CN108044128A - A kind of ultra-fine branch palladium-platinum duplex metal nano granule and its preparation method and application - Google Patents
A kind of ultra-fine branch palladium-platinum duplex metal nano granule and its preparation method and application Download PDFInfo
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- CN108044128A CN108044128A CN201711373197.3A CN201711373197A CN108044128A CN 108044128 A CN108044128 A CN 108044128A CN 201711373197 A CN201711373197 A CN 201711373197A CN 108044128 A CN108044128 A CN 108044128A
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- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000008187 granular material Substances 0.000 title claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 46
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 27
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 20
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 210000001787 dendrite Anatomy 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 89
- 239000000243 solution Substances 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 9
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- -1 H first2PdCl4 Chemical compound 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 239000003643 water by type Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 3
- 229930003268 Vitamin C Natural products 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- 235000019154 vitamin C Nutrition 0.000 description 3
- 239000011718 vitamin C Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/33—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
Abstract
The invention discloses a kind of ultra-fine branch palladium platinum duplex metal nano granules and its preparation method and application.Pass through CTAC, H first2PdCl4, NaOH and NaBH4Prepare seed solution；Then CTAC, H are passed through2PdCl4, NaOH, seed solution and ascorbic acid prepare growth solution；Finally by growth solution, H2PtCl6, ascorbic acid ultra-fine branch palladium platinum duplex metal nano granule is prepared.Its pattern be spherical palladium nanoparticle marginal growth have 4~5nm nano platinum particle dendrite, a diameter of 0.5~0.8nm of dendrite.This method is prepared simply, and reaction condition is mild, and the appearance and size ratio of the ultra-fine branch palladium platinum duplex metal nano granule of gained can be changed by adjusting the size of Pd balls or the amount of chloroplatinic acid of addition, has excellent performance compared with business platinum carbon to methanol oxidation.
Description
Technical field
The invention belongs to field of inorganic nano material and electrochemical applications research field, and in particular to a kind of ultra-fine branch
Palladium-platinum duplex metal nano granule and its preparation method and application.
Background technology
The artificial energy demand and continuing to increase for CO2 emissions of accumulation have triggered non-fossil fuel resource
Active demand.Including solar energy, wind energy, geothermal energy, the alternative substitute including wave energy source and fuel cell actively chases after
It asks.Fuel cell is considered as leading replacement green energy resource technology, is had wide range of applications including transport, portable power and solid
Fixed power generation.
At present, the elctro-catalyst based on Pt is occupied an leading position, but expensive, and supply is limited.As an alternative, use
The design Pt and Pd based nano-materials of high activity and the catalyst stablized have become an interesting field.
But synthesis electrochemical catalyst has following problem at present：First, required synthetic material is expensive；Second, it closes
It is harsher into condition；3rd, synthetic yield is not high and purification step is comparatively laborious.Therefore, urged to greatly improve electrochemistry
The application of agent must just develop a kind of cheap and simple electrochemical catalyst synthetic method of synthesis.
The content of the invention
For above deficiency, the present invention provides a kind of ultra-fine branch palladium-platinum duplex metal nano granules and preparation method thereof
And application.This method is easy to operate, required synthesis temperature is relatively low, at low cost, and different rulers can be obtained by changing synthesis condition
Very little duplex metal nano granule.
The technical solution that the present invention takes is：
A kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, the preparation method comprise the following steps：
S1：Prepare seed solution：CTAC aqueous solutions, H are sequentially added into deionized water2PdCl4Aqueous solution, NaOH are water-soluble
Liquid and the NaBH newly configured4Aqueous solution after mixing, stands 10~15s, you can it is molten to obtain seed in 30~35 DEG C of constant temperature
Liquid；
S2：Prepare growth solution：CTAC aqueous solutions, H are sequentially added into deionized water2PdCl4Aqueous solution, NaOH are water-soluble
Liquid and seed solution add in aqueous ascorbic acid under stirring condition, and after stirring evenly, 7~10 are stood in 30~35 DEG C of constant temperature
Hour, you can obtain growth solution；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：It is added in the growth solution obtained to step S2
H2PtCl6Aqueous solution adds in aqueous ascorbic acid under stirring condition, and after stirring evenly, 5~10 are stood in 30~35 DEG C of constant temperature
Hour, it can obtain the ultra-fine branch palladium-platinum duplex metal nano granule after centrifugation.
In the step S1, CTAC aqueous solutions, H2PdCl4Aqueous solution, NaOH aqueous solutions and NaBH4Aqueous solution it is mole dense
The ratio between degree is (0.8~1.2)：(0.005~0.015)：(0.01~0.15)：(0.005~0.015).
In the step S1, deionized water, CTAC aqueous solutions, H2PdCl4Aqueous solution, NaOH aqueous solutions and NaBH4Aqueous solution
The ratio between volume be (5~10)：(1.25~1.5)：(0.2~0.3)：(0.2~0.4)：(0.5~0.8).
In the step S2, CTAC aqueous solutions, H2PdCl4Mole of aqueous solution, NaOH aqueous solutions and aqueous ascorbic acid
The ratio between concentration is (0.8~1.2)：(0.005~0.015)：(0.005~0.015)：(0.08~0.15).
In the step S2, deionized water, CTAC aqueous solutions, H2PdCl4Aqueous solution, NaOH aqueous solutions, ascorbic acid are water-soluble
The ratio between volume of liquid and seed solution is (35~55)：(0.2~0.4)：(1~2)：(0.2~0.4)：(0.3~0.6)：
(0.05~0.2).
In the step S3, H2PtCl6The ratio between molar concentration of aqueous solution and aqueous ascorbic acid for (0.005~
0.015)：(0.08~0.15).
In the step S3, growth solution, H2PtCl6The ratio between volume of aqueous solution and aqueous ascorbic acid for (20~
25)：(0.02~0.8)：(0.4~0.6).
Further, spherical palladium nanoparticle ion is can obtain after the growth solution that the step S2 is obtained is centrifuged,
A diameter of 20~45nm.
The present invention also provides the ultra-fine branch palladium-platinum duplex metal nano granules being prepared according to above-mentioned preparation method.
The pattern of the ultra-fine branch palladium-platinum duplex metal nano granule is to have 4~5nm's in the marginal growth of spherical palladium nanoparticle
The dendrite of nano platinum particle, a diameter of 0.5~0.8nm of dendrite.
The present invention also provides the ultra-fine branch palladium-platinum duplex metal nano granule as catalysis methanol oxidation reaction
Application in terms of catalyst.It is substantially better than business palladium-carbon catalyst to the catalytic oxidation performance of methanol.
Compared with prior art, the present invention has the following advantages：
1st, this method is prepared simple, and reaction condition is mild, and required equipment is simple；
2nd, synthesized ultra-fine branch palladium-platinum duplex metal nano granule cost of material is low, and size is than more uniform；
3rd, the appearance of the ultra-fine branch palladium-platinum duplex metal nano granule of gained and size ratio can be by adjusting the Pd balls added in
Size or the amount of chloroplatinic acid and change, to methanol oxidation compared with business platinum carbon have excellent performance.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (left side) and transmission electron microscope picture of the obtained palladium nano-particles of step S2 in embodiment 1
(right side)；
Fig. 2 is the scanning electron microscope (SEM) photograph of ultra-fine branch palladium-platinum duplex metal nano granule in embodiment 1；
Fig. 3 is the transmission electron microscope picture of ultra-fine branch palladium-platinum duplex metal nano granule in embodiment 1；
Fig. 4 is ultra-fine branch palladium-platinum duplex metal nano granule obtained by embodiment 1,6~9 and business platinum carbon in 0.5M sulphur
Cyclic voltammogram in acid solution；
Fig. 5 be the gained of embodiment 1,6~9 ultra-fine branch palladium-platinum duplex metal nano granule and business platinum carbon in methanol and
Cyclic voltammogram in the mixed solution of sulfuric acid；
Fig. 6 be the gained of embodiment 1,6~9 ultra-fine branch palladium-platinum duplex metal nano granule and business platinum carbon in methanol and
Mass activity and area activated block diagram in the mixed solution of sulfuric acid；
Fig. 7 be the gained of embodiment 1,6~9 ultra-fine branch palladium-platinum duplex metal nano granule and business platinum carbon in methanol and
Chronoa mperometric plot in the mixed solution of sulfuric acid.
Specific embodiment
With reference to embodiment and Figure of description, the present invention is described in detail.
A kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, the preparation method comprise the following steps：
S1：Prepare seed solution：Sequentially added into 5~10mL deionized waters 1.25~1.5mL concentration for 0.8~
The CTAC aqueous solutions of 1.2mol/L, the H that 0.2~0.3mL concentration is 0.005~0.015mol/L2PdCl4Aqueous solution, 0.2~
The concentration that the NaOH aqueous solutions and 0.5~0.8mL that 0.4mL concentration is 0.01~0.15mol/L newly configure is 0.005~
The NaBH of 0.015mol/L4Aqueous solution after mixing, stands 10~15s, you can it is molten to obtain seed in 30~35 DEG C of constant temperature
Liquid；
S2：Prepare growth solution：Sequentially added into 35~55 deionized waters 0.2~0.4mL concentration for 0.8~
The CTAC aqueous solutions of 1.2mol/L, the H that 1~2mL concentration is 0.005~0.015mol/L2PdCl4Aqueous solution, 0.2~0.4mL are dense
It spends for the NaOH aqueous solutions of 0.005~0.015mol/L and 0.04~0.2mL seed solutions, add in 0.3 under stirring condition~
0.6mL concentration is the aqueous ascorbic acid of 0.08~0.15mol/L, and after stirring evenly, 7~10 are stood in 30~35 DEG C of constant temperature
Hour, you can obtain growth solution；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：Add in the growth solution obtained to 20~25 step S2
Enter the H that 0.02~0.8mL concentration is 0.005~0.015mol/L2PtCl6It is dense to add in 0.4~0.6mL under stirring condition for aqueous solution
The aqueous ascorbic acid for 0.08~0.15mol/L is spent, after stirring evenly, when 30~35 DEG C of constant temperature standings 5~10 are small, from
The ultra-fine branch palladium-platinum duplex metal nano granule is can obtain after the heart.
Embodiment 1
A kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, the preparation method comprise the following steps：
S1：Prepare seed solution：The CTAC water that 1.25mL concentration is 1.0mol/L is sequentially added into 7.5mL deionized waters
Solution, the H that 0.25mL concentration is 0.01mol/L2PdCl4Aqueous solution, 0.3mL concentration be 0.01mol/L NaOH aqueous solutions and
The concentration that 0.6mL is newly configured is the NaBH of 0.01mol/L4Aqueous solution, after mixing, constant temperature stands 10s in 30 DEG C of baking ovens,
It can obtain seed solution；
S2：Prepare growth solution：The CTAC that 0.24mL concentration is 1.0mol/L is sequentially added into 38.8mL deionized waters
Aqueous solution, the H that 1.2mL concentration is 0.01mol/L2PdCl4Aqueous solution, 0.3mL concentration be 0.01mol/L NaOH aqueous solutions and
0.04mL seed solutions add in the aqueous ascorbic acid that 0.4mL concentration is 0.1mol/L under stirring condition, after stirring evenly,
When constant temperature standing 8 is small in 35 DEG C of baking ovens, you can obtain growth solution；After growth solution is centrifuged, by gained Pd nano particle
Solid disperses in aqueous solution and tests its SEM and TEM, and test result is as shown in Figure 1, the palladium obtained as can be seen from Figure 1 is received
Rice corpuscles is the spheric granules of a diameter of 20~45nm；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：It is added in the growth solution obtained to 20mL steps S2
0.15mL concentration is the H of 0.01mol/L2PtCl6Aqueous solution adds in the Vitamin C that 0.5mL concentration is 0.1mol/L under stirring condition
After stirring evenly, when constant temperature standing 6 is small in 35 DEG C of baking ovens, the ultra-fine branch palladium-platinum is can obtain after centrifugation for aqueous acid
Duplex metal nano granule.With inductively coupled plasma atomic emission spectrometry (ICP-AES) to ultra-fine branch palladium-platinum of gained
Duplex metal nano granule is tested, and the corresponding molar ratio of Pd, Pt is as shown in table 1 after the result of test and calculating.As a result
The molar ratio of display wherein Pd, Pt are Pd80-Pt20.And the progress of ultra-fine branch palladium-platinum duplex metal nano granule to gained
SEM and TEM tests, as shown in Figure 2,3, the pattern of palladium-platinum duplex metal nano granule is in ball to test result as can be seen from Figure 3
The marginal growth of the palladium nanoparticle of shape has the dendrite of the nano platinum particle of 4~5nm, a diameter of 0.5~0.8nm of dendrite.
Embodiment 2
A kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, the preparation method comprise the following steps：
S1：Prepare seed solution：It is water-soluble that the CTAC that 1.5mL concentration is 0.8mol/L is sequentially added into 5mL deionized waters
Liquid, the H that 0.2mL concentration is 0.005mol/L2PdCl4Aqueous solution, 0.2mL concentration be 0.01mol/L NaOH aqueous solutions and
The concentration that 0.5mL is newly configured is the NaBH of 0.005mol/L4Aqueous solution after mixing, 15s is stood in 30 DEG C of constant temperature, you can
Obtain seed solution；
S2：Prepare growth solution：It is water-soluble that the CTAC that 0.2mL concentration is 0.8mol/L is sequentially added into 35mL deionized waters
Liquid, the H that 1mL concentration is 0.005mol/L2PdCl4Aqueous solution, 0.2mL concentration be 0.005mol/L NaOH aqueous solutions and
0.04mL seed solutions add in the aqueous ascorbic acid that 0.3mL concentration is 0.08mol/L under stirring condition, after stirring evenly,
When 30 DEG C of constant temperature standings 10 are small, you can obtain growth solution；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：It is added in the growth solution obtained to 20mL steps S2
0.1mL concentration is the H of 0.005mol/L2PtCl6Aqueous solution, it is the anti-bad of 0.08mol/L that 0.4mL concentration is added under stirring condition
Hematic acid aqueous solution after stirring evenly, when 30 DEG C of constant temperature standings 8 are small, can obtain the double gold of the ultra-fine branch palladium-platinum after centrifugation
Metal nano-particle.
Embodiment 3
A kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, the preparation method comprise the following steps：
S1：Prepare seed solution：It is water-soluble that the CTAC that 1.5mL concentration is 1.0mol/L is sequentially added into 8mL deionized waters
Liquid, the H that 0.25mL concentration is 0.01mol/L2PdCl4Aqueous solution, 0.25mL concentration be 0.15mol/L NaOH aqueous solutions and
The concentration that 0.6mL is newly configured is the NaBH of 0.01mol/L4Aqueous solution after mixing, 10s is stood in 35 DEG C of constant temperature, you can
To seed solution；
S2：Prepare growth solution：It is water-soluble that the CTAC that 0.3mL concentration is 1.0mol/L is sequentially added into 40mL deionized waters
Liquid, the H that 1.5mL concentration is 0.01mol/L2PdCl4Aqueous solution, the NaOH aqueous solutions and 0.1mL that 0.3mL concentration is 0.01mol/L
Seed solution adds in the aqueous ascorbic acid that 0.4mL concentration is 0.12mol/L under stirring condition, after stirring evenly, in 35 DEG C
When constant temperature standing 7 is small, you can obtain growth solution；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：It is added in the growth solution obtained to 22mL steps S2
0.4mL concentration is the H of 0.01mol/L2PtCl6Aqueous solution adds in the Vitamin C that 0.5mL concentration is 0.10mol/L under stirring condition
After stirring evenly, when 30 DEG C of constant temperature standings 8 are small, the ultra-fine branch palladium-platinum bimetallic is can obtain after centrifugation for aqueous acid
Nano particle.
Embodiment 4
A kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, the preparation method comprise the following steps：
S1：Prepare seed solution：It is water-soluble that the CTAC that 1.5mL concentration is 1.2mol/L is sequentially added into 10mL deionized waters
Liquid, the H that 0.3mL concentration is 0.015mol/L2PdCl4Aqueous solution, 0.4mL concentration be 0.15mol/L NaOH aqueous solutions and
The concentration that 0.8mL is newly configured is the NaBH of 0.015mol/L4Aqueous solution after mixing, 10s is stood in 35 DEG C of constant temperature, you can
Obtain seed solution；
S2：Prepare growth solution：It is water-soluble that the CTAC that 0.4mL concentration is 1.2mol/L is sequentially added into 55mL deionized waters
Liquid, the H that 2mL concentration is 0.015mol/L2PdCl4Aqueous solution, the NaOH aqueous solutions and 0.2mL that 0.4mL concentration is 0.015mol/L
Seed solution adds in the aqueous ascorbic acid that 0.6mL concentration is 0.15mol/L under stirring condition, after stirring evenly, in 35 DEG C
When constant temperature standing 8 is small, you can obtain growth solution；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：It is added in the growth solution obtained to 25mL steps S2
0.5mL concentration is the H of 0.015mol/L2PtCl6Aqueous solution, it is the anti-bad of 0.15mol/L that 0.6mL concentration is added under stirring condition
Hematic acid aqueous solution after stirring evenly, when 35 DEG C of constant temperature standings 7 are small, can obtain the double gold of the ultra-fine branch palladium-platinum after centrifugation
Metal nano-particle.
Embodiment 5
A kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, the preparation method comprise the following steps：
S1：Prepare seed solution：It is water-soluble that the CTAC that 0.4mL concentration is 0.8mol/L is sequentially added into 7mL deionized waters
Liquid, the H that 0.3mL concentration is 0.01mol/L2PdCl4Aqueous solution, the NaOH aqueous solutions and 0.8mL that 0.3mL concentration is 0.15mol/L
The concentration newly configured is the NaBH of 0.015mol/L4Aqueous solution after mixing, stands 15s, you can planted in 30 DEG C of constant temperature
Sub- solution；
S2：Prepare growth solution：It is water-soluble that the CTAC that 1.4mL concentration is 1.0mol/L is sequentially added into 45mL deionized waters
Liquid, the H that 1.5mL concentration is 0.015mol/L2PdCl4Aqueous solution, 0.4mL concentration be 0.01mol/L NaOH aqueous solutions and
0.1mL seed solutions add in the aqueous ascorbic acid that 0.4mL concentration is 0.10mol/L under stirring condition, after stirring evenly,
When 30 DEG C of constant temperature standings 10 are small, you can obtain growth solution；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：It is added in the growth solution obtained to 22mL steps S2
0.4mL concentration is the H of 0.01mol/L2PtCl6Aqueous solution adds in the Vitamin C that 0.5mL concentration is 0.1mol/L under stirring condition
After stirring evenly, when 30 DEG C of constant temperature standings 6 are small, the ultra-fine branch palladium-platinum bimetallic is can obtain after centrifugation for aqueous acid
Nano particle.
Embodiment 6
Other steps and raw material dosage are with embodiment 1, simply H in step s32PtCl6The addition of aqueous solution is 37.5 μ
L.With ultra-fine branch palladium-platinum duplex metal nano granule of ICP-AES test gained, Pd, Pt molar ratio therein is Pd94-
Pt6。
Embodiment 7
Other steps and raw material dosage are with embodiment 1, simply H in step s32PtCl6The addition of aqueous solution is 75 μ L.
With ultra-fine branch palladium-platinum duplex metal nano granule of ICP-AES test gained, Pd, Pt molar ratio therein is Pd89-Pt11。
Embodiment 8
Other steps and raw material dosage are with embodiment 1, simply H in step s32PtCl6The addition of aqueous solution is 300 μ
L.With ultra-fine branch palladium-platinum duplex metal nano granule of ICP-AES test gained, Pd, Pt molar ratio therein is Pd67-
Pt33。
Embodiment 9
Other steps and raw material dosage are with embodiment 1, simply H in step s32PtCl6The addition of aqueous solution is 600 μ
L.With ultra-fine branch palladium-platinum duplex metal nano granule of ICP-AES test gained, Pd, Pt molar ratio therein is Pd50-
Pt50。
Table 1ICP-AES is to ultra-fine branch palladium-platinum duplex metal nano granule in embodiment 1, embodiment 6~9
Test result
Embodiment 10
Ultra-fine branch palladium-platinum duplex metal nano granule and business palladium carbon exist respectively made from measurement embodiment 1,6~10
Cyclic voltammetry curve in 0.5M sulfuric acid solutions (for reference area activity).And them are tested respectively in 1M methanol and 0.5M sulfuric acid
Mixed solution in cyclic voltammetry curve (for calculating mass activity, area activated) and chronoa mperometric plot.
The preparation of 0.5M sulfuric acid solutions：The 6.315mL concentrated sulfuric acids (concentration 98%) are added in into the deionized water of 244ml to shake up
Cooling；
The preparation of the mixed solution of 1M methanol and 0.5M sulfuric acid：It is dense that 6.315ml is sequentially added into the deionized water of 239ml
Sulfuric acid (concentration 98%) and 5.006mL methanol shake up cooling.
Test condition is：Electrochemical measurement uses Zennium, and ZAHNER electrochemical analysers carry out.All electrochemistry are real
It tests and is carried out under 35 DEG C of logical saturation nitrogen in solution.Using a diameter of 3mm glassy carbon electrodes as working electrode, Ag/AgCl is reference
Electrode, platinum electrode be auxiliary electrode, the three-electrode system of composition.
The preparation method of working electrode is, first with 1 and 0.05 micron of Al2O3Powder (Al2O3Mixed with DI water) by glass
Glass carbon electrode (3mm diameters, Pine Instrument) polishes 30 minutes, then with ultrasonic cleaning 3 times, one time 10 seconds；Separately
On the one hand, by the ultra-fine branch palladium of preparation-platinum duplex metal nano granule solution (20mL) centrifugation twice to remove excessive CTAC,
And redisperse is into deionized water (400 or 800 μ L)；Then it is concentrated on the GCE after 3 μ L are added drop-wise to polishing, then uses beaker
Nafion aqueous solutions (0.2wt%, 5 μ L) after natural drying, are poured into above-mentioned GCE electrodes by covering to control rate of drying
On surface, and dry in air for further use.
With above-mentioned three-electrode system test in 0.5M sulfuric acid solutions cyclic voltammetry curve (for reference area activity),
Cyclic voltammetry curve in the mixed solution of 1M methanol and 0.5M sulfuric acid (for calculating mass activity, area activated) and timing electricity
Stream, solution leads to nitrogen deoxygenation at least 20 minutes before test.
The ultra-fine branch palladium-sulfuric acid of platinum duplex metal nano granule and business platinum carbon in 0.5M is molten made from example 1,6~10
It is as shown in Figure 4 that liquid measures its corresponding active area.
Then the cyclic voltammogram of methanol catalytic oxidation is tested successively in the mixed solution of 0.5M sulfuric acid and 1M methanol again,
As shown in Figure 5.Methanol oxidation peak is higher, and the mass activity of catalyst is higher；Then in mixed solution under the voltage of 0.5V
The chrono-amperometric of middle test 3000s, as shown in Figure 7.Fig. 6 is the mass activity of all catalyst and area activated block diagram.
As it can be seen that activity (mass activity and area activated) base of ultra-fine branch palladium-platinum duplex metal nano granule catalyst from Fig. 5~6
This is higher than business palladium carbon, and wherein palladium platinum molar ratio reaches 80：Activity is optimal when 20.From figure 7, it is seen that ultra-fine branch
The 3000s mass electric currents of palladium-platinum duplex metal nano granule catalyst are substantially higher than business palladium carbon, wherein palladium, platinum molar ratio
Reach 80:Electric current is optimal when 20.To sum up, palladium platinum molar ratio reaches 80：20 ultra-fine branch palladium-platinum bimetal nano
Grain has the chemical property that more excellent methanol aoxidizes.
Above-mentioned reference embodiment is to a kind of ultra-fine branch palladium-platinum duplex metal nano granule and its preparation method and application progress
Detailed description, be illustrative rather than limited, can include several embodiments according to limited scope, thus
The change and modification under present general inventive concept are not departed from, should be belonged within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ultra-fine branch palladium-platinum duplex metal nano granule, which is characterized in that the preparation method include with
Lower step：
S1：Prepare seed solution：CTAC aqueous solutions, H are sequentially added into deionized water2PdCl4Aqueous solution, NaOH aqueous solutions and
The NaBH newly configured4Aqueous solution after mixing, stands 10~15s, you can obtain seed solution in 30~35 DEG C of constant temperature；
S2：Prepare growth solution：CTAC aqueous solutions, H are sequentially added into deionized water2PdCl4Aqueous solution, NaOH aqueous solutions and
Seed solution adds in aqueous ascorbic acid under stirring condition, after stirring evenly, in 30~35 DEG C of constant temperature stand 7~10 it is small when,
It can obtain growth solution；
S3：The preparation of ultra-fine branch palladium-platinum duplex metal nano granule：H is added in the growth solution obtained to step S22PtCl6Water
Solution adds in aqueous ascorbic acid under stirring condition, after stirring evenly, in 30~35 DEG C of constant temperature stand 5~10 it is small when, centrifugation
It can obtain the ultra-fine branch palladium-platinum duplex metal nano granule afterwards.
2. preparation method according to claim 1, which is characterized in that in the step S1, CTAC aqueous solutions, H2PdCl4Water
Solution, NaOH aqueous solutions and NaBH4The ratio between molar concentration of aqueous solution is (0.8~1.2)：(0.005~0.015)：(0.01~
0.15)：(0.005~0.015).
3. preparation method according to claim 1 or 2, which is characterized in that in the step S1, deionized water, CTAC water
Solution, H2PdCl4Aqueous solution, NaOH aqueous solutions and NaBH4The ratio between volume of aqueous solution is (5~10)：(1.25~1.5)：(0.2
~0.3)：(0.2~0.4)：(0.5~0.8).
4. preparation method according to claim 1, which is characterized in that in the step S2, CTAC aqueous solutions, H2PdCl4Water
The ratio between molar concentration of solution, NaOH aqueous solutions and aqueous ascorbic acid is (0.8~1.2)：(0.005~0.015)：
(0.005~0.015)：(0.08~0.15).
5. the preparation method according to claim 1 or 4, which is characterized in that in the step S2, deionized water, CTAC water
Solution, H2PdCl4Aqueous solution, NaOH aqueous solutions, the ratio between the volume of aqueous ascorbic acid and seed solution are (35~55)：
(0.2~0.4)：(1~2)：(0.2~0.4)：(0.3~0.6)：(0.04~0.2).
6. preparation method according to claim 1, which is characterized in that in the step S3, H2PtCl6Aqueous solution with it is anti-bad
The ratio between molar concentration of hematic acid aqueous solution is (0.005~0.015)：(0.08~0.15).
7. the preparation method according to claim 1 or 6, which is characterized in that in the step S3, growth solution, H2PtCl6
The ratio between volume of aqueous solution and aqueous ascorbic acid is (20~25)：(0.02~0.8)：(0.4~0.6).
8. preparation method according to claim 1, which is characterized in that after the growth solution centrifugation for obtaining the step S2
It can obtain spherical Pd nano particle, a diameter of 20~45nm.
9. ultra-fine branch palladium-platinum duplex metal nano granule that preparation method according to claim 1 is prepared, feature
Be, the pattern of the ultra-fine branch palladium-platinum duplex metal nano granule be spherical palladium nanoparticle marginal growth have 4~
The dendrite of the nano platinum particle of 5nm, a diameter of 0.5~0.8nm of dendrite.
10. ultra-fine branch palladium-platinum duplex metal nano granule according to claim 9 is urged as catalysis methanol oxidation reaction
Application in terms of agent.
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