CN106784879B - A kind of preparation method of the palladium ruthenium catalyst of titanium plate load - Google Patents
A kind of preparation method of the palladium ruthenium catalyst of titanium plate load Download PDFInfo
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- CN106784879B CN106784879B CN201710032037.6A CN201710032037A CN106784879B CN 106784879 B CN106784879 B CN 106784879B CN 201710032037 A CN201710032037 A CN 201710032037A CN 106784879 B CN106784879 B CN 106784879B
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- palladium
- titanium plate
- ruthenium
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- plate load
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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
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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
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- 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)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of preparation methods of the palladium ruthenium catalyst of titanium plate load; it is using titanium plate as carrier; using palladium salt and ruthenium salt as presoma; oleic acid is added or oleate forms jelly; then jelly is uniformly coated in titanium plate; isothermal holding 0.5h ~ 2h under 160 ~ 320 DEG C, protective gas obtains the palladium ruthenium nanocatalyst of titanium plate load.Compared with traditional thermolysis process, the method of the present invention can significantly reduce thermal decomposition temperature, make the palladium ruthenium particle size uniformity obtained, average grain diameter is in 10nm or less, and palladium ruthenium can be made evenly dispersed in titanium plate, to realize the higher catalytic activity to Aalcohols fuels such as ethyl alcohol and methanol.Raw material of the present invention is easy to get, and operating method is easy, can reach the requirement of industrialization production.
Description
Technical field
The invention belongs to be catalyzed and energy industry material preparation field, and in particular to a kind of palladium ruthenium nanometer of titanium plate load is urged
The preparation method of agent.
Background technique
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, there is 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, leads to that it is expensive, increases 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 causes during as catalyst carrier thereon because its corrosion resistance is poor
The catalyst activity substance 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 electric conductivity with higher and corrosion-resistant, can
Hope the novel carriers material for becoming fuel cell.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of the palladium ruthenium nanocatalyst of titanium plate load, can make to be made
Palladium ruthenium grain diameter it is uniform, and be dispersed in it on carrier, to significantly improve the catalytic activity of gained catalyst.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of the palladium ruthenium catalyst of titanium plate load, is to be dissolved in palladium salt under ultrasonic agitation with ruthenium salt
In organic solvent, solution A is obtained；By oleic acid or oleate ultrasonic dissolution in organic solvent, solution B is obtained；Dropwise by solution A
It is added in solution B, is stirred 1h ~ 4h, obtains colloidal solution C；In titanium plate after colloidal solution C to be evenly applied to etching,
It is dried to obtain substance D；Substance D is transferred in tube furnace, isothermal holding 0.5h after 160 ~ 320 DEG C are warming up under gas shield
~ 2h obtains the palladium ruthenium catalyst of titanium plate load；Itself specific steps are as follows:
(1) titanium plate is etched 1-2 hours in the oxalic acid solution of 20wt% ~ 60wt% of boiling, after washing is dry, is carved
Titanium plate after erosion；
(2) by mass volume ratio 1:1:10 by palladium salt, ruthenium salt ultrasonic mixing in organic solution, obtain solution A；By quality
Oleic acid or oleate ultrasonic dissolution in organic solvent, are obtained solution B by volume ratio 1:10；
(3) agitating solution B, and solution A is added dropwise in solution B, it is then stirred 1h ~ 4h, obtains glue
Solution C；
(4) it in the titanium plate after colloidal solution C to be evenly coated in etching, is put into drying box, dry 2h, obtains object at 60 DEG C
Matter D；
(5) substance D is put into corundum ceramic boat, is transferred in tube furnace, be passed through protective gas, then with 2 DEG C/min
Rate be warming up to 160 DEG C ~ 320 DEG C, isothermal holding 0.5h ~ 2h, the palladium ruthenium catalyst of titanium plate load is obtained after cooling.
The palladium salt is one of palladium chloride, sodium tetrachloropallate and palladium acetate or several.
The ruthenium salt is one of ruthenium trichloride, acetic acid ruthenium and iodate ruthenium or several.
The oleate is one of potassium oleate, calcium oleate and enuatrol or several.
The organic solvent is dehydrated alcohol or ethylene glycol.
Protective gas used is the one or several kinds of argon gas, hydrogen, nitrogen.
The molar ratio of palladium salt, ruthenium salt and oleic acid or oleate used is 1:1:1 ~ 1:1:10.
Coated weight of the colloidal solution C in titanium plate is 1 ~ 10g/m2。
Palladium in gained catalyst, ruthenium particle average grain diameter be respectively less than 10nm.
Remarkable advantage of the invention is:
Compared with traditional thermolysis process, the method for the present invention can not only significantly reduce thermal decomposition temperature, make the palladium ruthenium obtained
Particle size uniformity, average grain diameter is less than 10nm, and palladium ruthenium particle can be made evenly dispersed in titanium plate, to give full play to the conjunction of palladium ruthenium
The Lattice Contraction effect and surface coordination effect of gold, thus to the Aalcohols fuels such as ethyl alcohol and methanol catalytic activity with higher.
Meanwhile the high corrosion-resistant of titanium-based material can also enhance the stability of catalyst 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.
Detailed description of the invention
Fig. 1 is the SEM figure of the palladium ruthenium catalyst of titanium plate load prepared by the present invention.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution 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 60wt% of boiling, after ethanol wash drying, is etched
Titanium plate afterwards；
(2) by palladium acetate and iodate ruthenium ultrasonic mixing in dehydrated alcohol, obtaining palladium acetate and iodate ruthenium concentration is 1g/
The solution A of 10mL；By oleic acid ultrasonic dissolution in dehydrated alcohol, the solution B that concentration is 1g/10mL is obtained；
(3) agitating solution B, and solution A is added dropwise in solution B, it is then stirred 1h, obtains colloidal solution
C；Wherein oleic acid and palladium acetate, the molar ratio of iodate ruthenium are 1:1:1；
(4) coated weight 1g/m is pressed2In titanium plate after colloidal solution C to be evenly coated in etching, it is put into drying box, at 60 DEG C
Dry 2h, obtains substance D；
(5) substance D is put into corundum ceramic boat, is transferred in tube furnace, be passed through argon gas and protected, then with 2 DEG C/
The rate of min is warming up to 160 DEG C, isothermal holding 2h, and the palladium ruthenium catalyst of titanium plate load is obtained after cooling.Gained catalyst is to second
The specific activity of alcohol catalysis is 25 mAcm-2, the attenuation rate of continuous operation 12 hours (65 DEG C of 10.65V) is only 10%.
Fig. 1 is the SEM figure of gained catalyst.As seen from the figure, palladium ruthenium nano-particle is uniformly dispersed, and average grain diameter is in 10nm
Left and right.
Embodiment 2
(1) titanium plate is etched 1 hour in the oxalic acid solution of the 40wt% of boiling, after ethanol wash drying, is etched
Titanium plate afterwards；
(2) it by palladium chloride and ruthenium trichloride ultrasonic mixing in dehydrated alcohol, obtains palladium chloride and ruthenium trichloride is dense
Degree is the solution A of 1g/10mL；By potassium oleate ultrasonic dissolution in ethylene glycol, the solution B that concentration is 1g/10mL is obtained；
(3) agitating solution B, and solution A is added dropwise in solution B, it is then stirred 2h, obtains colloidal solution
C；Wherein the molar ratio of potassium oleate and palladium chloride, ruthenium trichloride is 10:1:1；
(4) coated weight 10g/m is pressed2In titanium plate after colloidal solution C to be evenly coated in etching, it is put into drying box, 60 DEG C
Lower dry 2h, obtains substance D；
(5) substance D is put into corundum ceramic boat, is transferred in tube furnace, be passed through nitrogen and protected, then with 2 DEG C/
The rate of min is warming up to 320 DEG C, isothermal holding 0.5h, and the palladium ruthenium catalyst of titanium plate load is obtained after cooling.Gained catalyst pair
The specific activity of alcohol catalysis is 20 mAcm-2, the attenuation rate of continuous operation 12 hours (65 DEG C, 0.65V) is only 8%.
Embodiment 3
(1) titanium plate is etched 2 hours in the oxalic acid solution of the 20wt% of boiling, after ethanol wash drying, is etched
Titanium plate afterwards；
(2) by palladium acetate and acetic acid ruthenium ultrasonic mixing in ethylene glycol, obtaining palladium acetate and acetic acid ruthenium concentration is 1g/
The solution A of 10mL；By enuatrol ultrasonic dissolution in ethylene glycol, the solution B that concentration is 1g/10mL is obtained；
(3) agitating solution B, and solution A is added dropwise in solution B, it is then stirred 4h, obtains colloidal solution
C；Wherein enuatrol and palladium acetate, the molar ratio of acetic acid ruthenium are 5:1:1；
(4) coated weight 5g/m is pressed2In titanium plate after colloidal solution C to be evenly coated in etching, it is put into drying box, at 60 DEG C
Dry 2h, obtains substance D；
(5) substance D is put into corundum ceramic boat, is transferred in tube furnace, argon gas progress is passed through, then with 2 DEG C/min
Rate be warming up to 180 DEG C, isothermal holding 1h, the palladium ruthenium catalyst of titanium plate load is obtained after cooling.Gained catalyst is to ethyl alcohol
The specific activity of catalysis is 14 mAcm-2, the attenuation rate of continuous operation 12 hours (65 DEG C, 0.65V) is only 5%.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (7)
1. a kind of preparation method of the palladium ruthenium catalyst of titanium plate load, it is characterised in that: by palladium salt and ruthenium salt under ultrasonic agitation
It is dissolved in organic solvent, obtains solution A；By oleic acid or oleate ultrasonic dissolution in organic solvent, solution B is obtained；It will be molten
Liquid A is added dropwise in solution B, is stirred 1h ~ 4h, obtains colloidal solution C；After colloidal solution C is evenly applied to etching
In titanium plate, it is dried to obtain substance D；Substance D is transferred in tube furnace, is kept the temperature after 160 ~ 320 DEG C are warming up under gas shield
0.5h ~ 2h is handled, the palladium ruthenium catalyst of titanium plate load is obtained；
The molar ratio of palladium salt, ruthenium salt and oleic acid or oleate used is 1:1:1 ~ 1:1:10；
Coated weight of the colloidal solution C in titanium plate is 1 ~ 10g/m2。
2. the preparation method of the palladium ruthenium catalyst of titanium plate load according to claim 1, it is characterised in that: the palladium salt is two
One of palladium chloride, sodium tetrachloropallate and palladium acetate are several.
3. the preparation method of the palladium ruthenium catalyst of titanium plate load according to claim 1, it is characterised in that: the ruthenium salt is three
One of ruthenic chloride, acetic acid ruthenium and iodate ruthenium are several.
4. the preparation method of the palladium ruthenium catalyst of titanium plate load according to claim 1, it is characterised in that: the oleate is
One of potassium oleate, calcium oleate and enuatrol are several.
5. the preparation method of the palladium ruthenium catalyst of titanium plate load according to claim 1, it is characterised in that: the organic solvent
For dehydrated alcohol or ethylene glycol.
6. the preparation method of the palladium ruthenium catalyst of titanium plate load according to claim 1, it is characterised in that: protective gas used
For the one or several kinds of argon gas, hydrogen, nitrogen.
7. the preparation method of the palladium ruthenium catalyst of titanium plate load according to claim 1, it is characterised in that: in gained catalyst
Palladium, ruthenium particle average grain diameter be respectively less than 10nm.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102698745A (en) * | 2012-06-06 | 2012-10-03 | 厦门大学 | Titanium dioxide nanotube carried palladium nano catalyst and preparation method of same |
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| JP2001224963A (en) * | 2000-02-16 | 2001-08-21 | Nissan Motor Co Ltd | Catalytic composition, its manufacturing method and its using method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| "直接甲酸燃料电池阳极Pd基催化剂的性能研究";孙丹丹;《中国优秀硕士学位论文全文数据库》;20160216;第C042-1628页 * |
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