学院长春应用化学研究所 The method that the revolving method that flows back prepares efficiently non-platinum oxygen reduction catalyst
CN110404534B (en) * 2019-07-03 2021-03-30 浙江大学 High-efficiency chlorine poisoning resistant volatile organic compound catalytic oxidation catalyst and preparation method thereof
CN111628187A (en) * 2020-05-05 2020-09-04 江苏大学 Carbon-supported ruthenium oxide catalyst and preparation method thereof
CN112103520B (en) * 2020-09-24 2022-05-24 扬州大学 Anode catalyst of alcohol fuel cell

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1326816A (en) * 2001-05-18 2001-12-19 清华大学 Method for preparing CO poisoning resisting platinum-ruthenium electro-catalyst
CN1418725A (en) * 2002-12-12 2003-05-21 北方交通大学 Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube
CN1915521A (en) * 2006-08-09 2007-02-21 华南理工大学 Method for preparing catalyst in classes of platinum, carbon in use for fuel cell through solid phase reduction
JP2007217194A (en) * 2006-02-14 2007-08-30 Japan Advanced Institute Of Science & Technology Hokuriku Method for producing surface-modified carbon nano-material and pt-based catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1326816A (en) * 2001-05-18 2001-12-19 清华大学 Method for preparing CO poisoning resisting platinum-ruthenium electro-catalyst
CN1418725A (en) * 2002-12-12 2003-05-21 北方交通大学 Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube
JP2007217194A (en) * 2006-02-14 2007-08-30 Japan Advanced Institute Of Science & Technology Hokuriku Method for producing surface-modified carbon nano-material and pt-based catalyst
CN1915521A (en) * 2006-08-09 2007-02-21 华南理工大学 Method for preparing catalyst in classes of platinum, carbon in use for fuel cell through solid phase reduction

Also Published As

Publication number Publication date
CN101130164A (en) 2008-02-27

Similar Documents

Publication Publication Date Title
KR100691117B1 (en) Ruthenium-rhodium alloy electrode catalyst and fuel cell comprising the same
CN100512956C (en) Method for producing direct methanol fuel cell positive pole catalysts
CN101964423A (en) Direct methanol fuel cell anode catalyst Pt/ MnO2-RuO2/ CNTs and preparation method thereof
CN103441287A (en) Preparation method of membrane electrode of direct methanol fuel cell
CN112331858B (en) Fuel cell electrode with catalyst in-situ grown on ordered structure microporous layer and preparation method of membrane electrode
CN101641816B (en) Process for the electrochemical catalysts of fuel cells based on polymer electrolytes
JP2007250274A (en) Electrode catalyst for fuel cell with enhanced noble metal utilization efficiency, its manufacturing method, and solid polymer fuel cell equipped with this
KR20060097588A (en) A preparing method of electrocatalyst for proton exchange membrane fuel cells
CN100464841C (en) Noble metal electrocatalyst based on nano carbon fiber and its preparing method
JP2006210135A (en) Catalyst electrode material, catalyst electrode, manufacturing method thereof, support material for electrode catalyst and electrochemical device
CN100441291C (en) Active carbon fiber platinum-carrying electrocatalyst and its preparing method
CN100474670C (en) Method for producing carbon-carrying platinum-based alloy electrode
CN101380584B (en) High activity methanol-resistance direct methanol fuel cell cathode catalyst and production method thereof
JP5158334B2 (en) Method for producing electrode catalyst for fuel cell
CN101162780B (en) Direct methanol fuel battery anode catalyst and method for producing the same
CN101337184A (en) Composite electrocatalyst capable of increasing cathode mass-transfer performance of fuel cell
TW201306368A (en) Fuel cell and electrocatalyst
Tan et al. High-performance polymer fiber membrane based direct methanol fuel cell system with non-platinum catalysts
Chai et al. Heterogeneous Ir3Sn–CeO2/C as alternative Pt-free electrocatalysts for ethanol oxidation in acidic media
US8273679B2 (en) Porous catalyst for a fuel cell and method for producing the catalyst thereof
CN108746659B (en) Flower-shaped AgPd nano alloy and preparation and use methods thereof
CN1171671C (en) Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube
CN101181679B (en) Meso-porous C/WO3 electro-catalyst and preparation method thereof
CN101694880A (en) Electrode catalyst of fuel cell
KR20060097589A (en) A co tolerant electrocatalyst for proton exchange membrane fuel cells and its preparation

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090715

Termination date: 20140929

EXPY Termination of patent right or utility model