CN109663598A - PtNiAu nano hollow sphere material and preparation method and application thereof - Google Patents
PtNiAu nano hollow sphere material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 142
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 150000002815 nickel Chemical class 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 25
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 25
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 23
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 19
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 12
- 229920000557 Nafion® Polymers 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 238000003756 stirring Methods 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002844 PtNi Inorganic materials 0.000 abstract 1
- 239000002077 nanosphere Substances 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 18
- 239000002086 nanomaterial Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000001788 irregular Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000010953 base metal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/33—
-
- B01J35/51—
-
- 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
- B22F1/0549—Hollow particles, including tubes and shells
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
- B22F1/0655—Hollow 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
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
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Abstract
The invention provides a PtNiAu nano hollow sphere material and a preparation method and application thereof, wherein a nickel salt solution and a citric acid solution are mixed according to a certain proportion; secondly, adding a sodium borohydride solution under the protection of nitrogen, and continuously magnetically stirring at room temperature to obtain a brown solution, namely a nickel nanoparticle template; dripping chloroplatinic acid solution with certain concentration to obtain black solution, namely the PtNi nano hollow sphere; and (3) continuing to magnetically stir at room temperature for a certain time, then dripping a certain amount of chloroauric acid solution, reacting for a period of time, and then carrying out centrifugal cleaning on the obtained black mixed solution to obtain the PtNiAu hollow nanospheres. The method has the advantages of simple and convenient operation, controllable appearance, lower energy consumption, safety and environmental protection.
Description
Technical field
The present invention relates to new energy field of functional materials, it is related to that a kind of method is easy to operate, and morphology controllable, energy consumption is lower,
The preparation method of the PtNiAu nano hollow sphere material of safety and environmental protection.
Background technique
Noble metal nano catalyst electric conductivity with higher, catalytic activity and stability, thus it is widely used as fuel
Cell catalyst.However, the problems such as due to energy resource crisis is increasingly severe, Precious Metals Resources are increasingly deficient, it is expensive in addition
Price so that research is that the hollow structure noble metal catalyst that prepare of template is warm as research in recent years using base metal
Point.Due to the limitation in diadactic structure regulation space, introduces Section 3 metal and then develop a kind of morphology controllable, there is hollow knot
Structure, bigger serface, high activity ternary metallic catalyst, be of great significance.Currently, advanced optimizing the catalytic of material
It can be one of the problem of hollow structure noble metal catalyst still faces.Based on prepare at present hollow structure frequently with sacrifice template
Method at room temperature, is prepared for PtNiAu nano hollow sphere material, and join by modulation process in conjunction with chemical reduction method
Number realizes the controllable preparation of product morphology.
Summary of the invention
The present invention overcomes deficiency in the prior art, provide a method easy to operate, morphology controllable, energy consumption compared with
It is low, safety and environmental protection, PtNiAu nano hollow sphere material.
The purpose of the present invention is achieved by following technical proposals.
PtNiAu nano hollow sphere material and preparation method thereof carries out as steps described below:
Step 1, under anaerobic, sodium borohydride solution is added to the mixed solution of nickel salt solution and citric acid solution
In, then platinum acid chloride solution is added into above-mentioned solution, at 20-25 DEG C of room temperature after magnetic agitation 1-2h, black mixed solution is obtained,
Wherein, nickel salt solution concentration is 0.1-0.3mol/L, and citric acid solution concentration is 0.3-0.5mmol/L, and sodium borohydride solution is dense
Degree is 0.02-0.04mol/L, and platinum acid chloride solution concentration is 8-12mmol/L, and nickel salt solution, citric acid solution, sodium borohydride are molten
The volume ratio of liquid and platinum acid chloride solution is (1-3): (400-600): (40-60): (20-30)；
Step 2, chlorauric acid solution is instilled into the black mixed solution that step 1 is prepared, after reacting 0-40min, from
After the heart, cleaning to get arrive PtNiAu nano hollow sphere material, wherein chlorauric acid solution concentration be 0.5-12mmol/L, additional amount
For 0.05-1.5mL.
In step 1, oxygen free condition is provided for reaction system using inert protective gas, such as nitrogen, helium or argon gas.
In step 1, nickel salt solution concentration is 0.2mol/L, and citric acid solution concentration is 0.4mmol/L, and sodium borohydride is molten
Liquid concentration is 0.03mol/L, and platinum acid chloride solution concentration is 10mmol/L；Nickel salt uses nickel sulfate.
In step 1, the volume ratio of nickel salt solution, citric acid solution, sodium borohydride solution and platinum acid chloride solution is 1:
500:50:25；Magnetic agitation 1.5h at 20-25 DEG C of room temperature.
In step 2, chlorauric acid solution is instilled into black mixed solution, reacts 0-30min.
In step 2, centrifugal rotational speed 16000-20000rpm, after centrifugation time is 8-12min, then it is clear with deionized water
It washes 3-5 times.
In step 2, chlorauric acid solution concentration is 1-10mmol/L, additional amount 0.1-1mL.
Application of the PtNiAu nano hollow sphere material in the oxidation of electro-catalysis methanol, the preparation method of working electrode: will
PdNiAu nano hollow sphere material is mixed with organic solvent, deionized water and binder, and slurry is obtained after ultrasonic disperse, by slurry
Uniformly drop invests on glass-carbon electrode, up to working electrode after drying.
Organic solvent uses isopropanol, and organic solvent and deionized water volume ratio are (1-3): 1, preferably 2:1, PtNiAu receive
The additional amount of rice hollow ball material is 8-12 parts by weight, and binder uses mass fraction for the Nafion solution of 0.1-0.3wt%.
The invention has the benefit that being prepared for the PtNiAu of high pt utilization by a kind of simple and easy process
Nano-hollow ball methanol oxidation catalyst, and by regulating and controlling the controllable of few realization of process parameters product morphology component
It is standby.
Detailed description of the invention
Fig. 1 is the PtNiAu nano-hollow ball X-ray diffractogram that the embodiment of the present invention 3 is prepared；
Fig. 2 is the transmission electron microscope picture for the PtNiAu nano-hollow ball that the embodiment of the present invention 3 is prepared；
Fig. 3 is the transmission electron microscope picture of the PtNiAu nano-hollow ball of 4 method of embodiment of the present invention preparation；
Fig. 4 is the transmission electron microscope picture of the PtNiAu nano-hollow ball of 5 method of embodiment of the present invention preparation.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention, and signified solution is water in text
Solution, in the case where not indicating especially.
Embodiment 1
1) 0.2mL 0.2mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 100mL 0.4mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.03mol/L takes 10mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 5mL 10mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1.5h；
4) chlorauric acid solution of 10mmol/L that 0.1mL is prepared in advance is instilled in above-mentioned dark solution, do not stir and
It is centrifuged under 18000rpm, is cleaned with deionized water, is repeated several times to get the incomplete PtNiAu nano-hollow ball material of growth is arrived
Material.
5) the 10ug PtNiAu nano material and isopropanol obtained step 4), deionized water (the two volume ratio is 2:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
The embodiment finally obtains the incomplete PtNiAu nano hollow sphere material of growth.
Embodiment 2
1) 0.2mL 0.2mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 100mL 0.4mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.03mol/L takes 10mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 5mL 10mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1.5h；
4) chlorauric acid solution for the 1mmol/L that 1mL is prepared in advance is instilled in above-mentioned dark solution, magnetic force stirs at room temperature
Mix 30min；
5) gained mixed solution is centrifuged at 18000rpm, is cleaned with deionized water, is repeated several times to get PtNiAu is arrived
Nano hollow sphere material.
6) the 10ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 2:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
The embodiment finally obtains the irregular PtNiAu nano material of pattern.
Embodiment 3
1) 0.2mL 0.2mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 100mL 0.4mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.03mol/L takes 10mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 5mL 10mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1.5h；
4) chlorauric acid solution for the 10mmol/L that 0.1mL is prepared in advance is instilled in above-mentioned dark solution, at room temperature magnetic
Power stirs 10min；
5) gained mixed solution is centrifuged at 18000rpm, is cleaned with deionized water, is repeated several times to get PtNiAu is arrived
Nano hollow sphere material；
6) the 10ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 2:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
As shown in Fig. 2, the embodiment finally obtains the PtNiAu nano material of regular appearance, and little particle outside hollow sphere
It grows more irregular.
Embodiment 4
1) 0.2mL 0.2mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 100mL 0.4mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.03mol/L takes 10mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 5mL 10mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1.5h；
4) chlorauric acid solution for the 1mmol/L that 1mL is prepared in advance is instilled in above-mentioned dark solution, magnetic force stirs at room temperature
Mix 10min；
5) gained mixed solution is centrifuged at 18000rpm, is cleaned with deionized water, is repeated several times to get PtNiAu is arrived
Nano hollow sphere material.
6) the 10ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 2:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
As shown in figure 3, the embodiment finally obtains the PtNiAu nano material of regular appearance, and the growth of hollow ball surface compared with
More little particles.
Embodiment 5
1) 0.2mL 0.2mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 100mL 0.4mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.03mol/L takes 10mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 5mL 10mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1.5h；
4) chlorauric acid solution for the 1mmol/L that 0.5mL is prepared in advance is instilled in above-mentioned dark solution, at room temperature magnetic force
Stir 10min；
5) gained mixed solution is centrifuged at 18000rpm, cleaned with deionized water, is repeated several times to get attached to surface
There is the PtNiAu nano hollow sphere material of more nano particle.
6) the 10ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 2:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
Being characterized respectively to its object phase and pattern using X-ray diffractometer (XRD) and transmission electron microscope (TEM) can
Know, this method has successfully prepared the PtNiAu nano-hollow ball of morphological rules.Fig. 1 is the PtNiAu of 3 method of embodiment preparation
The X-ray diffractogram of nano-hollow ball.Fig. 2 is the transmission electron microscope picture for the PtNiAu nano-hollow ball that embodiment 3 is prepared, by
PtNiAu nano-hollow ball is formd known to figure, little particle growth is more irregular outside hollow sphere.From the figure 3, it may be seen that embodiment 4
The PtNiAu nano-hollow ball of method preparation, pattern is that more little particle is distributed in hollow ball surface, more regular.By Fig. 4
Know that 5 method of embodiment is prepared for the PtNiAu nano-hollow ball of regular appearance, and the growth of hollow ball surface is more compared with embodiment 4
Little particle, illustrate that the component of product is changed.
Embodiment 6
1) 0.2mL 0.3mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 80mL 0.5mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.04mol/L takes 8mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 4mL 12mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1h；
4) chlorauric acid solution for the 12mmol/L that 0.05mL is prepared in advance is instilled in above-mentioned dark solution, at room temperature magnetic
Power stirs 1min；
5) gained mixed solution is centrifuged at 16000rpm 12min, cleans 3 times with deionized water to get PtNiAu is arrived
Nano hollow sphere material.
6) the 8ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 3:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
Embodiment 7
1) 0.6mL 0.1mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 120mL 0.3mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.02mol/L takes 12mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 6mL 8mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature magnetic
Power stirs 2h；
4) chlorauric acid solution for the 0.5mmol/L that 1.5mL is prepared in advance is instilled in above-mentioned dark solution, at room temperature magnetic
Power stirs 10min；
5) gained mixed solution is centrifuged at 20000rpm 8min, cleans 5 times with deionized water and is received to get to PtNiAu
Rice hollow ball material；
6) the 12ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 1:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
Embodiment 8
1) 0.2mL 0.2mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 100mL 0.4mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.03mol/L takes 10mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 5mL 10mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1.5h；
4) chlorauric acid solution for the 1mmol/L that 1mL is prepared in advance is instilled in above-mentioned dark solution, magnetic force stirs at room temperature
Mix 40min；
5) gained mixed solution is centrifuged at 18000rpm, is cleaned with deionized water, is repeated several times to get PtNiAu is arrived
Nano hollow sphere material.
6) the 9ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 2:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
Embodiment 9
1) 0.2mL 0.2mol/L nickel salt solution (nickel sulfate solution) and the citric acid solution of 100mL 0.4mmol/L is equal
Even mixing；
2) sodium borohydride solution for preparing 0.03mol/L takes 10mL that above-mentioned mixing is added molten under conditions of nitrogen protection
Magnetic agitation is carried out simultaneously in liquid, solution is in brown at this time；
3) 5mL 10mmol/L platinum acid chloride solution is taken, brown mixed solution is instilled and obtains dark solution, at room temperature
Magnetic agitation 1.5h；
4) chlorauric acid solution for the 10mmol/L that 0.5mL is prepared in advance is instilled in above-mentioned dark solution, at room temperature magnetic
Power stirs 20min；
5) gained mixed solution is centrifuged at 18000rpm, cleaned with deionized water, is repeated several times to get attached to surface
There is the PtNiAu nano hollow sphere material of more nano particle.
6) the 11ug PtNiAu nano material and isopropanol obtained step 5), deionized water (the two volume ratio is 2:
1) and 50uL Nafion is mixed, and obtains slurry after ultrasonic disperse；Slurry is uniformly dripped and is invested in pretreated platinum carbon, it is dry
Afterwards up to the working electrode.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1.PtNiAu nano hollow sphere material, it is characterised in that: carry out as steps described below:
Step 1, under anaerobic, sodium borohydride solution is added in the mixed solution of nickel salt solution and citric acid solution,
Platinum acid chloride solution is added into above-mentioned solution again, at 20-25 DEG C of room temperature after magnetic agitation 1-2h, obtains black mixed solution,
In, nickel salt solution concentration is 0.1-0.3mol/L, and citric acid solution concentration is 0.3-0.5mmol/L, sodium borohydride solution concentration
For 0.02-0.04mol/L, platinum acid chloride solution concentration is 8-12mmol/L, nickel salt solution, citric acid solution, sodium borohydride solution
Volume ratio with platinum acid chloride solution is (1-3): (400-600): (40-60): (20-30)；
Step 2, chlorauric acid solution is instilled into the black mixed solution that step 1 is prepared, and after reacting 0-40min, is centrifuged, is clear
To get arriving PtNiAu nano hollow sphere material after washing, wherein chlorauric acid solution concentration is 0.5-12mmol/L, and additional amount is
0.05-1.5mL。
2. PtNiAu nano hollow sphere material according to claim 1, it is characterised in that: in step 1, protected using inertia
It protects gas and provides oxygen free condition for reaction system, such as nitrogen, helium or argon gas.
3. PtNiAu nano hollow sphere material according to claim 1, it is characterised in that: in step 1, nickel salt solution is dense
Degree is 0.2mol/L, and citric acid solution concentration is 0.4mmol/L, and sodium borohydride solution concentration is 0.03mol/L, platinum acid chloride solution
Concentration is 10mmol/L；Nickel salt uses nickel sulfate；Nickel salt solution, citric acid solution, sodium borohydride solution and platinum acid chloride solution
Volume ratio is 1:500:50:25；Magnetic agitation 1.5h at 20-25 DEG C of room temperature.
4. PtNiAu nano hollow sphere material according to claim 1, it is characterised in that: in step 2, mixed to black
Chlorauric acid solution is instilled in solution, reacts 0-30min；Centrifugal rotational speed is 16000-20000rpm, centrifugation time 8-12min
Afterwards, then with deionized water it cleans 3-5 times；Chlorauric acid solution concentration is 1-10mmol/L, additional amount 0.1-1mL.
The preparation method of 5.PtNiAu nano hollow sphere material, it is characterised in that: carry out as steps described below:
Step 1, under anaerobic, sodium borohydride solution is added in the mixed solution of nickel salt solution and citric acid solution,
Platinum acid chloride solution is added into above-mentioned solution again, at 20-25 DEG C of room temperature after magnetic agitation 1-2h, obtains black mixed solution,
In, nickel salt solution concentration is 0.1-0.3mol/L, and citric acid solution concentration is 0.3-0.5mmol/L, sodium borohydride solution concentration
For 0.02-0.04mol/L, platinum acid chloride solution concentration is 8-12mmol/L, nickel salt solution, citric acid solution, sodium borohydride solution
Volume ratio with platinum acid chloride solution is (1-3): (400-600): (40-60): (20-30)；
Step 2, chlorauric acid solution is instilled into the black mixed solution that step 1 is prepared, and after reacting 0-40min, is centrifuged, is clear
To get arriving PtNiAu nano hollow sphere material after washing, wherein chlorauric acid solution concentration is 0.5-12mmol/L, and additional amount is
0.05-1.5mL。
6. the preparation method of PtNiAu nano hollow sphere material according to claim 5, it is characterised in that: in step 1,
Oxygen free condition is provided for reaction system using inert protective gas, such as nitrogen, helium or argon gas.
7. the preparation method of PtNiAu nano hollow sphere material according to claim 5, it is characterised in that: in step 1,
Nickel salt solution concentration is 0.2mol/L, and citric acid solution concentration is 0.4mmol/L, and sodium borohydride solution concentration is 0.03mol/L,
Platinum acid chloride solution concentration is 10mmol/L；Nickel salt uses nickel sulfate；Nickel salt solution, citric acid solution, sodium borohydride solution and chlorine
The volume ratio of platinic acid solution is 1:500:50:25；Magnetic agitation 1.5h at 20-25 DEG C of room temperature.
8. the preparation method of PtNiAu nano hollow sphere material according to claim 5, it is characterised in that: in step 2,
Chlorauric acid solution is instilled into black mixed solution, reacts 0-30min；Centrifugal rotational speed is 16000-20000rpm, centrifugation time
After 8-12min, then cleaned 3-5 times with deionized water；Chlorauric acid solution concentration is 1-10mmol/L, additional amount 0.1-1mL.
9. application of the PtNiAu nano hollow sphere material in the oxidation of electro-catalysis methanol as described in Claims 1-4 is any,
It is characterized in that: PdNiAu nano hollow sphere material being mixed with organic solvent, deionized water and binder, is obtained after ultrasonic disperse
Slurry is uniformly dripped and is invested on glass-carbon electrode by slurry, up to working electrode after drying.
10. application according to claim 9, it is characterised in that: organic solvent uses isopropanol, organic solvent and deionization
Water volume ratio is (1-3): 1, preferably 2:1, and the additional amount of PtNiAu nano hollow sphere material is 8-12 parts by weight, and binder uses
Mass fraction is the Nafion solution of 0.1-0.3wt%.
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| US20090247401A1 (en) * | 2008-03-26 | 2009-10-01 | Wu Mei | Methanol oxidation catalyst |
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| US20090247401A1 (en) * | 2008-03-26 | 2009-10-01 | Wu Mei | Methanol oxidation catalyst |
| CN102430413A (en) * | 2011-10-08 | 2012-05-02 | 南京师范大学 | PtNi alloy/graphene combined nanometer catalyst with hollow structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113937311A (en) * | 2021-10-11 | 2022-01-14 | 福州大学 | Preparation method of two-dimensional porous silica non-carbon carrier supported platinum-copper-nickel catalyst |
| CN113937311B (en) * | 2021-10-11 | 2023-01-31 | 福州大学 | Preparation method of two-dimensional porous silica non-carbon carrier supported platinum-copper-nickel catalyst |
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