CN104022295A - Direct methanol fuel cell PdAg/TiO2 nanotube electrode and preparation method thereof - Google Patents

Direct methanol fuel cell PdAg/TiO2 nanotube electrode and preparation method thereof Download PDF

Info

Publication number
CN104022295A
CN104022295A CN201410188912.6A CN201410188912A CN104022295A CN 104022295 A CN104022295 A CN 104022295A CN 201410188912 A CN201410188912 A CN 201410188912A CN 104022295 A CN104022295 A CN 104022295A
Authority
CN
China
Prior art keywords
pdag
tio
nanotube
tio2
titanium plate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410188912.6A
Other languages
Chinese (zh)
Other versions
CN104022295B (en
Inventor
鞠剑峰
石玉军
高强
吴东辉
苏广均
华平
李建华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nantong University
Original Assignee
Nantong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nantong University filed Critical Nantong University
Priority to CN201410188912.6A priority Critical patent/CN104022295B/en
Publication of CN104022295A publication Critical patent/CN104022295A/en
Application granted granted Critical
Publication of CN104022295B publication Critical patent/CN104022295B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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 a direct methanol fuel cell PdAg/TiO2 nanotube electrode and a preparation method thereof. The PdAg/TiO2 nanotube electrode is formed in a manner that a positive pole of a titanium plate is oxidized to form nanotubes on the surface, and a nanometer PdAg alloy is deposited though electroplating. After the positive pole of the titanium plate is oxidized by roasting, a thin layer of TiO2 nanotubes with high specific surfaces is formed on the surface of the titanium plate, the electrical conductivity of the TiO2 nanotubes is improved by the PdAg alloy deposited on the surface of the TiO2 nanotubes in an electroplating manner, and a catalytic oxidation of TiO2 on methyl alcohol is greatly improved through the synergistic effect of the PdAg alloy on TiO2; meanwhile, intermediate products, such as CO, generated by methyl alcohol oxidation are adsorbed and transferred to the surfaces of the PdAg/TiO2 nanotubes and are deeply oxidized to obtain a final product CO2, and a CO toxicity resisting capacity of the catalyst is improved; the price of PdAg is lower than that of noble metals such as Pt and Ru, and the dosage of PdAg in the PdAg/TiO2 nanotubes is small, so that the cost of the catalyst is greatly reduced; the PdAg/TiO2 nanotube electrode is utilized as a direct methanol fuel cell anode, and the property of the cell is improved.

Description

A kind of direct methanol fuel cell PdAg/TiO 2nanotube electrode and preparation method thereof
Technical field
The present invention relates to direct methanol fuel cell PdAg/TiO 2nanotube electrode 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 DEG C) and has excellent catalytic performance under cryogenic conditions, the electrode catalyst of DMFC is all taking 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, be considered to the catalyst of current DMFC the best, but due to defects such as it is expensive, Ru 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.TiO 2doping is as PtRuTiO x/ C and Au/TiO 2ptRu catalyst or as carrier as PtNi/TiO 2, PdNi/TiO 2, PdAg/TiO 2deng, can reduce the consumption of precious metals pt in catalyst or prepare non-platinum catalyst, reduce catalyst manufacturing cost, improve catalytic performance and resisting CO poison ability, there is application prospect.PdAg/TiO 2nanotube electrode can be used as transducer or direct methanol fuel cell anode, and methyl alcohol is had to good catalytic performance and resisting CO poison performance, have not been reported.
Summary of the invention
The object of the present invention is to provide one to can be used as direct methanol fuel cell anode, reduce direct methanol fuel cell catalyst cost, improve the direct methanol fuel cell PdAg/TiO of its catalytic activity and resisting CO poison ability 2nanotube electrode and preparation method.
Technical solution of the present invention is:
The present invention first forms nanotube with the anodic oxidation of titanium plate on surface, then electroplating deposition nanometer PdAg alloy forms.After titanium plate anodic oxidation roasting, form the TiO of skim high-ratio surface on titanium plate surface 2nanotube, TiO 2the PdAg alloy of nanotube surface electroplating deposition can improve TiO 2the conductivity of nanotube and PdAg alloy are to TiO 2synergy improve TiO 2to the catalytic oxidation performance of methyl alcohol, meanwhile, the intermediate products such as the CO that methanol oxidation produces are adsorbed, transfer to PdAg/TiO 2nanotube surface, and be end product CO by deep oxidation 2, can improve the resisting CO poison ability of catalyst, because the price of PdAg is far below the noble metal such as Pt, Ru, and at PdAg/TiO 2in nanotube, amount is less, therefore can greatly reduce the cost of catalyst, PdAg/TiO 2nanotube electrode, as direct methanol fuel cell anode, can improve battery performance.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
(1) pre-treatment of titanium plate: titanium plate is polished with abrasive paper for metallograph, ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean, and the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried.
(2) TiO 2the preparation of nanotube/Ti: the titanium plate of handling well is carried out to anodic oxidation in electrolyte.The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L 2sO 4.Electrolytic potential 20 V, electrolysis time 30 minutes.Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500-600 DEG C of roasting obtains TiO for 3 hours 2nanotube/Ti.
(3) PdAg/TiO 2the preparation of nanotube electrode: by the TiO preparing 2nanotube/Ti electroplates as negative electrode, and the volume of plating solution is 50 mL.The composition of electroplate liquid:
AgNO 3 0.01 mol/L
Pd(NO 3) 2 0.01 mol/L
H 3BO 3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm 2
T:30 minute
Electroplate completely, deionized water washing, dries, and obtains PdAg/TiO 2nanotube electrode.
Embodiment 2:
(1) pre-treatment of titanium plate: titanium plate is polished with abrasive paper for metallograph, ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean, and the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried.
(2) TiO 2the preparation of nanotube/Ti: the titanium plate of handling well is carried out to anodic oxidation in electrolyte.The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L 2sO 4.Electrolytic potential 20 V, electrolysis time 120 minutes.Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500-600 DEG C of roasting obtains TiO for 3 hours 2nanotube/Ti.
(3) PdAg/TiO 2the preparation of nanotube electrode: by the TiO preparing 2nanotube/Ti electroplates as negative electrode, and the volume of plating solution is 50 mL.The composition of electroplate liquid:
AgNO 3 0.01 mol/L
Pd(NO 3) 2 0.01 mol/L
H 3BO 3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm 2
T:60 minute
Electroplate completely, deionized water washing, dries, and obtains PdAg/TiO 2nanotube electrode.
Embodiment 3:
(1) pre-treatment of titanium plate: titanium plate is polished with abrasive paper for metallograph, ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean, and the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried.
(2) TiO 2the preparation of nanotube/Ti: the titanium plate of handling well is carried out to anodic oxidation in electrolyte.The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L 2sO 4.Electrolytic potential 20 V, electrolysis time 60 minutes.Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500-600 DEG C of roasting obtains TiO for 3 hours 2nanotube/Ti.
(3) PdAg/TiO 2the preparation of nanotube electrode: by the TiO preparing 2nanotube/Ti electroplates as negative electrode.The composition of electroplate liquid:
AgNO 3 0.01 mol/L
Pd(NO 3) 2 0.01 mol/L
H 3BO 3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm 2
T:90 minute
Electroplate completely, deionized water washing, dries, and obtains PdAg/TiO 2nanotube electrode.

Claims (3)

1. a direct methanol fuel cell PdAg/TiO 2nanotube electrode, is characterized in that: described nanotube electrode first forms nanotube on surface by the anodic oxidation of titanium plate, and then electroplating deposition nanometer PdAg alloy forms.
2. a kind of direct methanol fuel cell PdAg/TiO according to claim 1 2nanotube electrode, is characterized in that: described titanium plate size 20 mm × 20 mm, thickness 0.3 mm, purity 99.5 %.
3. a kind of direct methanol fuel cell PdAg/TiO according to claim 1 2the preparation method of nanotube electrode, is characterized in that, described preparation method comprises the following steps:
(1) pre-treatment of titanium plate: titanium plate is polished with abrasive paper for metallograph, ultrasonic oil removing 15 minutes in acetone, methyl alcohol or ethanol clean, and the HF of 1 mol/L processes 10 minutes, and redistilled water ultrasonic cleaning 3 times is dried;
(2) TiO 2the preparation of nanotube/Ti: the titanium plate of handling well is carried out to anodic oxidation in electrolyte; The HF of the composition of electrolyte: 0.5%-1%, the H of 1mol/L 2sO 4, electrolytic potential 20 V, electrolysis time 30-120 minute; Electrolysis is complete, and deionized water washing, dries, and in Muffle furnace, 500-600 DEG C of roasting obtains TiO for 3 hours 2nanotube/Ti;
(3) PdAg/TiO 2the preparation of nanotube electrode: by the TiO preparing 2nanotube/Ti electroplates as negative electrode, and the volume of plating solution is 50 mL, the composition of electroplate liquid:
AgNO 3 0.01 mol/L
Pd(NO 3) 2 0.01 mol/L
H 3BO 3 20g/L
PH: 4.4
T: room temperature
Current density: 5 mA/cm 2
t: 30-90 min
Electroplate completely, deionized water washing, dries, and obtains PdAg/TiO 2nanotube 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410188912.6A CN104022295B (en) 2014-05-07 2014-05-07 A kind of DMFC PdAg/TiO2the preparation method of nanotube electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410188912.6A CN104022295B (en) 2014-05-07 2014-05-07 A kind of DMFC PdAg/TiO2the preparation method of nanotube electrode

Publications (2)

Publication Number Publication Date
CN104022295A true CN104022295A (en) 2014-09-03
CN104022295B CN104022295B (en) 2016-10-19

Family

ID=51438941

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410188912.6A Expired - Fee Related CN104022295B (en) 2014-05-07 2014-05-07 A kind of DMFC PdAg/TiO2the preparation method of nanotube electrode

Country Status (1)

Country Link
CN (1) CN104022295B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105562111A (en) * 2015-12-11 2016-05-11 长春工业大学 Preparation method of Pd/ZIF-67/TiO2 nanotube composite catalyst
CN111129509A (en) * 2019-12-31 2020-05-08 南通大学 Direct methanol fuel cell anode catalyst and preparation method thereof
CN112146197A (en) * 2020-09-14 2020-12-29 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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113533450A (en) * 2021-07-12 2021-10-22 南通大学 Sensitive electrode, formaldehyde flexible sensor and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102257647A (en) * 2008-12-19 2011-11-23 古河电气工业株式会社 Optical semiconductor device lead frame and manufacturing method thereof
CN102553649A (en) * 2011-12-26 2012-07-11 河海大学 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102257647A (en) * 2008-12-19 2011-11-23 古河电气工业株式会社 Optical semiconductor device lead frame and manufacturing method thereof
CN102553649A (en) * 2011-12-26 2012-07-11 河海大学 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHUNKAI SHI等: "Promotion Effects of Air and H2 Nonthermal Plasmas on TiO2 Supported Pd and Pd-Ag Catalysts for Selective Hydrogenation of Acetylene", 《IND. ENG. CHEM. RES.》 *
JIANFENG JU等: "A novel PdAg/TiO2 nanotube electrocatalyst for methanol electro-oxidation"，T. Tsyjino等，《Journal of Molecular Catalysis", 《FUEL》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105562111A (en) * 2015-12-11 2016-05-11 长春工业大学 Preparation method of Pd/ZIF-67/TiO2 nanotube composite catalyst
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
CN111129509A (en) * 2019-12-31 2020-05-08 南通大学 Direct methanol fuel cell anode catalyst and preparation method thereof
CN111129509B (en) * 2019-12-31 2022-05-17 南通大学 Direct methanol fuel cell anode catalyst and preparation method thereof
CN112146197A (en) * 2020-09-14 2020-12-29 南通大学 Noise elimination disinfection self-purification air purifier
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

Also Published As

Publication number Publication date
CN104022295B (en) 2016-10-19

Similar Documents

Publication Publication Date Title
Rao et al. Hydrotalcite-like Ni (OH) 2 nanosheets in situ grown on nickel foam for overall water splitting
CN103924260B (en) Compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper and cobalt and preparation method thereof
CN102677092B (en) Preparation method of titanium anode
CN102251266B (en) Method for preparing nano platinum/titanium dioxide nanotube electrode by pulse electrodeposition
Qin et al. TiO2 nanotube arrays supported Pd nanoparticles for ethanol electrooxidation in alkaline media
CN105297107B (en) A kind of method of cyclic voltammetric electrodeposited nanocrystalline platinum nickel/titanium dioxide nanotube electrode
CN104022295A (en) Direct methanol fuel cell PdAg/TiO2 nanotube electrode and preparation method thereof
CN104759272B (en) A kind of membrane electrode of membrane electrode low-voltage electrolysis formula ozone generator and its production method of anode and anode
CN102703942B (en) Method for preparing nano-platinum/palladium titanium dioxide nanotube composite electrode by pulse electrodeposition
CN104022289A (en) Direct methanol fuel cell RuNi/TiO2 nanotube electrode and preparation method thereof
CN104037428B (en) Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof
CN107159227B (en) High-efficiency and long-life CoWB/NF catalyst for hydrogen production by sodium borohydride hydrolysis and preparation method thereof
Li et al. Highly efficient NiFe nanoparticle decorated Si photoanode for photoelectrochemical water oxidation
Zhang et al. Preparation of Pt catalysts decorated TiO2 nanotube arrays by redox replacement of Ni precursors for proton exchange membrane fuel cells
CN105734606A (en) Structure of ultrathin membrane electrode for SPE water electrolysis and preparation and application of structure
CN106048690B (en) A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof
Hou et al. Electrocatalytic performance of Ni-Ti-O nanotube arrays/NiTi alloy electrode annealed under H2 atmosphere for electro-oxidation of methanol
CN102703953B (en) Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition
CN102899683A (en) Preparation method of Ti-based nano-CeO2/PbO2 modified electrode
Telli et al. Investigation of noble metal loading CoWZn electrode for HER
Low et al. A gold-coated titanium oxide nanotube array for the oxidation of borohydride ions
CN106191945A (en) A kind of pulse electrodeposition prepares the method for titania nanotube immobilized platinum nickel bimetal combination electrode
CN100386849C (en) Process for preparing mesoporous metal counter electrode for dye-sensitized solar cell
CN104022297A (en) Direct methanol fuel cell PdNi/TiO2 nanotube electrode and preparation method thereof
CN103255457B (en) A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20161019

Termination date: 20170507