CN1889295A - Efficient direct methyl alcohol fuel battery negative pole catalyst and producing method thereof - Google Patents
Efficient direct methyl alcohol fuel battery negative pole catalyst and producing method thereof Download PDFInfo
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- CN1889295A CN1889295A CNA2006100192986A CN200610019298A CN1889295A CN 1889295 A CN1889295 A CN 1889295A CN A2006100192986 A CNA2006100192986 A CN A2006100192986A CN 200610019298 A CN200610019298 A CN 200610019298A CN 1889295 A CN1889295 A CN 1889295A
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Abstract
The present invention provides a high efficiency direct methanol fuel cell cathode catalyzer and preparation method. It features the active ingredient being metal macrocyclic compound modified nano platinum granule. Due to platinum surface exists metal macrocyclic compound and uniformly distributes on molecular level, it makes platinum surficial activity potential only small molecule space structure oxygen interaction, but large space structure methanol unable contacting with platinic activity potential, obstructing methanol diffusing to platinum surface and reducing platinic poisoning. Furthermore metal macrocyclic compound (such as phthalocyanine, porphyrin and derivans) oxidation-reduction potential is lower than platinic potential, it promoting catalyst poisoning methanol and oxidative product speeding up oxidization, greatly relieving platinum poisoning. Coordination between platinum-metal macrocyclic compound colloid catalyzer is used in methanol fuel cell, which greatly raises cathodal dynamics catalytic speed, thereby reducing cathodal polarization and raising battery output performance.
Description
Technical field
The invention belongs to a kind of cathode in direct methanol fuel cells Catalysts and its preparation method
Background technology
Along with fossil fuel consumption increases day by day exhausted with reserves gradually, and people are to the pay attention to day by day of environmental protection, and people more and more thirst for the friendly and reproducible energy of environment for use.At present, one of people's energy of posting hope most is Hydrogen Energy.Some developed countries of the world have all dropped into great amount of manpower and material resources and financial resources in the research and development of Hydrogen Energy, to quicken the arrival of hydrogen energy era.The member state of International Energy Agency (IEA) takes out financial budget 7% every year and is used to research and develop new forms of energy.China also classifies the applied basic research of scale preparation, accumulating and the associated fuel battery of Hydrogen Energy as great brainstorm subject.Because hydrogen is difficult to store and explosion limit is very big, the safety in transportation and storage of hydrogen and scale are used the restriction bottleneck that becomes Hydrogen Energy economy.In addition, hydrogen is not prime energy, and just as electric energy, it is a kind of energy carrier, need swap out from other energy transfer, is one yet a difficult problem to be solved is arranged and strengthen conversion efficiency in these conversion process of energy.Direct methanol fuel cell (DMFC) is a kind of fuel cell that grows up on Proton Exchange Membrane Fuel Cells (PEMFC) basis.It is a fuel with the methyl alcohol of cheapness, need not heavy fuel reforming or hydrogen storage system; Simple in structure, in light weight, energy efficiency is high, is desirable compact power, no matter in civilian still military field great application prospect is arranged all.
At present, the conventional amberplex that uses is the perfluorinated sulfonic acid proton exchange membrane among the DMFC, especially is the Nafion of DuPond company
TMThe catalyst that film, cathod catalyst generally use is Pt/C.Although DMFC has the irreplaceable advantage of many PEMFC in actual applications, it is methanol crossover that but DMFC has a fatal shortcoming in actual applications, be that methyl alcohol sees through perfluorinated sulfonic acid proton exchange membrane arrival negative electrode from anode, reduction and methanol oxidation at cathode catalysis layer generation oxygen, produce mixed potential, reduce the output voltage of DMFC, more seriously methyl alcohol and methyl alcohol are at the serious Poisoning cathode catalyst of product of negative electrode, the destruction of causing cathod catalyst to be difficult to recover is reduced the power output of battery greatly.Therefore, preparing the cathod catalyst that anti-methyl alcohol and methanol oxidation product poison is an eager problem that solves.
The research of fuel-cell catalyst is that the catalysis expert studies focus all the time, and the research of DMFC cathod catalyst mainly concentrates on: platinum and alloy thereof.[US3992331, US5641723, US5068161, CN1346706A, CN1577928, CN1425499A] introduced the preparation method of loaded platinum catalyst.As mentioned above, methanol crossover easily causes the inefficacy of platinum catalyst; The sulphur-containing alloys of transition metal, as MRu5S5 (M=Rh, Re) and oxide with Ca-Ti ore type, spinel-type, pyrochlore constitution, less as cathod catalyst research, may be that their catalytic activity is lower, unstable easily dissolving loss [Egdell R.G in sour environment, Goodenough J.B., Hamnett A.et al., J.Chem.Soc.FaradayTrans., 1983, I79:893-912]; Transition metal macrocycle is as porphyrin, phthalocyanine etc.Because these transition metal macrocycles are cheap and easy to get, and can anti-methyl alcohol, so this compounds enjoys common people to pay close attention to as the DMFC cathod catalyst.
CN1387273A has introduced a kind of preparation method of carbon supported platinum-transition metal macrocyclic compound catalyst of the DMFC of being applied to negative electrode.This method utilizes platinum and transition metal macrocyclic compound all to have high catalytic activity to hydrogen reduction; and the good anti-methyl alcohol ability of macrocyclic compound; heat-treat carrying the inert gas shielding different temperatures after the two physical mixed, obtain a class and carry platinum-transition metal macrocyclic compound catalyst than the active height of pure carbon platinum carried catalysis hydrogen reduction, the strong carbon of anti-methyl alcohol ability.This method platinum and transition metal macrocyclic compound are physical mixed only, in conjunction with not tight, can not well bring into play the protective capability of transition metal macrocyclic compound to platinum between the two, make that the ability of anti-methyl alcohol is unsatisfactory.[CN1472212A, CN1472211A] introduced the preparation method of a kind of porphyrin metal complex of mimic biology enzyme design as the DMFC cathod catalyst.It utilizes the cloud density that increases porphyrin ring in the coordination that connects the nitrogen-atoms of imidazole ring on a plurality of electron-donating groups and the central ion on the metalloporphyrin molecule in activated centre, though improved the catalytic performance of porphyrin to a certain extent, but it separately as the cathod catalyst of DMFC, is not still reached the DMFC performance requirement.
Summary of the invention
The objective of the invention is to overcome DMFC methyl alcohol in application process and see through perfluorinated sulfonic acid proton exchange membrane arrival negative electrode from anode, methyl alcohol and methyl alcohol are at the serious Poisoning cathode catalyst of product of negative electrode, the destruction of causing cathod catalyst to be difficult to recover, reduce the defective of the power output of battery greatly, a kind of cathode in direct methanol fuel cells Catalysts and its preparation method is provided, and accelerates cathode catalysis speed.
The principle that realizes above-mentioned purpose is that the cathode in direct methanol fuel cells catalyst becomes the nano-platinum particle that transition metal macrocycle is modified, the i.e. form of platinum grain surface clad macrocyclic compound.Because the platinum surface exists transition metal macrocycle, and on the molecule rank, distribute equably, make the active sites on platinum surface to interact with the little oxygen of spatial configuration of molecules, and the big methyl alcohol of space structure can't contact with the active sites of platinum, intercepted the diffusion of methyl alcohol, reduced the poisoning of platinum to the platinum surface.And the oxidation-reduction potential of transition metal macrocycle (as phthalocyanine, porphyrin and derivative thereof) is lower than the current potential of platinum, promotes the methyl alcohol of catalyst poisoning and the accelerated oxidation of oxidation product thereof, and platinosis alleviates greatly.Synergy between the platinum one transition metal macrocycle colloid catalyst is applied to the dynamics catalysis speed that methanol fuel cell will improve negative electrode greatly, thereby reduces the output performance of the polarization raising battery of negative electrode.
The technical scheme of invention is:
A kind of cathode in direct methanol fuel cells catalyst is characterized in that, its active component is the nano-platinum particle that transition metal macrocycle is modified, and promptly the form of platinum grain surface clad macrocyclic compound adopts following method preparation, and preparation process is:
Step 1, to select the water-soluble metal macrocyclic compound for use be protective agent, configuration transition metal macrocycle and platinum presoma salt mixed solution, the content of platinum is 0.01～10 grams per liter in the mixed solution, the content of transition metal macrocycle is 0.01～10 grams per liter, wherein, the mol ratio 0.1～10: 1 of transition metal macrocycle and metal platinum, solvent are the deionized water of conductivity＞18 megaohms;
Step 2, add the reducing agent excessive 2～10 times with respect to the molal quantity of platinum in the mixed solution of step 1, slowly add alkaline matter while stirring, regulate pH＞7, reflux finishes to colloidal solid is synthetic under the nitrogen protection;
Step 3, the colloidal solution that step 2 is synthetic are reduced to room temperature, then colloidal solution are filtered and with deionized water wash 3～5 times, 60～90 ℃ of vacuumizes obtain non-supported catalyst; Perhaps, add carrier then in colloidal solution, vigorous stirring 10～20 hours filters and deionized water wash 3～5 times, and 60～90 ℃ of vacuumizes obtain supported catalyst, and wherein, carrier and metal platinum particles mass ratio are 10: 1～100:
The heat treatment 1～4 hour under 100～1200 ℃ of argon shields of step 4, catalyst that step 3 is obtained promptly obtains the cathode in direct methanol fuel cells catalyst:
Wherein, described transition metal macrocycle is a water soluble compound, comprise band sulfonate radical, the quaternary ammonium root of phthalocyanine, porphyrin, the water soluble compound and the derivative thereof of carboxylate radical side chain, transition metal macrocycle is a central metallic ions with Cr, Mo, Mn, Fe, Co, Ni, Cu, Ru, Rh, Ir or Pt respectively.
Described platinum presoma salt is H
2PtCl
4, H
2PtCl
6, Pt (OAC)
2, Pt (acac)
2, Na
2PtCl
6, K
2PtCl
6, platinum carbonyls or platinum and amine complex compound.
Described reducing agent is NaBH
4, N
2H
2H
2O, H
2, formaldehyde, formic acid, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, glycerol, butanediol, triethanolamine or trishydroxymethylaminomethane dihydroxylic alcohols, trihydroxy alcohol, tetrahydroxy alcohol.
Described carrier is graphite, carbon black, carbon nano-tube, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2Or molecular sieve.
The used alkaline matter of described adjusting pH is K
2CO
3, Na
2CO
3, NaHCO
3, Li
2CO
3, NaOH or KOH.
The platinum grain surface clad macrocyclic compound degree of this cathode in direct methanol fuel cells catalyst is by regulating the proportional control of platinum presoma salt and transition metal macrocycle.
Cathode in direct methanol fuel cells Preparation of catalysts method of the present invention comprises the steps:
Step 1, be protective agent with the water-soluble metal macrocyclic compound, configuration transition metal macrocycle and platinum presoma salt mixed solution, the content of platinum is 0.01～10 grams per liter in the mixed solution, the content of transition metal macrocycle is 0.01～10 grams per liter, wherein, the mol ratio 0.1～10: 1 of transition metal macrocycle and metal platinum, solvent are the deionized water of conductivity＞18 megaohms;
Step 2, add the reducing agent excessive 2～10 times with respect to the molal quantity of platinum in the mixed solution of step 1, slowly add alkaline matter while stirring, regulate pH＞7, reflux finishes to colloidal solid is synthetic under the nitrogen protection;
Step 3, the colloidal solution that step 2 is synthetic are reduced to room temperature, then colloidal solution are filtered and deionized water wash 3～5 times, and 60～90 ℃ of vacuumizes obtain non-supported catalyst; Perhaps, add carrier then in colloidal solution, vigorous stirring 10～20 hours filters and deionized water wash 3～5 times, and 60～90 ℃ of vacuumizes obtain supported catalyst, and wherein, carrier and metal platinum particles mass ratio are 10: 1～100;
The heat treatment 1～4 hour under 100～1200 ℃ of argon shields of step 4, catalyst that step 3 is obtained promptly obtains the cathode in direct methanol fuel cells catalyst;
Wherein, described transition metal macrocycle is a water soluble compound, comprise band sulfonate radical, the quaternary ammonium root of phthalocyanine, porphyrin, the water soluble compound and the derivative thereof of carboxylate radical side chain, transition metal macrocycle is a central metallic ions with Cr, Mo, Mn, Fe, Co, Ni, Cu, Ru, Rh, Ir, Pt respectively; Described platinum presoma salt is H
2PtCl
4, H
2PtCl
6, Pt (OAC)
2, Pt (acac)
2, Na
2PtCl
6, K
2PtCl
6, platinum carbonyls or platinum and amine complex compound; Described reducing agent is NaBH
4, N
2H
2H
2O, H
2, formaldehyde, formic acid, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, glycerol, butanediol, triethanolamine or trishydroxymethylaminomethane dihydroxylic alcohols, trihydroxy alcohol, tetrahydroxy alcohol; Described carrier is graphite, carbon black, carbon nano-tube, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2Or molecular sieve; Described alkaline matter is K
2CO
3, Na
2CO
3, NaHCO
3, Li
2CO
3, NaOH or KOH.
Platiniferous presoma salt recited above electronation in transition metal macrocycle solution becomes platinum grain, forms platinum grain surface clad macrocyclic compound.By regulating the proportional control platinum grain surface clad macrocyclic compound degree of platinum presoma salt and transition metal macrocycle, improve anti-methyl alcohol of platinum based catalyst and the methanol oxidation product that transition metal macrocycle is modified thereby reach, accelerate cathode catalysis speed.
Characteristics of the present invention are that transition metal macrocycle is coated on around the platinum grain closely, and by regulating the proportional control platinum grain surface clad macrocyclic compound degree of platinum presoma salt and transition metal macrocycle.On the one hand, transition metal macrocycle is at the special dispersing mode on platinum surface, make the active sites on platinum surface to interact, and the big methyl alcohol of space structure can't contact, and has intercepted the diffusion of methyl alcohol to the platinum surface with the active sites of platinum with the little oxygen of spatial configuration of molecules; On the other hand, poisoned platinum, also can have been fallen, made platinum catalyst recover catalytic performance again by platinum surface metal macrocyclic compound catalytic reaction even poison the material of platinum catalyst.Synergy between platinum-transition metal macrocycle colloid catalyst will be accelerated cathode catalysis speed.Obtained by the cathodic polarization curve that records: reduction take-off potential and the platinum of oxygen on platinum-transition metal macrocycle colloid catalyst is basic identical, in whole voltage range, the reduction current and the platinum catalyst of platinum-transition metal macrocycle colloid catalyst are suitable, even greater than platinum catalyst; When methyl alcohol existed, the reduction of oxygen on platinum-transition metal macrocycle colloid catalyst was unaffected substantially.
Description of drawings
Fig. 1 is the phthalocyanine agent structure, and central ion M is Ni (II)
The branched structure of Fig. 2 for introducing
Fig. 3 is the transmission electron microscope photo of embodiment one
Fig. 4 is the porphyrin agent structure, and central ion M is Fe (II)
Embodiment
Following embodiment further specifies of the present invention.
Embodiment 1
Get 100 milliliters of the nickel phthalocyanine derivative solutions of 0.01 mol, the phthalocyanine agent structure as shown in Figure 1, central ion M is Ni (II), the side chain of introducing as shown in Figure 2, R1=R2=R3=R4=R.Electromagnetic agitation 10 minutes adds the H of 0.01 mol
2PtCl
6100 milliliters of solution continue to stir 10 minutes; Add 90 milliliters of absolute ethyl alcohols as reducing agent, stirring after 5 minutes with NaOH regulation system pH value is 8.5.Reflux to colloid generates under nitrogen protection; treat that colloid cooling back adds 0.6 gram Vulcan XC-72 carbon dust, vigorous stirring 15 hours is filtered and with deionized water rinsing 3 times; 80 ℃ of following vacuumizes are at last with catalyst heat treatment 2 hours under 300 ℃ of argon shields.The reduction take-off potential of oxygen on the catalyst of preparation is 0.89 volt (with respect to standard hydrogen electrode), to carry platinum suitable with comparing the carbon of answering, at current potential is 0.6 volt of place, the corresponding carbon supported platinum catalyst of hydrogen reduction current ratio has increased by 25%: when methyl alcohol exists, the reduction starting voltage of oxygen on carbon supported platinum catalyst is 0.7 volt, and the reduction starting voltage of oxygen on the catalyst of preparation is 0.85 volt, is 0.6 volt of place at current potential, and the latter's hydrogen reduction electric current is the former 2.1 times.Fig. 3 is the transmission electron microscope photo of embodiment one.
Embodiment 2
Get 100 milliliters of the ferriporphyrin derivative solutions of 0.05 mol, the porphyrin agent structure as shown in Figure 4, central ion M is Fe (II), the side chain R1=R2=R3=R4=R=SO of introducing
3-H.Electromagnetic agitation 10 minutes adds the H of 0.03 mol
2PtCl
4100 milliliters of solution continue to stir 10 minutes; The NaBH that adds 0.1 mol
420 milliliters as reducing agent, stirs and uses Na after 5 minutes
2CO
3Regulation system pH value is 8.Reflux to colloid generates under nitrogen protection, treats that colloid cooling back adds the carbon fiber of 0.8 gram, and vigorous stirring 20 hours is filtered and with deionized water rinsing 5 times, and 80 ℃ of following vacuumizes are at last with catalyst heat treatment 4 hours under 500 ℃ of argon shields.The reduction take-off potential of oxygen on the catalyst of preparation is 0.85 volt (with respect to standard hydrogen electrode), to carry platinum suitable with corresponding carbon, at current potential is 0.6 volt of place, the corresponding carbon supported platinum catalyst of hydrogen reduction current ratio has increased by 20%: when methyl alcohol exists, the reduction starting voltage of oxygen on the catalyst of preparation is 0.84 volt, at current potential is 0.6 volt of place, and oxygen is on corresponding platinum catalyst 1.9 times at the reduction current on the composite catalyst.
Claims (7)
1, a kind of cathode in direct methanol fuel cells catalyst is characterized in that, described catalyst is the nanometer platinum colloid that transition metal macrocycle is modified, and promptly the form of platinum grain surface clad macrocyclic compound makes with following method, and its preparation process is:
Step 1, to select the water-soluble metal macrocyclic compound for use be protective agent, configuration transition metal macrocycle and platinum presoma salt mixed solution, the content of platinum is 0.01～10 grams per liter in the mixed solution, the content of transition metal macrocycle is 0.01～10 grams per liter, wherein, the mol ratio 0.1～10: 1 of transition metal macrocycle and metal platinum, solvent are the deionized water of conductivity＞18M Ω;
Step 2, add the reducing agent excessive 2～10 times with respect to the molal quantity of platinum in the mixed solution of step 1, slowly add alkaline matter while stirring, regulate pH＞7, reflux finishes to colloidal solid is synthetic under the nitrogen protection;
Step 3, the colloidal solution that step 2 is synthetic are reduced to room temperature, then colloidal solution are filtered and with deionized water wash 3～5 times, 60～90 ℃ of vacuumizes obtain non-supported catalyst; Perhaps, add carrier then in colloidal solution, vigorous stirring 10～20 hours filters and deionized water wash 3～5 times, and 60～90 ℃ of vacuumizes obtain supported catalyst, and wherein, carrier and metal platinum particles mass ratio are 10: 1～100;
The heat treatment 1～4 hour under 100～1200 ℃ of argon shields of step 4, catalyst that step 3 is obtained promptly obtains the cathode in direct methanol fuel cells catalyst;
Described transition metal macrocycle is a water soluble compound, comprise band sulfonate radical, the quaternary ammonium root of phthalocyanine, porphyrin, the water soluble compound and the derivative thereof of carboxylate radical side chain, transition metal macrocycle is a central metallic ions with Cr, Mo, Mn, Fe, Co, Ni, Cu, Ru, Rh, Ir or Pt respectively.
2, cathode in direct methanol fuel cells catalyst as claimed in claim 1 is characterized in that, described platinum presoma salt is H
2PtCl
4, H
2PtCl
6, Pt (OAC)
2, Pt (acac)
2, Na
2PtCl
6, K
2PtCl
6, platinum carbonyls or platinum and amine complex compound.
3, cathode in direct methanol fuel cells catalyst as claimed in claim 1 is characterized in that, described reducing agent is NaBH
4, N
2H
2H
2O, H
2, formaldehyde, formic acid, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, glycerol, butanediol, triethanolamine or trishydroxymethylaminomethane dihydroxylic alcohols, trihydroxy alcohol, tetrahydroxy alcohol.
4, cathode in direct methanol fuel cells catalyst as claimed in claim 1 is characterized in that, described carrier is graphite, carbon black, carbon nano-tube, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2Or molecular sieve.
5, cathode in direct methanol fuel cells catalyst as claimed in claim 1 is characterized in that, the used alkaline matter of described adjusting pH is K
2CO
3, Na
2CO
3, NaHCO
3, Li
2CO
3, NaOH or KOH.
6, cathode in direct methanol fuel cells catalyst as claimed in claim 1 is characterized in that, platinum grain surface clad macrocyclic compound degree is by regulating the proportional control of platinum presoma salt and transition metal macrocycle.
7, the described cathode in direct methanol fuel cells Preparation of catalysts of claim 1 method is characterized in that it comprises the steps:
Step 1, be protective agent with the water-soluble metal macrocyclic compound, configuration transition metal macrocycle and platinum presoma salt mixed solution, the content of platinum is 0.01～10 grams per liter in the mixed solution, the content of transition metal macrocycle is 0.01～10 grams per liter, wherein, the mol ratio 0.1～10: 1 of transition metal macrocycle and metal platinum, solvent are the deionized water of conductivity＞18M Ω;
Step 2, add the reducing agent excessive 2～10 times with respect to the molal quantity of platinum in the mixed solution of step 1, slowly add alkaline matter while stirring, regulate pH＞7, reflux finishes to colloidal solid is synthetic under the nitrogen protection;
Step 3, the colloidal solution that step 2 is synthetic are reduced to room temperature, then colloidal solution are filtered and deionized water wash 3～5 times, and 60～90 ℃ of vacuumizes obtain non-supported catalyst; Perhaps, add carrier then in colloidal solution, vigorous stirring 10～20 hours filters and deionized water wash 3～5 times, and 60～90 ℃ of vacuumizes obtain supported catalyst, and wherein, carrier and metal platinum particles mass ratio are 10: 1～100;
The heat treatment 1～4 hour under 100～1200 ℃ of argon shields of step 4, catalyst that step 3 is obtained promptly obtains the cathode in direct methanol fuel cells catalyst;
Wherein, described transition metal macrocycle is a water soluble compound, comprise band sulfonate radical, the quaternary ammonium root of phthalocyanine, porphyrin, the water soluble compound and the derivative thereof of carboxylate radical side chain, transition metal macrocycle is a central metallic ions with Cr, Mo, Mn, Fe, Co, Ni, Cu, Ru, Rh, Ir or Pt respectively; Described platinum presoma salt is H
2PtCl
4, H
2PtCl
6, Pt (OAC)
2, Pt (acac)
2, Na
2PtCl
6, K
2PtCl
6, platinum carbonyls or platinum and amine complex compound; Described reducing agent is NaBH
4, N
2H
2H
2O, H
2, formaldehyde, formic acid, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, glycerol, butanediol, triethanolamine or trishydroxymethylaminomethane dihydroxylic alcohols, trihydroxy alcohol, tetrahydroxy alcohol; Described carrier is graphite, carbon black, carbon nano-tube, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2Or molecular sieve; Described alkaline matter is K
2CO
3, Na
2CO
3, NaHCO
3, Li
2CO
3, NaOH or KOH.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109499595A (en) * | 2018-11-16 | 2019-03-22 | 中国林业科学研究院林产化学工业研究所 | A kind of oxygen reduction reaction (ORR) catalyst GPNCS and preparation method thereof |
| CN112805857A (en) * | 2018-10-08 | 2021-05-14 | 丰田自动车工程及制造北美公司 | Stepped adsorption mechanism for overcoming activation energy barrier in oxygen reduction reaction |
| US11196054B2 (en) | 2015-10-06 | 2021-12-07 | International Business Machines Corporation | Proton exchange membrane materials |
| CN114284514A (en) * | 2021-12-27 | 2022-04-05 | 格林美股份有限公司 | Fuel cell electrocatalyst Pt3M-N/C and preparation method thereof |
| WO2022087784A1 (en) * | 2020-10-26 | 2022-05-05 | 浙江大学 | Homogeneous catalyst and anion exchange membrane fuel cell catalyst layer |
| CN114551909A (en) * | 2022-01-26 | 2022-05-27 | 浙江天能氢能源科技有限公司 | Fuel cell catalyst and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1387273A (en) * | 2002-04-05 | 2002-12-25 | 中国科学院长春应用化学研究所 | Process for preparing methanol-resistant electrocatalyst for cathode of direct methanol fuel battery |
| CN1260842C (en) * | 2002-07-09 | 2006-06-21 | 中国科学院长春应用化学研究所 | Process for praparing non-Pt composite electrocatalyst for cathode of fuel battery |
| CN1234709C (en) * | 2002-07-29 | 2006-01-04 | 山东理工大学 | Biporphin metal coordination compound with bridge linking face-face structure and its use |
| CN1199973C (en) * | 2002-07-29 | 2005-05-04 | 山东理工大学 | Substituted carbolnie metal complex and application thereof |
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2006
- 2006-06-09 CN CNB2006100192986A patent/CN100386910C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11196054B2 (en) | 2015-10-06 | 2021-12-07 | International Business Machines Corporation | Proton exchange membrane materials |
| CN112805857A (en) * | 2018-10-08 | 2021-05-14 | 丰田自动车工程及制造北美公司 | Stepped adsorption mechanism for overcoming activation energy barrier in oxygen reduction reaction |
| CN109499595A (en) * | 2018-11-16 | 2019-03-22 | 中国林业科学研究院林产化学工业研究所 | A kind of oxygen reduction reaction (ORR) catalyst GPNCS and preparation method thereof |
| CN109499595B (en) * | 2018-11-16 | 2021-10-08 | 中国林业科学研究院林产化学工业研究所 | Oxygen Reduction Reaction (ORR) catalyst GPNCS and preparation method thereof |
| WO2022087784A1 (en) * | 2020-10-26 | 2022-05-05 | 浙江大学 | Homogeneous catalyst and anion exchange membrane fuel cell catalyst layer |
| CN114284514A (en) * | 2021-12-27 | 2022-04-05 | 格林美股份有限公司 | Fuel cell electrocatalyst Pt3M-N/C and preparation method thereof |
| CN114551909A (en) * | 2022-01-26 | 2022-05-27 | 浙江天能氢能源科技有限公司 | Fuel cell catalyst and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100386910C (en) | 2008-05-07 |
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