CN101239312A - Direct methanol fuel cell anode catalyst and preparation - Google Patents
Direct methanol fuel cell anode catalyst and preparation Download PDFInfo
- Publication number
- CN101239312A CN101239312A CNA2008100196346A CN200810019634A CN101239312A CN 101239312 A CN101239312 A CN 101239312A CN A2008100196346 A CNA2008100196346 A CN A2008100196346A CN 200810019634 A CN200810019634 A CN 200810019634A CN 101239312 A CN101239312 A CN 101239312A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- porous nano
- nano tio
- sio
- tio
- 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.)
- Granted
Links
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
Landscapes
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The present invention provides a direct methanol fuel cell anode catalyst and its preparing method, the product is composed of a porous-nano TiO2 or porous-nano TiO2-SiO2 and active carbon, Pt, Ru. A multivariant catalyst is formed by combined highly active porous-nano TiO2 or porous-nano TiO2-SiO2 and active carbon, Pt, Ru, the surface of TiO2 or TiO2-SiO2 deposits a little noble metal Pt, Ru, the PtRu/TiO2 or PtRu/TiO-SiO2 composite powder of high activity is formed, noble metal Pt and CO generated by methanol anodic oxidation are absorbed, transferred to the surface of composite powder, and overoxidized to final product CO2, reduces the use of noble metal such as Pt, Ru, greatly enhances CO inhibiting ability of catalyst.
Description
Technical field:
The present invention relates to a kind of DMFC anode catalyst and preparation method.
Background technology:
DMFC (Direct Methanol Fuel Cell, DMFC) have that less energy consumption, energy density height, methyl alcohol source are abundant, low price, simple, the convenient and low noise advantages of operation of system, be considered to following automobile power and the most promising electrochmical power source of other vehicles, cause people's extensive concern.One of material of DMFC most critical is an electrode catalyst, and it directly influences performance, stability, service life and the manufacturing cost of battery.Precious metals pt (less than 80 ℃) under cryogenic conditions has excellent catalytic performance, the electrode catalyst of DMFC all is main component with Pt at present, wherein the PtRu catalyst has stronger anti-CO poisoning performance and the catalytic activity of Geng Gao than pure Pt, the catalyst that is considered to present DMFC the best, but because it costs an arm and a leg, the utilization rate in DMFC does not also reach business-like requirement.People have carried out big quantity research and have prepared polynary composite catalyst to improve its catalytic activity, improve the resisting CO poison ability.Prepared PtRu-NdO if any report
x/ C catalyst, the Nd oxide exists with amorphous form, can reduce the consumption of precious metals pt in the catalyst.Other has report to prepare the PtRu-Ni/C composite catalyst, has reduced noble metal dosage, and the PtRu-Ni/C catalyst is than PtRu/C catalyst activity height, and the resisting CO poison ability is strong.
Summary of the invention:
The object of the present invention is to provide a kind of load capacity that reduces noble metal such as Pt, Ru in the catalyst, improve the DMFC anode catalyst and the preparation method of its resisting CO poison ability.
Technical solution of the present invention is:
A kind of DMFC anode catalyst is characterized in that: by porous nano TiO
2Or porous nano TiO
2-SiO
2Form with active carbon, Pt, Ru.
Porous nano TiO
2Or porous nano TiO
2-SiO
2Content be 5～10%, the content of active carbon is 80%, the content sum of Pt, Ru is 10～15%, above-mentioned content is weight percentage.
A kind of preparation method of DMFC anode catalyst is characterized in that: comprise the following steps:
1) porous nano TiO
2Or porous nano TiO
2-SiO
2Preparation: adopt sol-gel process, the butyl titanate of amount of calculation or butyl titanate, silester be dissolved in absolute ethyl alcohol, add template agent CTAB, after the stirring and dissolving, stir the mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water down, behind the formation colloidal sol, continue to stir, behind the gel of not having a flowability to be formed, left standstill 2～3 days, 100 ℃ of vacuum drying 12 hours, in the mortar levigate after, 500 ℃ of air roastings of Muffle furnace 3 hours make porous nano TiO
2Or porous nano TiO
2-SiO
2
2) processing of carbon carrier: place high-pressure steam to handle 3-10 hour active carbon, taking-up final vacuum drying was handled 20 minutes to 1 hour in air atmosphere then, and the carbon carrier of handling joins in the ethylene glycol in the ratio of 5-15 mg/ml, ultrasonic being uniformly dispersed forms the carbon slurry;
3) with H
2PtCl
6Be dissolved in the ethylene glycol, form the H of 5-10 milligram platinum/milliliter
2PtCl
6/ ethylene glycol solution;
4) with RuCl
3Be dissolved in the ethylene glycol, form the RuCl of 2-4 milligram Ru/ milliliter
3/ ethylene glycol solution;
5) ratio of n (Pt): n (Ru)=1: 1 is measured H in molar ratio
2PtCl
6/ ethylene glycol solution and RuCl
3/ ethylene glycol solution mixes, by last synthetic catalyst W (PtRu)=10%～15% and W (TiO
2) or W (TiO
2-SiO
2)=10%～5% takes by weighing porous nano TiO
2Or porous nano TiO
2-SiO
2Add in the mixed liquor, be added drop-wise to after ultrasonic being uniformly dispersed in the carbon slurry and form suspension;
6) NaOH is dissolved in the ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
7) the prepared NaOH ethylene glycol solution is added drop-wise in the suspension that step 5) obtains, regulating the pH value is 8.5-12;
8) with KBH
4Be dissolved into and be mixed with KBH in the ethylene glycol
4Concentration is the KBH of 0.2-0.5mol/L
4/ ethylene glycol solution;
9) stir, inert gas shielding under 80-90 ℃, is to drip KBH in the mixing suspension of 8.5-12 to pH value
4/ ethylene glycol solution reacted 2-6 hour;
10) filter after reaction finishes, deionized water washs to filter liquor does not have chlorion, and 80-120 ℃ of vacuum drying makes catalyst.
The consumption of template agent CTAB is the porous nano TiO that makes in the step 1)
2Or porous nano TiO
2-SiO
21%～3% of weight; Preparation porous nano TiO in the step 1)
2-SiO
2The time butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water, silester the consumption mol ratio be: n (butyl titanate): n (absolute ethyl alcohol): n (glacial acetic acid): n (deionized water): n (silester)=1: 20～40: 1～2.5: 2～6: 0.1～0.25; Preparation porous nano TiO
2The time butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water the consumption mol ratio be: n (butyl titanate): n (absolute ethyl alcohol): n (glacial acetic acid): n (deionized water)=1: 20～40: 1～2.5: 2～6.
Active carbon produces Vulcan XC-72 for cabot company.
The present invention is with highly active porous nano TiO
2Or porous nano TiO
2-SiO
2Be compounded to form multicomponent catalyst with Pt, Ru etc., at this moment TiO
2Or TiO
2-SiO
2Surface deposition small amount of precious metals Pt, Ru form highly active PtRu/TiO
2Or PtRu/TiO
2-SiO
2Composite granule, precious metals pt and methyl alcohol are adsorbed, transfer to the composite granule surface at the CO that anodic oxidation produces, and the direct deep oxidation of quilt is end product CO
2, therefore can reduce the consumption of noble metals such as Pt, Ru, improve catalyst resisting CO poison ability greatly.
The invention will be further described below in conjunction with embodiment.
The specific embodiment:
(1) porous nano TiO
2Or porous nano TiO
2-SiO
2Preparation: adopt sol-gel process, the butyl titanate of amount of calculation or butyl titanate, silester be dissolved in absolute ethyl alcohol, add template agent CTAB, after the stirring and dissolving, stir the mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water down, behind the formation colloidal sol, continue to stir, behind the gel of not having a flowability to be formed, left standstill 2～3 days, 100 ℃ of vacuum drying 12 hours, in the mortar levigate after, 500 ℃ of air roastings of Muffle furnace 3 hours make porous nano TiO
2Or porous nano TiO
2-SiO
2The consumption of template agent CTAB is the porous nano TiO that makes
2Or porous nano TiO
2-SiO
21%～3% of weight; Preparation porous nano TiO
2-SiO
2The time butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water, silester the consumption mol ratio be: n (butyl titanate): n (absolute ethyl alcohol): n (glacial acetic acid): n (deionized water): n (silester)=1: 20～40: 1～2.5: 2～6: 0.1～0.25; Preparation porous nano TiO
2The time butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water the consumption mol ratio be: n (butyl titanate): n (absolute ethyl alcohol): n (glacial acetic acid): n (deionized water)=1: 20～40: 1～2.5: 2～6.
(2) processing of carbon carrier: place high-pressure steam to handle 3-10 hour active carbon, taking-up final vacuum drying was handled 20 minutes to 1 hour in air atmosphere then, and the carbon carrier of handling joins in the ethylene glycol in the ratio of 5-15 mg/ml, ultrasonic being uniformly dispersed forms the carbon slurry; Active carbon produces Vulcan XC-72 for cabot company.
(3) with H
2PtCl
6Be dissolved in the ethylene glycol, form the H of 5-10 milligram platinum/milliliter
2PtCl
6/ ethylene glycol solution;
(4) with RuCl
3Be dissolved in the ethylene glycol, form the RuCl of 2-4 milligram Ru/ milliliter
3/ ethylene glycol solution;
(5) ratio of n (Pt): n (Ru)=1: 1 is measured H in molar ratio
2PtCl
6/ ethylene glycol solution and RuCl
3/ ethylene glycol solution mixes, by last synthetic catalyst W (PtRu)=15% and W (TiO
2) or W (TiO
2-SiO
2)=5% takes by weighing porous nano TiO
2Or porous nano TiO
2-SiO
2Add in the mixed liquor, be added drop-wise to after ultrasonic being uniformly dispersed in the carbon slurry and form suspension; The consumption of carbon slurry is that to make active carbon content in the catalyst of making be 80%;
(6) NaOH is dissolved in the ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
(7) the prepared NaOH ethylene glycol solution is added drop-wise in the suspension that step (5) obtains, regulating the pH value is 8.5-12;
(8) with KBH
4Be dissolved into and be mixed with KBH in the ethylene glycol
4Concentration is the KBH of 0.2-0.5mol/L
4/ ethylene glycol solution;
(9) stir, inert gas shielding under 80-90 ℃, is the excessive KBH of dropping in the mixing suspension of 8.5-12 to pH value
4/ ethylene glycol solution (its KBH
4Molal quantity is 20～30 times of Pt molal quantity in the solution, 80-90 ℃ of reaction 2-6 hour;
(10) filter after reaction finishes, deionized water washs to filter liquor does not have chlorion, and 80-120 ℃ of vacuum drying makes catalyst.
Embodiment 2:
Press last synthetic catalyst W (PtRu)=10% and W (TiO in the step (5)
2) or W (TiO
2-SiO
2)=10% takes by weighing porous nano TiO
2Or porous nano TiO
2-SiO
2, all the other are with embodiment 1.
Embodiment 3:
Press last synthetic catalyst W (PtRu)=12.5% and W (TiO in the step (5)
2) or W (TiO
2-SiO
2)=7.5% takes by weighing porous nano TiO
2Or porous nano TiO
2-SiO
2, all the other are with embodiment 1.
Claims (5)
1, a kind of DMFC anode catalyst is characterized in that: by porous nano TiO
2Or porous nano TiO
2-SiO
2Form with active carbon, Pt, Ru.
2, a kind of DMFC anode catalyst according to claim 1 is characterized in that: porous nano TiO
2Or porous nano TiO
2-SiO
2Content be 5～10%, the content of active carbon is 80%, the content sum of Pt, Ru is 10～15%, above-mentioned content is weight percentage.
3, a kind of preparation method of DMFC anode catalyst is characterized in that: comprise the following steps:
1) porous nano TiO
2Or porous nano TiO
2-SiO
2Preparation: adopt sol-gel process, the butyl titanate of amount of calculation or butyl titanate, silester be dissolved in absolute ethyl alcohol, add template agent CTAB, after the stirring and dissolving, stir the mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water down, behind the formation colloidal sol, continue to stir, behind the gel of not having a flowability to be formed, left standstill 2～3 days, 100 ℃ of vacuum drying 12 hours, in the mortar levigate after, 500 ℃ of air roastings of Muffle furnace 3 hours make porous nano TiO
2Or porous nano TiO
2-SiO
2
2) processing of carbon carrier: place high-pressure steam to handle 3-10 hour active carbon, taking-up final vacuum drying was handled 20 minutes to 1 hour in air atmosphere then, and the carbon carrier of handling joins in the ethylene glycol in the ratio of 5-15 mg/ml, ultrasonic being uniformly dispersed forms the carbon slurry;
3) with H
2PtCl
6Be dissolved in the ethylene glycol, form the H of 5-10 milligram platinum/milliliter
2PtCl
6/ ethylene glycol solution;
4) with RuCl
3Be dissolved in the ethylene glycol, form the RuCl of 2-4 milligram Ru/ milliliter
3/ ethylene glycol solution;
5) ratio of n (Pt): n (Ru)=1: 1 is measured H in molar ratio
2PtCl
6/ ethylene glycol solution and RuCl
3/ ethylene glycol solution mixes, by last synthetic catalyst W (PtRu)=10%～15% and W (TiO
2) or W (TiO
2-SiO
2)=10%～5% takes by weighing porous nano TiO
2Or porous nano TiO
2-SiO
2Add in the mixed liquor, be added drop-wise to after ultrasonic being uniformly dispersed in the carbon slurry and form suspension;
6) NaOH is dissolved in the ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
7) the prepared NaOH ethylene glycol solution is added drop-wise in the suspension that step 5) obtains, regulating the pH value is 8.5-12;
8) with KBH
4Be dissolved into and be mixed with KBH in the ethylene glycol
4Concentration is the KBH of 0.2-0.5mol/L
4/ ethylene glycol solution;
9) stir, inert gas shielding under 80-90 ℃, is to drip KBH in the mixing suspension of 8.5-12 to pH value
4/ ethylene glycol solution reacted 2-6 hour;
10) filter after reaction finishes, deionized water washs to filter liquor does not have chlorion, and 80-120 ℃ of vacuum drying makes catalyst.
4, the preparation method of a kind of DMFC anode catalyst according to claim 3 is characterized in that: the consumption of template agent CTAB is the porous nano TiO that makes in the step 1)
2Or porous nano TiO
2-SiO
21%～3% of weight; Preparation porous nano TiO in the step 1)
2-SiO
2The time butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water, silester the consumption mol ratio be: n (butyl titanate): n (absolute ethyl alcohol): n (glacial acetic acid): n (deionized water): n (silester)=1: 20～40: 1～2.5: 2～6: 0.1～0.25; Preparation porous nano TiO
2The time butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water the consumption mol ratio be: n (butyl titanate): n (absolute ethyl alcohol): n (glacial acetic acid): n (deionized water)=1: 20～40: 1～2.5: 2～6.
5, according to the preparation method of claim 3 or 4 described a kind of DMFC anode catalysts, it is characterized in that: active carbon produces Vulcan XC-72 for cabot company.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100196346A CN101239312B (en) | 2008-03-07 | 2008-03-07 | Direct methanol fuel cell anode catalyst and preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100196346A CN101239312B (en) | 2008-03-07 | 2008-03-07 | Direct methanol fuel cell anode catalyst and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101239312A true CN101239312A (en) | 2008-08-13 |
| CN101239312B CN101239312B (en) | 2010-12-29 |
Family
ID=39931306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100196346A Expired - Fee Related CN101239312B (en) | 2008-03-07 | 2008-03-07 | Direct methanol fuel cell anode catalyst and preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101239312B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361089A (en) * | 2011-09-09 | 2012-02-22 | 南通大学 | PdNi / TiO2 nanofiber anode catalyst for direct methanol fuel cell and preparation method thereof |
| CN104022293A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported RuNi direct methanol fuel cell anode catalyst and preparation method thereof |
| CN104022292A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported PdAg direct methanol fuel cell anode catalyst and preparation method thereof |
| CN104022298A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported RuAg direct methanol fuel cell anode catalyst and preparation method thereof |
| CN104022296A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported PdRu direct methanol fuel cell anode catalyst and preparation method thereof |
| CN111584888A (en) * | 2020-05-27 | 2020-08-25 | 湖南大学 | Preparation method of silicon dioxide doped/coated platinum-carbon catalyst |
-
2008
- 2008-03-07 CN CN2008100196346A patent/CN101239312B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361089A (en) * | 2011-09-09 | 2012-02-22 | 南通大学 | PdNi / TiO2 nanofiber anode catalyst for direct methanol fuel cell and preparation method thereof |
| CN102361089B (en) * | 2011-09-09 | 2012-11-21 | 南通大学 | PdNi / TiO2 nanofiber anode catalyst for direct methanol fuel cell and preparation method thereof |
| CN104022293A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported RuNi direct methanol fuel cell anode catalyst and preparation method thereof |
| CN104022292A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported PdAg direct methanol fuel cell anode catalyst and preparation method thereof |
| CN104022298A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported RuAg direct methanol fuel cell anode catalyst and preparation method thereof |
| CN104022296A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | TiO2@C supported PdRu direct methanol fuel cell anode catalyst and preparation method thereof |
| CN104022296B (en) * | 2014-05-07 | 2017-01-04 | 南通大学 | A kind of TiO2@C load P dRu anode catalysts for direct methanol fuel cell and preparation method |
| CN111584888A (en) * | 2020-05-27 | 2020-08-25 | 湖南大学 | Preparation method of silicon dioxide doped/coated platinum-carbon catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101239312B (en) | 2010-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112952118A (en) | high-Pt-content high-performance catalyst with high stability and reverse polarity resistance and preparation method thereof | |
| CN102836708B (en) | Preparation method of PdAg/TiO2 nanotube direct methanol fuel cell anode catalyst | |
| CN100531914C (en) | solid phase reduction preparation method for platinum, carbon catalyst of fuel cell | |
| CN101239312B (en) | Direct methanol fuel cell anode catalyst and preparation | |
| CN102361089B (en) | PdNi / TiO2 nanofiber anode catalyst for direct methanol fuel cell and preparation method thereof | |
| CN101667644B (en) | High-performance low-platinum catalyst for methanol fuel cell and preparation method thereof | |
| CN102723504A (en) | Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method | |
| CN112186207A (en) | Low platinum/non-platinum composite catalyst and preparation method thereof | |
| CN107359356B (en) | A kind of anode catalysts for direct methanol fuel cell and preparation method | |
| CN103165914B (en) | Pt/Au/PdCo/C catalyst, and preparation and application thereof | |
| CN104393312B (en) | High activity, the high stability DMFC preparation method of very low platinum carrying amount Pt-CoP/C anode electrocatalyst | |
| WO2019179530A1 (en) | Platinum-based alloy catalyst and preparation method therefor, membrane electrode, and fuel cell | |
| CN103178274B (en) | Anode catalyst of PdMo/TiO2 nanowire direct methanol fuel cell and preparation method | |
| CN103579639B (en) | A kind of cathode catalyst for fuel cell and preparation method | |
| CN109499602B (en) | Synthesis method for systematically regulating and controlling number of atoms of load type iron atom cluster | |
| CN109244485B (en) | NiCo/TiO2Battery anode catalyst and preparation method 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 | |
| CN105845953A (en) | Preparation method for N-C-doped TiO<2> nanofiber loaded Pd@Ni positive electrode catalyst for direct methanol fuel cell | |
| CN104022292B (en) | A kind of preparation method of TiO2@C load P dAg anode catalysts for direct methanol fuel cell | |
| CN109301269B (en) | PtAgCo/C nanoflower structure catalytic material, preparation method thereof and application of catalytic material as fuel cell catalyst | |
| CN105244511A (en) | Alloy electrocatalyst and preparation method thereof | |
| CN104022296B (en) | A kind of TiO2@C load P dRu anode catalysts for direct methanol fuel cell and preparation method | |
| CN104022293A (en) | TiO2@C supported RuNi direct methanol fuel cell anode catalyst and preparation method thereof | |
| CN114284511A (en) | Method for synthesizing direct alcohol fuel cell anode catalyst based on ultrasonic assistance | |
| CN113745539A (en) | Fluorine-containing non-noble metal oxygen reduction electrocatalyst and preparation method and application thereof |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101229 Termination date: 20140307 |