CN106816605A - A kind of preparation method of the palladium nanocatalyst of titanium plate load - Google Patents

A kind of preparation method of the palladium nanocatalyst of titanium plate load Download PDF

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Publication number
CN106816605A
CN106816605A CN201710032038.0A CN201710032038A CN106816605A CN 106816605 A CN106816605 A CN 106816605A CN 201710032038 A CN201710032038 A CN 201710032038A CN 106816605 A CN106816605 A CN 106816605A
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titanium plate
palladium
plate load
solution
preparation
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CN106816605B (en
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张腾
张心愿
魏颖
李巍婷
温翠莲
唐电
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Fuzhou University
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Fuzhou 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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • 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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H01M8/1013—Other direct alcohol fuel cells [DAFC]
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of preparation method of the palladium nanocatalyst of titanium plate load; it is with titanium plate as carrier; with palladium salt as presoma; oleic acid or oleate is added to form jelly; then jelly is uniformly coated in titanium plate; in isothermal holding 0.5h ~ 2h under 180 ~ 350 DEG C, gas shield, the palladium nanocatalyst of titanium plate load is obtained.Compared with traditional thermolysis process, the inventive method can not only significantly reduce heat decomposition temperature, make the Pd particle size uniformities of acquisition, average grain diameter is less than 10nm, and Pd particles can be made dispersed in titanium plate, so as to have catalysis activity higher to Aalcohols fuels such as ethanol and methyl alcohol, and raw material of the present invention is easy to get, operating method is easy, can reach the requirement of industrialization production.

Description

A kind of preparation method of the palladium nanocatalyst of titanium plate load
Technical field
The invention belongs to be catalyzed and energy industry material preparing technical field, and in particular to a kind of palladium nanometer of titanium plate load The preparation method of catalyst.
Background technology
With the aggravation of global energy crisis, the new energy causes the extensive concern of society.Direct alcohol fuel cell （DMFCs/DEFCs）It is a kind of electrochemical reaction appts that the chemical energy of fuel can be directly changed into electric energy, with work Temperature is low, energy density is high and advantages of environment protection.In terms of fuel cell, the catalytic efficiency of platinum catalyst is higher, but It is the scarcity of resources of noble metal platinum, causes its expensive, increased the cost of fuel cell.Therefore, palladium is considered as low platinum Or even the critical material without platinum catalyst.
However, traditional carbon material carrier is poor because of its corrosion resistance, cause during as catalyst carrier thereon The catalyst activity material of load is easy to fall off, influences its catalytic performance.In recent years, numerous studies personnel to non-carbon support material such as Oxide, high stability metal and rare earth material etc. are studied.Wherein, titanium has electric conductivity higher and corrosion-resistant, can Hope the novel carriers material as fuel cell.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the palladium nanocatalyst of titanium plate load, it can make obtained Pd grain diameters are uniform, and it is dispersed on carrier, so as to significantly improve the catalysis activity of gained catalyst.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of the palladium nanocatalyst of titanium plate load, it is that palladium salt is dissolved in into organic solvent under ultrasonic agitation In, obtain solution A；By oleic acid or oleate ultrasonic dissolution in organic solvent, solution B is obtained；Solution A is added dropwise over solution In B, stirring mixing 1h ~ 4h obtains colloidal solution C；Colloidal solution C is evenly applied in the titanium plate after etching, is dried to obtain Material D；Material D is transferred in tube furnace, isothermal holding 0.5h ~ 2h, obtains after 180 ~ 350 DEG C are warming up under gas shield The palladium nanocatalyst of titanium plate load；Its concrete operation step is as follows：
（1）Titanium plate is etched 1-2 hours in the oxalic acid solution of the 20wt% ~ 60wt% of boiling, after washing is dried, after being etched Titanium plate；
（2）By mass volume ratio 1:10 by palladium salt ultrasonic mixing in organic solvent solution, obtain solution A；By mass volume ratio 1:10 by oleic acid or oleate ultrasonic dissolution in organic solvent, obtain solution B；
（3）Agitating solution B, and solution A is added dropwise in the middle of solution B, then stirring mixing 1h ~ 4h, obtains colloidal solution C；
（4）Colloidal solution C is evenly coated in the titanium plate after etching, is put into drying box, 2h is dried at 60 DEG C, obtain material D；
（5）Material D is put into corundum ceramic boat, is transferred in tube furnace, be passed through protective gas, then at room temperature with 2 DEG C/ The speed of min is warmed up to 180 DEG C ~ 350 DEG C, and isothermal holding 0.5h ~ 2h obtains the palladium nanocatalyst of titanium plate load after cooling.
The palladium salt be palladium chloride, tetrachloro-palladium acid sodium and palladium in one or several.
The oleate be potassium oleate, calcium oleate and enuatrol in one or several.
The organic solvent is absolute ethyl alcohol or ethylene glycol.
Protective gas used be argon gas, hydrogen, nitrogen in one or several.
Palladium salt used is 1 with the mol ratio of oleate:1~1:10.
Coated weights of the colloidal solution C in titanium plate is 1 ~ 10g/m2。
The average grain diameter of palladium particle is less than 10nm in gained catalyst.
Remarkable advantage of the invention is：
Compared with traditional thermolysis process, the inventive method can not only significantly reduce heat decomposition temperature, make the Pd particle chis of acquisition Very little uniform, average grain diameter is less than 10nm, and Pd particles can be made dispersed in titanium plate, and the nanocatalyst pair of high degree of dispersion The Aalcohols fuel such as ethanol and methyl alcohol has catalysis activity higher.Meanwhile, the high corrosion-resistant of titanium-based material can also strengthen catalyst Stability under the runtime environment.
Raw material of the present invention is easy to get, and operating method is easy, can reach the requirement of industrialization production.
Brief description of the drawings
Fig. 1 is the SEM figures of the palladium nanocatalyst of titanium plate load prepared by the present invention.
Specific embodiment
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to of the present invention Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
（1）Titanium plate is etched 1 hour in the oxalic acid solution of the 20wt% of boiling, after being dried with ethanol wash, after being etched Titanium plate；
（2）By palladium ultrasonic dissolution in absolute ethyl alcohol, the solution A that concentration is 1g/10mL is obtained；Oleic acid ultrasonic dissolution is existed In absolute ethyl alcohol, the solution B that concentration is 1g/10mL is obtained；
（3）Agitating solution B, and solution A is added dropwise in the middle of solution B, then stirring mixing 1h, obtains colloidal solution C；Its Middle oleic acid is 1 with the mol ratio of palladium:1；
（4）By coated weight 1g/m2Colloidal solution C is evenly coated in the titanium plate after etching, is put into drying box, dried at 60 DEG C 2h, obtains material D；
（5）Material D is put into corundum ceramic boat, is transferred in tube furnace, be passed through argon gas and protected, then at room temperature with The speed of 2 DEG C/min is warmed up to 180 DEG C, and isothermal holding 0.5h obtains the palladium nanocatalyst of titanium plate load after cooling.Gained is urged Agent is 12 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）Attenuation rate be only 20%.
Fig. 1 is the SEM figures of gained catalyst.As seen from the figure, Pd nano particles are uniformly dispersed, and its average grain diameter is left in 10nm It is right.
Embodiment 2
（1）Titanium plate is etched 2 hours in the mass fraction of boiling is for the oxalic acid solution of 60wt%, after being dried with ethanol wash, is obtained Titanium plate after to etching；
（2）By palladium chloride ultrasonic dissolution in absolute ethyl alcohol, the solution A that concentration is 1g/10mL is obtained；Potassium oleate ultrasound is molten Solution obtains the solution B that concentration is 1g/10mL in ethylene glycol；
（3）Agitating solution B, and solution A is added dropwise in the middle of solution B, then stirring mixing 4h, obtains colloidal solution C；Its Middle potassium oleate is 10 with the mol ratio of palladium chloride:1；
（4）By coated weight 10g/m2Colloidal solution C is evenly coated in the titanium plate after etching, is put into drying box, done at 60 DEG C Dry 2h, obtains material D；
（5）Material D is put into corundum ceramic boat, is transferred in tube furnace, be passed through nitrogen and protected, then at room temperature with The speed of 2 DEG C/min is warmed up to 350 DEG C, and isothermal holding 2h obtains the palladium nanocatalyst of titanium plate load after cooling.Gained is catalyzed Agent is 8 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）Attenuation rate be only 12%.
Embodiment 3
（1）Titanium plate is etched 1 hour in the mass fraction of boiling is for the oxalic acid solution of 40wt%, after washing is dried, is etched Titanium plate afterwards；
（2）By tetrachloro-palladium acid sodium ultrasonic dissolution in ethylene glycol, the solution A that concentration is 1g/10mL is obtained；Enuatrol ultrasound is molten Solution obtains the solution B that concentration is 1g/10mL in ethylene glycol；
（3）Agitating solution B, and solution A is added dropwise in the middle of solution B, then stirring mixing 2h, obtains colloidal solution C；Its Middle enuatrol is 5 with the mol ratio of tetrachloro-palladium acid sodium:1；
（4）By coated weight 5g/m2Colloidal solution C is evenly coated in the titanium plate after etching, is put into drying box, dried at 60 DEG C 2h, obtains material D；
（5）Material D is put into corundum ceramic boat, is transferred in tube furnace, be passed through nitrogen and protected, then at room temperature with The speed of 2 DEG C/min is warmed up to 200 DEG C, and isothermal holding 1h obtains the palladium nanocatalyst of titanium plate load after cooling.Gained is catalyzed Agent is 10 mAcm to the specific activity of alcohol catalysis-2, continuous operation 12 hours（65 DEG C, 0.65V）Attenuation rate be only 16%.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modification, should all belong to covering scope of the invention.

Claims (8)

1. the preparation method of the palladium nanocatalyst of a kind of titanium plate load, it is characterised in that：Palladium salt is dissolved under ultrasonic agitation In organic solvent, solution A is obtained；By oleic acid or oleate ultrasonic dissolution in organic solvent, solution B is obtained；By solution A by It is added dropwise in solution B, stirring mixing 1h ~ 4h obtains colloidal solution C；Colloidal solution C is evenly applied to the titanium plate after etching On, it is dried to obtain material D；Material D is transferred in tube furnace, isothermal holding after 180 ~ 350 DEG C are warming up under gas shield 0.5h ~ 2h, obtains the palladium nanocatalyst of titanium plate load.
2. according to claim 1 titanium plate load palladium nanocatalyst preparation method, it is characterised in that：The palladium salt is One or several in palladium chloride, tetrachloro-palladium acid sodium and palladium.
3. according to claim 1 titanium plate load palladium nanocatalyst preparation method, it is characterised in that：The oleate For one or several in potassium oleate, calcium oleate and enuatrol.
4. according to claim 1 titanium plate load palladium nanocatalyst preparation method, it is characterised in that：It is described organic molten Agent is absolute ethyl alcohol or ethylene glycol.
5. according to claim 1 titanium plate load palladium nanocatalyst preparation method, it is characterised in that：Protection gas used Body be argon gas, hydrogen, nitrogen in one or several.
6. according to claim 1 titanium plate load palladium nanocatalyst preparation method, it is characterised in that：Palladium salt used with The mol ratio of oleic acid or oleate is 1:1~1:10.
7. according to claim 1 titanium plate load palladium nanocatalyst preparation method, it is characterised in that：Colloidal solution C Coated weight in titanium plate is 1 ~ 10g/m2。
8. according to claim 1 titanium plate load palladium nanocatalyst preparation method, it is characterised in that：Gained catalyst The average grain diameter of middle palladium particle is less than 10nm.
CN201710032038.0A 2017-01-17 2017-01-17 A kind of preparation method of the palladium nanocatalyst of titanium plate load Expired - Fee Related CN106816605B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395322A (en) * 1981-11-18 1983-07-26 General Electric Company Catalytic electrode
CN102698745A (en) * 2012-06-06 2012-10-03 厦门大学 Titanium dioxide nanotube carried palladium nano catalyst and preparation method of same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395322A (en) * 1981-11-18 1983-07-26 General Electric Company Catalytic electrode
CN102698745A (en) * 2012-06-06 2012-10-03 厦门大学 Titanium dioxide nanotube carried palladium nano catalyst and preparation method of same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
黎华玲: ""具有特殊形貌的钯纳米花的合成及基于钯纳米花特殊形貌核壳结构低铂催化剂的制备"", 《中国优秀硕士学位论文全文数据库》 *

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