CN103041857A - Preparation method of graphite nano-plate-loaded nano-noble metal catalyst - Google Patents
Preparation method of graphite nano-plate-loaded nano-noble metal catalyst Download PDFInfo
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- CN103041857A CN103041857A CN2012105526245A CN201210552624A CN103041857A CN 103041857 A CN103041857 A CN 103041857A CN 2012105526245 A CN2012105526245 A CN 2012105526245A CN 201210552624 A CN201210552624 A CN 201210552624A CN 103041857 A CN103041857 A CN 103041857A
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Abstract
The invention provides a preparation method of a graphite nano-plate-loaded nano-noble metal catalyst. The preparation method comprises the following steps: uniformly performing ultrasonic dispersion on an active functional group-containing four-aromatic ring compound and a graphite nano-plate in different liquid phases respectively; mixing and performing ultrasonic dispersion on the two solutions, and adsorbing the four-aromatic ring compound on the surface of the graphite nano-plate through pi-pi conjugation; and loading the noble metal catalyst on the graphite nano-plate by an impregnation reduction method, wherein the four-aromatic ring compound has the chemical structure shown as FORMULA 1 or FORMULA 2, in which R1 is a side chain containing an active functional group and the active functional group is one of -COOH, -NH2, -OH, -C=O or -SO3H. The prepared catalyst nano-metal particles are uniform in distribution and relatively small in size; the catalyst has relatively high electrochemical surface area, high catalytic activity and high stability; and the prepared catalyst can be applied to the fields of low-temperature fuel batteries, metal-air batteries and the like.
Description
Technical field
The present invention relates to a kind of preparation method of Nano graphite plate nano-noble-metal-loaded catalyst, belong to catalyst preparation technical field and electrochemical energy technical field.
Background technology
Low-temperature fuel cell has efficiently, cleans, starts the advantages such as fast, have broad application prospects in fields such as electric automobile, dislocation generation equipment, but because their operating temperature is low, all must guarantee that as catalyst electrode surface has enough fast reaction rate with highly active noble metal such as Pt, Pd, Ru, Au etc. or its alloy.In order effectively to utilize the galvano-cautery on noble metal and the opposing electrode, noble metal catalyst is carrier mainly with carbon.Traditional carbon carrier is a kind of amorphous carbon, and degree of graphitization is low, with the binding ability of noble metal or its alloy a little less than, corrosion-vulnerable has affected catalytic capability and the stability of catalyst to hydrogen reduction simultaneously.
In order to improve the active and stable of catalyst, people are doing many research work aspect the selection of carbon carrier, as attempting with the carrier as catalyst such as CNT, carbon fiber, carbon gel.And Graphene is because its high-specific surface area (2630m
2/ g), high conductivity (1 * 10
4S/m), high heat conductance and high stability, be considered to best catalyst carbon carrier material.Although calculate the surface that is adsorbed on Graphene that noble metal clusters such as finding platinum can be stable by first principle, the Graphene surface has chemical inertness, and the noble metal nano particles size is larger during direct carried catalyst, and distributed pole is inhomogeneous.In order to reduce the size of noble metal granule, improve its dispersiveness, also for the convenience of carrier preparation, people adopt the graphene oxide after the reduction more simultaneously.Graphene oxide preparation process after this reduction is complicated, use strong acid, strong oxidizer, toxic reagent (such as hydrazine, hydrazine hydrate etc.).The Graphene of preparation has chemistry and physical imperfection simultaneously, has affected the performance of Graphene.
Nano graphite plate (multi-layer graphene, the number of plies〉10) can directly peel off from graphite and obtain, cheap and easy to get, the shortcomings of the graphene oxide after avoiding reducing when having the above-mentioned excellent properties of Graphene is the better selection of Graphene class catalyst carrier.Identical with Graphene, Nano graphite plate surface is carbon sp
2Hybrid structure has chemical inertness, and directly supported noble metal is infeasible.For not destroying its high graphitization structure, the useful diallyl dimethyl ammoniumchloride of forefathers is adsorbed on graphene nano plate surface, and then carries platinum, but polymer is easily crosslinked, and platinum grain distributes also inhomogeneous behind year platinum.Noble metal granule occur that self reunites, spatial distribution is inhomogeneous and chemical property low be Nano graphite plate supported noble metal catalyst problem in the urgent need to address.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of Nano graphite plate nano-noble-metal-loaded catalyst, its step comprises:
The four aromatic rings compounds that 1) will contain active function groups and Nano graphite plate be ultrasonic being uniformly dispersed in different liquid phases respectively; Then two kinds of solution are mixed and ultrasonic dispersion, make the four aromatic rings compounds that contain active function groups be adsorbed in Nano graphite plate surface by π-πconjugation;
The described chemical constitution that contains four aromatic rings compounds of active function groups:
Wherein, R
1For containing the side chain of active function groups, active function groups is-COOH ,-NH
2,-OH ,-C=O or-SO
3A kind of among the H;
2) immersion reduction method supported precious metal catalyst on the Nano graphite plate;
Further, the preparation method's of a Nano graphite plate nano-noble-metal-loaded catalyst of the present invention preferred steps is as follows: 1) with Nano graphite plate and the four aromatic rings compounds that contain active function groups by weight 10:(0.5 ~ 1.5) ultrasonic being uniformly dispersed in water and ethylene glycol solution respectively, wherein water and ethylene glycol volume ratio are 1:2; Then two kinds of solution are mixed and ultrasonic dispersion, the four aromatic rings compounds that contain active function groups are adsorbed on the surface of Nano graphite plate; 2) add the presoma of the noble metal of metering in the above-mentioned mixed solution, adopt immersion reduction method supported precious metal catalyst on the Nano graphite plate, the mass fraction of noble metal is 10% ~ 30% in the catalyst; 3) filter reacted solution, and dry cake, catalyst to be prepared namely obtained.
Further, another preferred steps of the preparation method of Nano graphite plate nano-noble-metal-loaded catalyst of the present invention is as follows: 1) with Nano graphite plate and the four aromatic rings compounds that contain active function groups by weight 10:(0.5 ~ 1.5) ultrasonic being uniformly dispersed in water and methanol solution respectively, wherein water and methyl alcohol volume ratio are 11:1; Then two kinds of solution are mixed and ultrasonic dispersion, the four aromatic rings compounds that contain active function groups are adsorbed on the surface of Nano graphite plate; 2) above-mentioned mixed solution heats and adds the presoma of the noble metal of metering in 40 ℃ water bath with thermostatic control, then dropwise drips NaBH
4The aqueous solution; NaBH
4Be 4:1 with the mole ratio of noble metal; The mass fraction of noble metal is 10 ~ 30% in the catalyst; 3) filter reacted solution and dry cake, namely obtain catalyst to be prepared.
Also have among the preparation method of Nano graphite plate nano-noble-metal-loaded catalyst of the present invention, the thickness of described Nano graphite plate is 3-20nm, is 0.5 μ m-20 μ m towards yardstick.Described noble metal catalyst is a kind of in platinum, palladium, rhodium, ruthenium, iridium and the Au catalyst, or contains the alloy catalyst of above-mentioned noble metal.
The present invention compared with prior art has the following advantages:
(1) the present invention does not need the Nano graphite plate is carried out complicated functionalization, has kept the high graphitization sp on Nano graphite plate surface
2Structure has kept electrical conductivity, thermal conductivity and the stability of Nano graphite plate.
(2) the catalyst noble metal granule of the present invention's preparation is tiny, narrow diameter distribution, and even in Nano graphite plate surface distributed.Solved noble metal nano particles self reunion and spatial distribution problem of non-uniform have occured.
(3) catalyst of the present invention preparation is tiny and use the carrier of high graphitization because of particle, so have higher electrochemical surface area, higher catalytic activity and stability preferably.
(4) method for preparing catalyst of the present invention is simple to operate, and treatment conditions are gentle, are easy to realize industrialization.
Description of drawings
Fig. 1 is the Nano graphite plate platinum catalyst TEM figure that embodiment 1 usefulness pyrene formic acid is modified;
Fig. 2 is the Nano graphite plate platinum catalyst TEM figure that embodiment 1 does not do modification;
Fig. 3 is Nano graphite plate platinum catalyst and the commodity Pt/C(JohnsonMatthey that embodiment 1 usefulness pyrene formic acid is modified) at 0.5mol/L H
2SO
4Cyclic voltammetry curve in the solution;
Fig. 4 is the Nano graphite plate platinum catalyst of embodiment 1 usefulness pyrene formic acid modification and the stable chart that commodity Pt/C catalyst characterizes with the quick aging method;
Fig. 5 is that the Nano graphite plate platinum catalyst modified of embodiment 1 usefulness pyrene formic acid and commodity Pt/C catalyst are at 0.5mol/L H
2SO
4Solution and 0.5mol/L H
2SO
4+ 1.0mol/L CH
3Polarization curves of oxygen reduction in the OH solution;
Fig. 6 is the Nano graphite plate platinum catalyst TEM figure that embodiment 2 usefulness pyrene formic acid are modified;
Fig. 7 is the Nano graphite plate platinum catalyst TEM figure that the amino pyrene of embodiment 3 usefulness 1-is modified;
Fig. 8 is the Nano graphite plate platinum catalyst TME figure that embodiment 4 usefulness 1-hydroxyl pyrenes are modified;
Fig. 9 is the Nano graphite plate platinum catalyst TME figure that embodiment 5 usefulness 1-pyrene sulfonic acid are modified.
The specific embodiment
The specific embodiments and the drawings of carrying platinum below in conjunction with preferred Nano graphite plate are further elaborated the present invention, but enforcement of the present invention is not limited to this.
Embodiment 1:
(1) 100mg Nano graphite plate (average thickness 10nm) is disperseed 30min in the 100mL deionized water for ultrasonic, obtain the aqueous dispersions of Nano graphite plate.With 12mg pyrene formic acid ultrasonic 30min in 200mL ethylene glycol, obtain pyrene formic acid ethylene glycol solution.Then Nano graphite plate aqueous dispersions and pyrene formic acid ethylene glycol solution are mixed, and magnetic agitation 24h, make pyrene formic acid be adsorbed on Nano graphite plate surface, obtain water, the ethylene glycol mixed dispersion liquid of the Nano graphite plate of pyrene formic acid modification.
(2) above-mentioned 300mL water, ethylene glycol mixed dispersion liquid are joined in the 500mL there-necked flask, in oil bath, add thermal agitation and water condensing reflux.When the mixed dispersion liquid temperature rises to 90 ℃, add the H of 12.8mL 0.01mol/L
2PtCl
6The aqueous solution.Begin calculating reacting time when oil bath temperature rises to 125 ℃, afterreaction finished in 4 hours, cooling final vacuum suction filtration.Filter cake was namely obtained the Nano graphite plate platinum catalyst (Pt20wt%) that pyrene formic acid is modified in 12 hours 100 ℃ of lower vacuum drying.
(3) Comparative Examples 1: as a comparison, prepare simultaneously the Nano graphite plate platinum catalyst of modifying without pyrene formic acid, its method is with step (1) and (2) among the above-mentioned embodiment 1, but the ethylene glycol in the step (1) does not contain pyrene formic acid.
Fig. 1 is the TEM figure of the Nano graphite plate platinum catalyst of pyrene formic acid modification, and Fig. 2 is not for being the Nano graphite plate platinum catalyst TEM figure of modification.Can find out from Fig. 1 and Fig. 2, during without pyrene formic acid, the platinum grain size is uncontrollable, distributes also extremely inhomogeneous.Behind pyrene formic acid modification Nano graphite plate, pyrene formic acid provides avtive spot for platinum, and platinum grain size homogeneous distributes also very even.
(4) get 10mg and be dissolved in the 5mL ethanol by the prepared catalyst of above-mentioned steps (2), make the uniform dispersion that catalyst content is 2mg/mL behind the ultrasonic 30min.Getting 3 μ L dispersant liquid drops is on the glass-carbon electrode of 3mm at diameter, and drying at room temperature drips 5 μ L 0.05wt%Nafion emulsions more thereon after 1 hour, and then drying at room temperature made the glass carbon working electrode that contains catalyst in 12 hours.As a comparison, the preparation glass carbon working electrode that uses the same method, its catalyst is the commodity Pt/C(Pt 20wt% of JohnsonMatthey company).
(5) adopt three-electrode system that catalyst is carried out cyclic voltammetry, characterize its electrochemical surface area.Working electrode is that reference electrode is saturated KCl calomel electrode, is platinum plate electrode to electrode by the glass-carbon electrode of above-mentioned steps (4) preparation.Test is at 0.5mol/L H
2SO
4Carry out in the solution, the scanning current potential is-0.24-0.96V(vs.SCE), and sweep speed is 50mV/s.Fig. 3 is the Nano graphite plate platinum catalyst of pyrene formic acid modification and the cyclic voltammogram of commodity Pt/C catalyst.Solid line is the Nano graphite plate platinum catalyst that pyrene formic acid is modified, and dotted line is the Pt/C catalyst.Fig. 3 shows, compares with commodity Pt/C catalyst, and the catalyst of the present invention's preparation has higher electrochemical surface area.
(6) adopt the quick aging method to characterize the stability of the catalyst of the present invention's preparation.Concrete grammar is, adopts the three-electrode system of step (5), applies the pulse potential of 0.85V-30s-1.4V-150s(vs.RHE), accelerates that it is aging, and carry out the cyclic voltammetry contrast aging before and after the variation of electrochemical surface area.Test is at 0.5mol/L H
2SO
4Carry out in the solution, applied pulse potential 20 hours, the same step of cyclic voltammetry (5).Fig. 4 is the Nano graphite plate platinum catalyst of pyrene formic acid modification and the residue electrochemical surface area stability chart that commodity Pt/C catalyst represents with percentage.Solid line is the Nano graphite plate platinum catalyst that pyrene formic acid is modified, and dotted line is the Pt/C catalyst.As can be seen from Figure 4, the catalyst of the present invention's preparation has the stability higher than Pt/C.
(7) characterize the catalyst of the present invention's preparation to catalytic activity and the anti-CO poisoning capability of oxygen by polarization curves of oxygen reduction.Concrete grammar is for adopting the three-electrode system of step (5), but is platinum electrode to electrode.Test is carried out in rotating disk electrode (r.d.e), and rotating speed is 1600rpm, and sweep speed 10mV/s, electrolyte solution are respectively 0.5mol/L H
2SO
4Solution and 0.5mol/L H
2SO
4+ 1.0mol/L CH
3OH solution, and logical pure oxygen is saturated.Fig. 5 is the Nano graphite plate platinum catalyst of pyrene formic acid modification and the polarization curves of oxygen reduction of commodity Pt/C catalyst.Among Fig. 5, solid line 1 and 3 is respectively Nano graphite plate platinum catalyst that pyrene formic acid modifies and Pt/C catalyst at 0.5mol/L H
2SO
4Polarization curves of oxygen reduction in the solution, dotted line 2 and 4 are respectively Nano graphite plate platinum catalyst that pyrene formic acid modifies and Pt/C catalyst at 0.5mol/LH
2SO
4+ 1.0mol/L CH
3Polarization curves of oxygen reduction in the OH solution.As can be seen from Figure 5, compare with Pt/C, the catalyst of the present invention's preparation has higher catalytic activity to oxygen, and in the situation that methyl alcohol exists, the variation of hydrogen reduction carrying current is less, namely has higher anti-CO poisoning capability.
Embodiment 2:
(1) 100mg Nano graphite plate is dispersed in the 275mL water, ultrasonic dispersion 30min obtains the aqueous dispersions of Nano graphite plate.12mg pyrene formic acid is dispersed in the 25mL methyl alcohol, and ultrasonic dispersion 30min obtains pyrene formic acid methanol solution.Then Nano graphite plate aqueous dispersions and pyrene formic acid methanol solution are mixed, and magnetic agitation 24h, make pyrene formic acid be adsorbed on Nano graphite plate surface, obtain water, the methyl alcohol mixed dispersion liquid of the Nano graphite plate of pyrene formic acid modification.
(2) above-mentioned 300mL water, methyl alcohol mixed dispersion liquid are joined in the there-necked flask of 500mL heated at constant temperature and magnetic agitation in 40 ℃ water-bath.When the mixed solution temperature rises to 40 ℃, add 12.8mL0.01mol/LH to it
2PtCl
6Behind the aqueous solution, dropwise drip the NaBH of 50mL 0.006mol/L
4The aqueous solution.After 4 hours, reaction finishes.
(3) solution that above-mentioned reaction is complete cooling final vacuum suction filtration, and remove wherein foreign ion with excessive washing.Filter cake namely made 100 ℃ of vacuum drying in 12 hours use NaBH
4The Nano graphite plate platinum catalyst (Pt 20wt%) that the pyrene formic acid of reduction is modified.
Fig. 6 is the catalyst TEM figure of as stated above preparation.
Embodiment 3:
(1) 100mg Nano graphite plate (average thickness 10nm) is disperseed 30min in the 100mL deionized water for ultrasonic, obtain the aqueous dispersions of Nano graphite plate.With the amino pyrene of 12mg1-ultrasonic 30min in 200mL ethylene glycol, obtain the ethylene glycol solution of the amino pyrene of 1-.Then the ethylene glycol solution with Nano graphite plate aqueous dispersions and 1-amino pyrene mixes, and magnetic agitation 24h, makes the amino pyrene of 1-be adsorbed on Nano graphite plate surface, obtains water, the ethylene glycol mixed dispersion liquid of the Nano graphite plate of the amino pyrene modification of 1-.
(2) above-mentioned 300mL water, ethylene glycol mixed dispersion liquid are joined in the 500mL there-necked flask, in oil bath, add thermal agitation and water condensing reflux.When the mixed dispersion liquid temperature rises to 90 ℃, add the H of 9.05mL 0.01mol/L
2PtCl
6The aqueous solution.Begin calculating reacting time when oil bath temperature rises to 125 ℃, afterreaction finished in 4 hours.
(3) the solution cooling final vacuum suction filtration that above-mentioned reaction is complete.Filter cake was namely obtained the Nano graphite plate platinum catalyst (Pt 15wt%) that the amino pyrene of 1-is modified in 12 hours 100 ℃ of lower vacuum drying.
The Nano graphite plate platinum catalyst TEM figure of Fig. 7 for modifying by the amino pyrene of the 1-of this method preparation.
Embodiment 4:
(1) 100mg Nano graphite plate (average thickness 10nm) is disperseed 30min in the 100mL deionized water for ultrasonic, obtain the aqueous dispersions of Nano graphite plate.With 12mg1-hydroxyl pyrene ultrasonic 30min in 200mL ethylene glycol, obtain the ethylene glycol solution of 1-hydroxyl pyrene.Then the ethylene glycol solution with Nano graphite plate aqueous dispersions and 1-hydroxyl pyrene mixes, and magnetic agitation 24h, makes 1-hydroxyl pyrene be adsorbed on Nano graphite plate surface, obtains water, the ethylene glycol mixed dispersion liquid of the Nano graphite plate of 1-hydroxyl pyrene modification.
(2) above-mentioned 300mL water, ethylene glycol mixed dispersion liquid are joined in the 500mL there-necked flask, in oil bath, add thermal agitation and water condensing reflux.When the mixed dispersion liquid temperature rises to 90 ℃, add the H of 5.70mL 0.01mol/L
2PtCl
6The aqueous solution.Begin calculating reacting time when oil bath temperature rises to 125 ℃, afterreaction finished in 4 hours.
(3) the solution cooling final vacuum suction filtration that above-mentioned reaction is complete.Filter cake was namely obtained the Nano graphite plate platinum catalyst (Pt 10wt%) that 1-hydroxyl pyrene is modified in 12 hours 100 ℃ of lower vacuum drying.
The Nano graphite plate platinum catalyst TEM figure of Fig. 8 for modifying by the 1-hydroxyl pyrene of this method preparation.
Embodiment 5:
(1) 100mg Nano graphite plate (average thickness 10nm) is disperseed 30min in the 100mL deionized water for ultrasonic, obtain the aqueous dispersions of Nano graphite plate.With 12mg1-pyrene sulfonic acid ultrasonic 30min in 200mL ethylene glycol, obtain the ethylene glycol solution of 1-pyrene sulfonic acid.Then the ethylene glycol solution with Nano graphite plate aqueous dispersions and 1-pyrene sulfonic acid mixes, and magnetic agitation 24h, makes 1-pyrene sulfonic acid be adsorbed on Nano graphite plate surface, obtains water, the ethylene glycol mixed dispersion liquid of the Nano graphite plate of 1-pyrene sulfonic acid modification.
(2) above-mentioned 300mL water, ethylene glycol mixed dispersion liquid are joined in the 500mL there-necked flask, in oil bath, add thermal agitation and water condensing reflux.When the mixed dispersion liquid temperature rises to 90 ℃, add the H of 12.8mL 0.01mol/L
2PtCl
6The aqueous solution.Begin calculating reacting time when oil bath temperature rises to 125 ℃, afterreaction finished in 4 hours.
(3) the solution cooling final vacuum suction filtration that above-mentioned reaction is complete.Filter cake was namely obtained the Nano graphite plate platinum catalyst (Pt 20wt%) that 1-pyrene sulfonic acid is modified in 12 hours 100 ℃ of lower vacuum drying.
The Nano graphite plate platinum catalyst TEM figure of Fig. 9 for modifying by the 1-pyrene sulfonic acid of this method preparation.
Although top invention has been described in conjunction with figure; but the present invention is not limited to the above-mentioned specific embodiment; the above-mentioned specific embodiment only is schematic; rather than restrictive; those of ordinary skill in the art is under enlightenment of the present invention; in the situation that do not break away from aim of the present invention, can also make a lot of distortion, these all belong within the protection of the present invention.
Claims (5)
1. the preparation method of a Nano graphite plate nano-noble-metal-loaded catalyst, its step comprises:
The four aromatic rings compounds that 1) will contain active function groups and Nano graphite plate be ultrasonic being uniformly dispersed in different liquid phases respectively; Then two kinds of solution are mixed and ultrasonic dispersion, make the four aromatic rings compounds that contain active function groups be adsorbed in Nano graphite plate surface by π-πconjugation;
The described chemical constitution that contains four aromatic rings compounds of active function groups:
Wherein, R
1For containing the side chain of active function groups, active function groups is-COOH ,-NH
2,-OH ,-C=O or-SO
3A kind of among the H;
2) immersion reduction method supported precious metal catalyst on the Nano graphite plate;
3) filtration and drying obtain catalyst product.
2. the preparation method of described Nano graphite plate nano-noble-metal-loaded catalyst according to claim 1 is characterized in that, its step is as follows:
1) with Nano graphite plate and the four aromatic rings compounds that contain active function groups by weight 10:(0.5～1.5) ultrasonic being uniformly dispersed in water and ethylene glycol solution respectively, wherein water and ethylene glycol volume ratio are 1:2; Then two kinds of solution are mixed and ultrasonic dispersion, the four aromatic rings compounds that contain active function groups are adsorbed on the surface of Nano graphite plate;
2) add the presoma of the noble metal of metering in the above-mentioned mixed solution, adopt immersion reduction method supported precious metal catalyst on the Nano graphite plate, the mass fraction of noble metal is 10% ~ 30% in the catalyst;
3) filter reacted solution, and dry cake, catalyst to be prepared namely obtained.
3. the preparation method of described Nano graphite plate nano-noble-metal-loaded catalyst according to claim 1 is characterized in that, its step is as follows:
1) with Nano graphite plate and the four aromatic rings compounds that contain active function groups by weight 10:(0.5 ~ 1.5) ultrasonic being uniformly dispersed in water and methanol solution respectively, wherein water and methyl alcohol volume ratio are 11:1; Then two kinds of solution are mixed and ultrasonic dispersion, the four aromatic rings compounds that contain active function groups are adsorbed on the surface of Nano graphite plate;
2) above-mentioned mixed solution heats and adds the presoma of the noble metal of metering in 40 ℃ water bath with thermostatic control, then dropwise drips NaBH
4The aqueous solution; NaBH
4Be 4:1 with the mole ratio of noble metal; The mass fraction of noble metal is 10 ~ 30% in the catalyst;
3) filter reacted solution and dry cake, namely obtain catalyst to be prepared.
4. the preparation method of each the described Nano graphite plate nano-noble-metal-loaded catalyst in 3 according to claim 1, wherein, the thickness of described Nano graphite plate is 3-20nm, is 0.5 μ m-20 μ m towards yardstick.
5. the preparation method of each the described Nano graphite plate nano-noble-metal-loaded catalyst in 3 according to claim 1, wherein, described noble metal catalyst is a kind of in platinum, palladium, rhodium, ruthenium, iridium and the Au catalyst, or contains the alloy catalyst of above-mentioned noble metal.
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| CN103623864A (en) * | 2013-11-25 | 2014-03-12 | 天津大学 | Method for preparing Pt-based anode catalyst of direct liquid flow methanol fuel cell |
| CN104810527A (en) * | 2014-01-23 | 2015-07-29 | 三星Sdi株式会社 | Electrode catalyst for fuel cell, electrode and fuel cell |
| CN106784893A (en) * | 2016-12-16 | 2017-05-31 | 中国石油大学(华东) | A kind of high activity for fuel cell anode is without metal N, P codope conjugated backbone material |
| CN111359669A (en) * | 2020-04-29 | 2020-07-03 | 河北工程大学 | Non-covalent supported GOx-Py-Co (Salen) catalyst and synthesis method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623864A (en) * | 2013-11-25 | 2014-03-12 | 天津大学 | Method for preparing Pt-based anode catalyst of direct liquid flow methanol fuel cell |
| CN104810527A (en) * | 2014-01-23 | 2015-07-29 | 三星Sdi株式会社 | Electrode catalyst for fuel cell, electrode and fuel cell |
| EP2899785A1 (en) * | 2014-01-23 | 2015-07-29 | Samsung SDI Co., Ltd. | Electrode catalyst for fuel cell, method of preparing the same, electrode for fuel cell including the electrolyte catalyst, and fuel cell including the electrode |
| CN106784893A (en) * | 2016-12-16 | 2017-05-31 | 中国石油大学(华东) | A kind of high activity for fuel cell anode is without metal N, P codope conjugated backbone material |
| CN111359669A (en) * | 2020-04-29 | 2020-07-03 | 河北工程大学 | Non-covalent supported GOx-Py-Co (Salen) catalyst and synthesis method thereof |
| CN111359669B (en) * | 2020-04-29 | 2022-11-11 | 河北工程大学 | Non-covalent supported GOx-Py-Co (Salen) catalyst and synthesis method thereof |
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Application publication date: 20130417 |