CN104022296A - TiO2@C supported PdRu direct methanol fuel cell anode catalyst and preparation method thereof - Google Patents

TiO2@C supported PdRu direct methanol fuel cell anode catalyst and preparation method thereof Download PDF

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CN104022296A
CN104022296A CN201410188915.XA CN201410188915A CN104022296A CN 104022296 A CN104022296 A CN 104022296A CN 201410188915 A CN201410188915 A CN 201410188915A CN 104022296 A CN104022296 A CN 104022296A
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ethylene glycol
porous hollow
catalyst
hollow tio
pdru
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CN104022296B (en
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鞠剑峰
石玉军
高强
吴东辉
苏广均
华平
李建华
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Nantong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

The invention discloses a multi-hole hollow TiO2@C supported PdRu direct methanol fuel cell anode catalyst and a preparation method thereof, and the catalyst is composed of a multi-hole hollow TiO2@C carrier and a PdRu nano-alloy. The multi-hole hollow TiO2@C nano-carrier with high specific surface and the PdRu nano-alloy can form the multi-element catalyst in a recombination manner. With the recombination of C and deposition of the PdAg alloy on the surface of the carrier, the electrical conductivity of TiO2 is improved; the catalytic oxidation of TiO2 on methyl alcohol is greatly improved through the synergistic effect on TiO2 from the recombination of C and the PdRu alloy; meanwhile, intermediate products, such as CO generated by methyl alcohol oxidation, are adsorbed and transferred to the surface of the composite catalyst and are directly deeply oxidized to obtain a final product CO2; in addition, the TiO2@C nano-carrier is stable, and is less prone to oxidation. The price of PdRu is greatly less than that of a precious metal Pt, and the dosage of RuNi in the catalyst is small, thus, the cost of the catalyst is greatly reduced, a CO toxicity resisting capacity of the catalyst is improved, the cost of the catalyst in a direct methanol fuel cell is greatly reduced, and the property of the direct methanol fuel cell is improved.

Description

A kind of TiO 2@C load P dRu anode catalysts for direct methanol fuel cell and preparation method
 
Technical field
The present invention relates to porous hollow TiO 2@C load P dRu anode catalysts for direct methanol fuel cell and preparation method.
Background technology
Direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) have that less energy consumption, energy density are high, methyl alcohol source is abundant, low price, system are simple, move convenient and low noise advantages, be considered to future automobile power and the most promising chemical power source of other vehicles, cause people's extensive concern.One of material of DMFC most critical is electrode catalyst, and it directly affects performance, stability, useful life and the manufacturing cost of battery.Precious metals pt (is less than 80 ℃) and has excellent catalytic performance under cryogenic conditions, the electrode catalyst of DMFC all be take Pt as main component at present, wherein PtRu catalyst has stronger anti-CO poisoning performance and the catalytic activity of Geng Gao than pure Pt, the catalyst that is considered to current DMFC the best, but due to defects such as it is expensive, Ag Yi Rong, the utilance in DMFC does not also reach business-like requirement.People have carried out large quantity research and have prepared multiplex catalyst to improve its catalytic activity, improve resisting CO poison ability.If any report, prepared PtAgTiO x/ C and Au/TiO 2ptAg catalyst, TiO 2the compound consumption that can reduce precious metals pt in catalyst, improve catalytic performance and resisting CO poison ability, but in these catalyst, the consumption of precious metals pt is still very high, and catalyst be take C as carrier, C carrier is oxidizable in actual application, affects the stability of catalyst and the performance of battery.Porous hollow TiO 2@C is that carrier is prepared the non-platinum anode catalyst of direct methanol fuel cell and be have not been reported.
 
Summary of the invention
The object of the present invention is to provide a kind of direct methanol fuel cell catalyst cost that reduces, improve its stability, to the non-platinum anode catalyst of the direct methanol fuel cell of the catalytic activity of methyl alcohol and resisting CO poison ability and preparation method.
Technical solution of the present invention is:
A kind of porous hollow TiO 2@C load P dRu anode catalysts for direct methanol fuel cell, described catalyst is by porous hollow TiO 2@C carrier and PdRu Nanoalloy form, and it is characterized in that: porous hollow TiO 2the content of@C carrier is 97 ~ 99 % of catalyst gross mass, porous hollow TiO 2mass ratio m with C tiO2: m cfor 1:1 ~ 3:7, the content sum of PdRu Nanoalloy is 1 ~ 3 % of catalyst gross mass, the mol ratio n of PdRu pd: n rufor 7:3,1:1, or 3:7.
Further, described C is Vulcan XC-72.
A kind of porous hollow TiO 2the preparation method of@C load P dRu anode catalysts for direct methanol fuel cell comprises the following steps:
(1) porous hollow TiO 2the preparation of nanosphere: adopt sol-gel process, the butyl titanate of amount of calculation is dissolved in to a certain amount of absolute ethyl alcohol, add a certain amount of Surfactant PEG-600 and Vulcan XC-72, stir the lower mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water, hydrolysis continues to stir after forming colloidal sol, standing 2-3 days after gel to be formed, after 80 ℃ of powder that obtain after vacuumize 8-10 hour grind in Muffle furnace 400-600 ℃ of air roasting 3 hours, make porous hollow TiO 2nanosphere; While preparing colloidal sol, the consumption mol ratio of butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water is: n butyl titanate: n absolute ethyl alcohol: n glacial acetic acid: n deionized water=1:20 ~ 40:1 ~ 2.5:2 ~ 6; PEG-600 consumption is 1% of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid cumulative volume; The consumption of Vulcan XC-72 is that butyl titanate complete hydrolysis finally generates TiO 230% of theoretical amount;
(2) porous hollow TiO 2the preparation of@C nano-carrier: take a certain amount of Vulcan XC-72 and join in deionized water, ultrasonic dispersion 30 minutes, adds the porous hollow TiO of amount of calculation under vigorous stirring 2nanosphere, forms slurries, continues to stir 1 hour, filter, and deionized water washing, 80 ℃ of vacuumizes, make porous hollow TiO 2@C nano-carrier; Porous hollow TiO wherein 2mass ratio m with C tiO2: m cfor 1:1 ~ 3:7;
(3) by porous hollow TiO 2@C nano-carrier joins in ethylene glycol in the ratio of 50-100 mg/ml, and ultrasonic being uniformly dispersed forms porous hollow TiO 2@C dispersion liquid;
(4) by Pd (NO 3) 2be dissolved in ethylene glycol, form the Pd (NO of 5-10 milligram Pd/ milliliter 3) 2/ ethylene glycol solution;
(5) by AgNO 3be dissolved in ethylene glycol, form the AgNO of 2-4 milligram Ag/ milliliter 3/ ethylene glycol solution;
(6) by last synthetic catalyst W pdRu=1 % ~ 3%, mole n pd: n rufor 7:3,1:1, or the ratio of 3:7 measures respectively Pd (NO 3) 2/ ethylene glycol solution and AgNO 3/ ethylene glycol solution, is added drop-wise to porous hollow TiO 2in@C dispersion liquid, ultrasonic dispersion;
(7) NaOH is dissolved in ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
(8) the NaOH ethylene glycol solution of preparation is added drop-wise in the dispersion liquid that step 6) obtains, regulating pH value is 8.5-12;
(9) by KBH 4be dissolved into and in ethylene glycol, be mixed with KBH 4concentration is the KBH of 0.2-0.5mol/L 4/ ethylene glycol solution;
(10) stir, inert gas shielding, at 80-90 ℃, drips KBH in the mixing suspension that is 8.5-12 to pH value 4/ ethylene glycol solution, reaction 2-6 hour;
(11) filter after completion of the reaction, deionized water wash in filter liquor without chloride ion and sulfate ion, 80-120 ℃ of vacuumize, makes catalyst.
Beneficial effect of the present invention is: the present invention is with the porous hollow TiO of high-ratio surface 2@C nano-carrier and PdRu Nanoalloy are compounded to form multicomponent catalyst.Compound and the PdRu alloy deposition of C can improve TiO at carrier surface 2conductivity, the compound and PdRu alloy deposition of C is to TiO 2synergy greatly improve TiO 2catalytic oxidation performance to methyl alcohol, meanwhile, the intermediate products such as CO that methanol oxidation produces are adsorbed, transfer to composite catalyst surface, and are end product CO by direct deep oxidation 2, in addition, TiO 2@C nano-carrier is stable, is difficult for oxidized.Because the price of PdRu is far below precious metals pt, and its consumption is less in catalyst, therefore can greatly reduce the cost of catalyst, improves stability, catalytic activity and the resisting CO poison ability of catalyst.
 
Embodiment
Embodiment 1:
(1) porous hollow TiO 2the preparation of nanosphere: adopt sol-gel process.The butyl titanate of amount of calculation is dissolved in to a certain amount of absolute ethyl alcohol, add a certain amount of Surfactant PEG-600 and Vulcan XC-72, stir the lower mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water, hydrolysis continues to stir after forming colloidal sol, after gel to be formed standing 2 days, after the powder that 80 ℃ of vacuumize obtained after 8 hours grinds in Muffle furnace 400 ℃ of air roastings 3 hours, make porous hollow TiO 2nanosphere.While preparing colloidal sol, the consumption mol ratio of butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water is: n butyl titanate: n absolute ethyl alcohol: n glacial acetic acid: n deionized water=1:20 ~ 40:1 ~ 2.5:2 ~ 6.PEG consumption is 1% of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid cumulative volume.The consumption of Vulcan XC-72 is that butyl titanate complete hydrolysis finally generates TiO 230% of theoretical amount.
(2) porous hollow TiO 2the preparation of@C nano-carrier: take a certain amount of Vulcan XC-72 and join in deionized water, ultrasonic dispersion 30 minutes, adds the porous hollow TiO of amount of calculation under vigorous stirring 2nanosphere, forms slurries, continues to stir 1 hour, filter, and deionized water washing, 80 ℃ of vacuumizes, make porous hollow TiO 2@C nano-carrier.Porous hollow TiO wherein 2mass ratio m with C tiO2: m cfor 1:1.
(3) by porous hollow TiO 2@C nano-carrier joins in ethylene glycol in the ratio of 50 mg/ml, and ultrasonic being uniformly dispersed forms porous hollow TiO 2@C dispersion liquid;
(4) by Pd (NO 3) 2be dissolved in ethylene glycol, form the Pd (NO of 5 milligrams of Pd/ milliliters 3) 2/ ethylene glycol solution;
(5) by AgNO 3be dissolved in ethylene glycol, form the AgNO of 2 milligrams of Ag/ milliliters 3/ ethylene glycol solution;
(6) by last synthetic catalyst W pdRu=1%, mol ratio n pd: n rufor the ratio of 7:3 measures respectively Pd (NO 3) 2/ ethylene glycol solution and AgNO 3/ ethylene glycol solution, is added drop-wise to porous hollow TiO 2in@C dispersion liquid, ultrasonic dispersion;
(7) NaOH is dissolved in ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
(8) the NaOH ethylene glycol solution of preparation is added drop-wise in the dispersion liquid that step (6) obtains, regulating pH value is 8.5;
(9) by KBH 4be dissolved into and in ethylene glycol, be mixed with KBH 4concentration is the KBH of 0.2mol/L 4/ ethylene glycol solution;
(10) stir, inert gas shielding, at 80 ℃, drips KBH in the mixing suspension that is 8.5 to pH value 4/ ethylene glycol solution, reacts 2 hours;
(11) filter after completion of the reaction, deionized water wash in filter liquor without chloride ion and sulfate ion, 80 ℃ of vacuumizes, make catalyst.
Embodiment 2:
(1) porous hollow TiO 2the preparation of nanosphere: adopt sol-gel process.The butyl titanate of amount of calculation is dissolved in to a certain amount of absolute ethyl alcohol, add a certain amount of Surfactant PEG-600 and Vulcan XC-72, stir the lower mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water, hydrolysis continues to stir after forming colloidal sol, after gel to be formed standing 3 days, after the powder that 80 ℃ of vacuumize obtained after 9 hours grinds in Muffle furnace 500 ℃ of air roastings 3 hours, make porous hollow TiO 2nanosphere.While preparing colloidal sol, the consumption mol ratio of butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water is: n butyl titanate: n absolute ethyl alcohol: n glacial acetic acid: n deionized water=1:20 ~ 40:1 ~ 2.5:2 ~ 6.PEG consumption is 1% of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid cumulative volume.The consumption of Vulcan XC-72 is that butyl titanate complete hydrolysis finally generates TiO 230% of theoretical amount.
(2) porous hollow TiO 2the preparation of@C nano-carrier: take a certain amount of Vulcan XC-72 and join in deionized water, ultrasonic dispersion 30 minutes, adds the porous hollow TiO of amount of calculation under vigorous stirring 2nanosphere, forms slurries, continues to stir 1 hour, filter, and deionized water washing, 80 ℃ of vacuumizes, make porous hollow TiO 2@C nano-carrier.Porous hollow TiO wherein 2mass ratio m with C tiO2: m cfor 2:3.
(3) by porous hollow TiO 2@C nano-carrier joins in ethylene glycol in the ratio of 80 mg/ml, and ultrasonic being uniformly dispersed forms porous hollow TiO 2@C dispersion liquid;
(4) by Pd (NO 3) 2be dissolved in ethylene glycol, form the Pd (NO of 8 milligrams of Pd/ milliliters 3) 2/ ethylene glycol solution;
(5) by AgNO 3be dissolved in ethylene glycol, form the AgNO of 3 milligrams of Ag/ milliliters 3/ ethylene glycol solution;
(6) by last synthetic catalyst W pdRu=2%, mol ratio n pd: n rufor the ratio of 1:1 measures respectively Pd (NO 3) 2/ ethylene glycol solution and AgNO 3/ ethylene glycol solution, is added drop-wise to porous hollow TiO 2in@C dispersion liquid, ultrasonic dispersion;
(7) NaOH is dissolved in ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
(8) the NaOH ethylene glycol solution of preparation is added drop-wise in the dispersion liquid that step (6) obtains, regulating pH value is 10;
(9) by KBH 4be dissolved into and in ethylene glycol, be mixed with KBH 4concentration is the KBH of 0.4mol/L 4/ ethylene glycol solution;
(10) stir, inert gas shielding, at 80 ℃, drips KBH in the mixing suspension that is 10 to pH value 4/ ethylene glycol solution, reacts 2 hours;
(11) filter after completion of the reaction, deionized water wash in filter liquor without chloride ion and sulfate ion, 100 ℃ of vacuumizes, make catalyst.
Embodiment 3:
(1) porous hollow TiO 2the preparation of nanosphere: adopt sol-gel process.The butyl titanate of amount of calculation is dissolved in to a certain amount of absolute ethyl alcohol, add a certain amount of Surfactant PEG-600 and Vulcan XC-72, stir the lower mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water, hydrolysis continues to stir after forming colloidal sol, after gel to be formed standing 3 days, after the powder that 80 ℃ of vacuumize obtained after 10 hours grinds in Muffle furnace 400 ℃ of air roastings 3 hours, make porous hollow TiO 2nanosphere.While preparing colloidal sol, the consumption mol ratio of butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water is: n butyl titanate: n absolute ethyl alcohol: n glacial acetic acid: n deionized water=1:20 ~ 40:1 ~ 2.5:2 ~ 6.PEG consumption is 1% of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid cumulative volume.The consumption of Vulcan XC-72 is that butyl titanate complete hydrolysis finally generates TiO 230% of theoretical amount.
(2) porous hollow TiO 2the preparation of@C nano-carrier: take a certain amount of Vulcan XC-72 and join in deionized water, ultrasonic dispersion 30 minutes, adds the porous hollow TiO of amount of calculation under vigorous stirring 2nanosphere, forms slurries, continues to stir 1 hour, filter, and deionized water washing, 80 ℃ of vacuumizes, make porous hollow TiO 2@C nano-carrier.Porous hollow TiO wherein 2mass ratio m with C tiO2: m cfor 3:7.
(3) by porous hollow TiO 2@C nano-carrier joins in ethylene glycol in the ratio of 100 mg/ml, and ultrasonic being uniformly dispersed forms porous hollow TiO 2@C dispersion liquid;
(4) by Pd (NO 3) 2be dissolved in ethylene glycol, form the Pd (NO of 10 milligrams of Pd/ milliliters 3) 2/ ethylene glycol solution;
(5) by AgNO 3be dissolved in ethylene glycol, form the AgNO of 4 milligrams of Ag/ milliliters 3/ ethylene glycol solution;
(6) by last synthetic catalyst W pdRu=3%, mol ratio n pd: n rufor the ratio of 3:7 measures respectively Pd (NO 3) 2/ ethylene glycol solution and AgNO 3/ ethylene glycol solution, is added drop-wise to porous hollow TiO 2in@C dispersion liquid, ultrasonic dispersion;
(7) NaOH is dissolved in ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
(8) the NaOH ethylene glycol solution of preparation is added drop-wise in the dispersion liquid that step (6) obtains, regulating pH value is 12;
(9) by KBH 4be dissolved into and in ethylene glycol, be mixed with KBH 4concentration is the KBH of 0.5mol/L 4/ ethylene glycol solution;
(10) stir, inert gas shielding, at 80 ℃, drips KBH in the mixing suspension that is 12 to pH value 4/ ethylene glycol solution, reacts 2 hours;
(11) filter after completion of the reaction, deionized water wash in filter liquor without chloride ion and sulfate ion, 120 ℃ of vacuumizes, make catalyst.

Claims (3)

1. a porous hollow TiO 2@C load P dRu anode catalysts for direct methanol fuel cell, described catalyst is by porous hollow TiO 2@C carrier and PdRu Nanoalloy form, and it is characterized in that: porous hollow TiO 2the content of@C carrier is 97 ~ 99 % of catalyst gross mass, porous hollow TiO 2mass ratio m with C tiO2: m cfor 1:1 ~ 3:7, the content sum of PdRu Nanoalloy is 1 ~ 3 % of catalyst gross mass, the mol ratio n of PdRu pd: n rufor 7:3,1:1, or 3:7.
2. a kind of porous hollow TiO according to claim 1 2@C load P dRu anode catalysts for direct methanol fuel cell, is characterized in that: described C is Vulcan XC-72.
3. a kind of porous hollow TiO according to claim 1 2the preparation method of@C load P dRu anode catalysts for direct methanol fuel cell, is characterized in that, described preparation method comprises the following steps:
(1) porous hollow TiO 2the preparation of nanosphere: adopt sol-gel process, the butyl titanate of amount of calculation is dissolved in to a certain amount of absolute ethyl alcohol, add a certain amount of Surfactant PEG-600 and Vulcan XC-72, stir the lower mixture that drips absolute ethyl alcohol, glacial acetic acid and deionized water, hydrolysis continues to stir after forming colloidal sol, standing 2-3 days after gel to be formed, after 80 ℃ of powder that obtain after vacuumize 8-10 hour grind in Muffle furnace 400-600 ℃ of air roasting 3 hours, make porous hollow TiO 2nanosphere; While preparing colloidal sol, the consumption mol ratio of butyl titanate, absolute ethyl alcohol, glacial acetic acid, deionized water is: n butyl titanate: n absolute ethyl alcohol: n glacial acetic acid: n deionized water=1:20 ~ 40:1 ~ 2.5:2 ~ 6; PEG-600 consumption is 1% of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid cumulative volume; The consumption of Vulcan XC-72 is that butyl titanate complete hydrolysis finally generates TiO 230% of theoretical amount;
(2) porous hollow TiO 2the preparation of@C nano-carrier: take a certain amount of Vulcan XC-72 and join in deionized water, ultrasonic dispersion 30 minutes, adds the porous hollow TiO of amount of calculation under vigorous stirring 2nanosphere, forms slurries, continues to stir 1 hour, filter, and deionized water washing, 80 ℃ of vacuumizes, make porous hollow TiO 2@C nano-carrier; Porous hollow TiO wherein 2mass ratio m with C tiO2: m cfor 1:1 ~ 3:7;
(3) by porous hollow TiO 2@C nano-carrier joins in ethylene glycol in the ratio of 50-100 mg/ml, and ultrasonic being uniformly dispersed forms porous hollow TiO 2@C dispersion liquid;
(4) by Pd (NO 3) 2be dissolved in ethylene glycol, form the Pd (NO of 5-10 milligram Pd/ milliliter 3) 2/ ethylene glycol solution;
(5) by AgNO 3be dissolved in ethylene glycol, form the AgNO of 2-4 milligram Ag/ milliliter 3/ ethylene glycol solution;
(6) by last synthetic catalyst W pdRu=1 % ~ 3%, mol ratio n pd: n rufor 7:3,1:1, or the ratio of 3:7 measures respectively Pd (NO 3) 2/ ethylene glycol solution and AgNO 3/ ethylene glycol solution, is added drop-wise to porous hollow TiO 2in@C dispersion liquid, ultrasonic dispersion;
(7) NaOH is dissolved in ethylene glycol, being mixed with NaOH concentration is the NaOH ethylene glycol solution of 2mol/L;
(8) the NaOH ethylene glycol solution of preparation is added drop-wise in the dispersion liquid that step 6) obtains, regulating pH value is 8.5-12;
(9) by KBH 4be dissolved into and in ethylene glycol, be mixed with KBH 4concentration is the KBH of 0.2-0.5mol/L 4/ ethylene glycol solution;
(10) stir, inert gas shielding, at 80-90 ℃, drips KBH in the mixing suspension that is 8.5-12 to pH value 4/ ethylene glycol solution, reaction 2-6 hour;
(11) filter after completion of the reaction, deionized water wash in filter liquor without chloride ion and sulfate ion, 80-120 ℃ of vacuumize, makes catalyst.
CN201410188915.XA 2014-05-07 2014-05-07 A kind of TiO2@C load P dRu anode catalysts for direct methanol fuel cell and preparation method Expired - Fee Related CN104022296B (en)

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CN109244485A (en) * 2018-10-16 2019-01-18 南通大学 A kind of NiCo/TiO2Cell anode catalyst and preparation method thereof
CN117065765A (en) * 2023-10-17 2023-11-17 佛山仙湖实验室 Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109244485A (en) * 2018-10-16 2019-01-18 南通大学 A kind of NiCo/TiO2Cell anode catalyst and preparation method thereof
CN109244485B (en) * 2018-10-16 2021-12-31 南通大学 NiCo/TiO2Battery anode catalyst and preparation method thereof
CN117065765A (en) * 2023-10-17 2023-11-17 佛山仙湖实验室 Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof

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