CN104022295B - A kind of DMFC PdAg/TiO2the preparation method of nanotube electrode - Google Patents

A kind of DMFC PdAg/TiO2the preparation method of nanotube electrode Download PDF

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Publication number
CN104022295B
CN104022295B CN201410188912.6A CN201410188912A CN104022295B CN 104022295 B CN104022295 B CN 104022295B CN 201410188912 A CN201410188912 A CN 201410188912A CN 104022295 B CN104022295 B CN 104022295B
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tio
nanotube
pdag
titanium plate
preparation
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CN104022295A (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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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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses DMFC nano Pd particle Ag/TiO2Nanotube electrode and preparation method, product is first formed nanotube on surface by titanium plate anodic oxidation, and then electroplating deposition nano Pd particle Ag alloy forms.Form the TiO of a thin layer high-ratio surface on titanium plate surface after titanium plate anodic oxidation roasting2Nanotube, TiO2The PdAg alloy of nanotube surface electroplating deposition can improve TiO2The electric conductivity of nanotube and PdAg alloy are to TiO2Synergism improve TiO2Catalytic oxidation performance to methanol, meanwhile, methanol aoxidizes the intermediate products such as the CO of generation and is adsorbed, transfers to PdAg/TiO2Nanotube surface, and be end product CO by deep oxidation2, the resisting CO poison ability of catalyst can be improved, owing to the price of PdAg is far below noble metals such as Pt, Ru, and at PdAg/TiO2Nanotube is measured less, therefore can be substantially reduced the cost of catalyst, PdAg/TiO2Nanotube electrode is used as DMFC anode, can improve battery performance.

Description

A kind of DMFC PdAg/TiO2The preparation method of nanotube electrode
Technical field
The present invention relates to DMFC PdAg/TiO2The preparation method of nanotube electrode.
Background technology
DMFC (Direct Methanol Fuel Cell, DMFC) have less energy consumption, energy density height, methanol abundance, low price, system are simple, run convenient and low noise advantages, it is considered as future automobile power and the most promising electrochmical power source of other vehicles, causes the extensive concern of people.One of material of DMFC most critical is electrode catalyst, and it directly affects the performance of battery, stability, service life and manufacturing cost.Precious metals pt has the catalytic performance of excellence under cryogenic (less than 80 DEG C), the electrode catalyst of DMFC is all with Pt as main component at present, wherein PtRu catalyst has higher CO tolerance catalysts performance and higher catalysis activity than pure Pt, it it is considered as catalyst optimal for current DMFC, but due to defects such as it are expensive, Ru is readily soluble, the utilization rate in DMFC does not also reach business-like requirement.People have carried out numerous studies and have prepared multiplex catalyst to improve its catalysis activity, raising resisting CO poison ability.TiO2Doping is such as PtRuTiOX/ C and Au/TiO2PtRu catalyst or as carrier such as PtNi/TiO2、PdNi/TiO2、PdAg/TiO2Deng, it is possible to reduce the consumption of precious metals pt or prepare non-platinum catalyst in catalyst, reduces catalyst manufacturing cost, improves catalytic performance and resisting CO poison ability, have application prospect.PdAg/TiO2Nanotube electrode can have good catalytic performance and resisting CO poison performance as sensor or DMFC anode, have not been reported methanol.
Summary of the invention
It is an object of the invention to provide one and can be used as DMFC anode, reduce DMFC catalyst cost, improve its catalysis activity and DMFC PdAg/TiO of resisting CO poison ability2Nanotube electrode and preparation method.
The technical solution of the present invention is:
The present invention first forms nanotube with titanium plate anodic oxidation on surface, and then electroplating deposition nano Pd particle Ag alloy forms.Form the TiO of a thin layer high-ratio surface on titanium plate surface after titanium plate anodic oxidation roasting2Nanotube, TiO2The PdAg alloy of nanotube surface electroplating deposition can improve TiO2The electric conductivity of nanotube and PdAg alloy are to TiO2Synergism improve TiO2Catalytic oxidation performance to methanol, meanwhile, methanol aoxidizes the intermediate products such as the CO of generation and is adsorbed, transfers to PdAg/TiO2Nanotube surface, and be end product CO by deep oxidation2, the resisting CO poison ability of catalyst can be improved, owing to the price of PdAg is far below noble metals such as Pt, Ru, and at PdAg/TiO2Nanotube is measured less, therefore can be substantially reduced the cost of catalyst, PdAg/TiO2Nanotube electrode is used as DMFC anode, can improve battery performance.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
(1) pre-treatment of titanium plate: titanium plate abrasive paper for metallograph is polished, ultrasonic oil removing 15 minutes in acetone, methanol or ethanol purge, the HF of 1mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried.
(2)TiO2The preparation of nanotube/Ti: the titanium plate handled well is carried out anodic oxidation in the electrolytic solution.The H of the HF of the composition of electrolyte: 0.5%-1%, 1mol/L2SO4.Electrolytic potential 20V, electrolysis time 30 minutes.It is electrolysed complete, deionized water wash, to dry, in Muffle furnace, 500-600 DEG C of roasting obtains TiO in 3 hours2Nanotube/Ti.
(3)PdAg/TiO2The preparation of nanotube electrode: the TiO that will prepare2Nanotube/Ti electroplates as negative electrode, and the volume of plating solution is 50mL.The composition of electroplate liquid:
Electroplate complete, deionized water wash, dry, obtain PdAg/TiO2Nanotube electrode.
Embodiment 2:
(1) pre-treatment of titanium plate: titanium plate abrasive paper for metallograph is polished, ultrasonic oil removing 15 minutes in acetone, methanol or ethanol purge, the HF of 1mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried.
(2)TiO2The preparation of nanotube/Ti: the titanium plate handled well is carried out anodic oxidation in the electrolytic solution.The H of the HF of the composition of electrolyte: 0.5%-1%, 1mol/L2SO4.Electrolytic potential 20V, electrolysis time 120 minutes.It is electrolysed complete, deionized water wash, to dry, in Muffle furnace, 500-600 DEG C of roasting obtains TiO in 3 hours2Nanotube/Ti.
(3)PdAg/TiO2The preparation of nanotube electrode: the TiO that will prepare2Nanotube/Ti electroplates as negative electrode, and the volume of plating solution is 50mL.The composition of electroplate liquid:
Electroplate complete, deionized water wash, dry, obtain PdAg/TiO2Nanotube electrode.
Embodiment 3:
(1) pre-treatment of titanium plate: titanium plate abrasive paper for metallograph is polished, ultrasonic oil removing 15 minutes in acetone, methanol or ethanol purge, the HF of 1mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried.
(2)TiO2The preparation of nanotube/Ti: the titanium plate handled well is carried out anodic oxidation in the electrolytic solution.The H of the HF of the composition of electrolyte: 0.5%-1%, 1mol/L2SO4.Electrolytic potential 20V, electrolysis time 60 minutes.It is electrolysed complete, deionized water wash, to dry, in Muffle furnace, 500-600 DEG C of roasting obtains TiO in 3 hours2Nanotube/Ti.
(3)PdAg/TiO2The preparation of nanotube electrode: the TiO that will prepare2Nanotube/Ti electroplates as negative electrode.The composition of electroplate liquid:
Electroplate complete, deionized water wash, dry, obtain PdAg/TiO2Nanotube electrode.

Claims (1)

1. a DMFC PdAg/TiO2The preparation method of nanotube electrode, its Being characterised by, described preparation method comprises the following steps:
(1) pre-treatment of titanium plate: titanium plate abrasive paper for metallograph is polished, ultrasonic oil removing 15 points in acetone Clock, methanol or ethanol purge, the HF of 1mol/L processes 10 minutes, and redistilled water is ultrasonic clearly Wash 3 times, dry；
(2)TiO2The preparation of nanotube/Ti: the titanium plate handled well is carried out anode in the electrolytic solution Oxidation；The H of the HF of the composition of electrolyte: 0.5%-1%, 1mol/L2SO4, electrolytic potential 20 V, electrolysis time 30-120 minute；It is electrolysed complete, deionized water wash, dry, Muffle furnace Middle 500-600 DEG C of roasting obtains TiO in 3 hours2Nanotube/Ti；
(3)PdAg/TiO2The preparation of nanotube electrode: the TiO that will prepare2Nanotube/Ti makees Electroplating for negative electrode, the volume of plating solution is 50mL, the composition of electroplate liquid:
Electroplate complete, deionized water wash, dry, obtain PdAg/TiO2Nanotube electrode.
CN201410188912.6A 2014-05-07 2014-05-07 A kind of DMFC PdAg/TiO2the preparation method of nanotube electrode Expired - Fee Related CN104022295B (en)

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CN105562111B (en) * 2015-12-11 2018-03-09 长春工业大学 Pd/ZIF‑67/TiO2The preparation method of nano-tube composite catalyst
CN111129509B (en) * 2019-12-31 2022-05-17 南通大学 Direct methanol fuel cell anode catalyst and preparation method thereof
CN112146197B (en) * 2020-09-14 2022-03-11 南通大学 Noise elimination disinfection self-purification air purifier
CN113363506A (en) * 2021-07-12 2021-09-07 南通大学 Direct methanol fuel cell electrode and preparation method thereof

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CN102553649B (en) * 2011-12-26 2013-09-25 河海大学 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof

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