CN113769760A - Preparation method of platinum-nickel alloy nanoparticle/graphene composite catalyst - Google Patents
Preparation method of platinum-nickel alloy nanoparticle/graphene composite catalyst Download PDFInfo
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- CN113769760A CN113769760A CN202111132392.3A CN202111132392A CN113769760A CN 113769760 A CN113769760 A CN 113769760A CN 202111132392 A CN202111132392 A CN 202111132392A CN 113769760 A CN113769760 A CN 113769760A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 11
- 229910002844 PtNi Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000004687 hexahydrates Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 50
- 229910052697 platinum Inorganic materials 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
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- 238000009825 accumulation Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
Abstract
The invention discloses a preparation method of a platinum-nickel alloy nanoparticle/graphene composite catalyst, which relates to the field of electrocatalysis, wherein a proper amount of graphene oxide is dispersed in deionized water to form a uniform mixed solution, ammonia water is used for adjusting to a proper pH value, ammonia water is used for complexing a PtNi alloy precursor, the PtNi alloy precursor is dissolved in the graphene oxide solution, oscillation and ultrasonic are carried out to uniformly disperse the PtNi alloy precursor, freeze drying is carried out to obtain catalyst precursor powder, the precursor powder is placed into IC-PECVD equipment, and proper parameters such as temperature, discharge power, time, gas flow and the like are adjusted to obtain the high-performance platinum-nickel alloy nanoparticle/graphene composite catalyst; according to the invention, ammonia water is firstly utilized to complex the platinum-nickel alloy precursor, the operation is simple, the time consumption is short, the batch preparation is easy, the plasma is used for assisting high-temperature reduction, the complexity and the environmental problems of hydrothermal reduction are avoided, a chemical reducing agent is not used for synthesizing an efficient methanol oxidation catalyst, and the synthesis time is greatly shortened.
Description
Technical Field
The invention relates to the field of electrocatalysis, in particular to a preparation method of a platinum-nickel alloy nanoparticle/graphene composite catalyst.
Background
In recent years, Direct Methanol Fuel Cells (DMFCs) have attracted considerable attention for their high energy conversion efficiency, ready availability, and environmental friendliness, and are expected to be one of the high-efficiency power sources instead of internal combustion engines. The anode Methanol Oxidation Reaction (MOR) is an important component of the work of the DMFC, and the reaction speed and stability directly determine the use value of the DMFC, so that the rapid and effective catalysis of the methanol oxidation reaction is the key point for popularizing the DMFC for commercial use, and relates to the activity and stability of an anode catalyst.
At present, a platinum-based catalyst is still one of the most effective anode catalysts of the DMFC, and has high catalytic activity, but the rarity and high price of the platinum noble metal seriously hinder the commercialization of the DMFC; moreover, pure platinum based electrocatalysts are susceptible to agglomeration, shedding, deactivation by CO during long term operation under strong acidic or strong basic conditions, leading to insufficient oxidation of the methanol of the anode and slow kinetics, in other words, in order to increase the catalytic activity and durability of MOR, leaching and Oswald ripening of the platinum based electrocatalysts must be mitigated or even avoided and their resistance to CO poisoning must be increased.
Researches find that the catalytic activity and stability of the platinum-based catalyst can be improved by regulating and controlling the composition, size, morphology and structure of the platinum-based catalyst, wherein the alloying of the platinum noble metal and 3d transition metal (Ni, Fe, Cu and Co) is one of effective measures for improving the activity and stability of the platinum-based catalyst. Through alloying, not only can an ordered alloy structure be formed, the electronic structure of platinum be improved, the adsorption of intermediate product CO is reduced, the catalytic activity and the stability are improved, but also the content of platinum can be reduced, so that the use cost of the catalyst is reduced, and the commercialization of DMFC is promoted.
The strong synergistic effect between the metal and the carrier is also an important guarantee for improving the activity and stability of the platinum-based catalyst, however, the traditional activated carbon material is difficult to meet the requirement of high-efficiency catalysis. Graphene has many excellent properties such as high specific surface area, carrier mobility, and chemical stability, and is suitable as a carrier for platinum-based metal electrocatalysis, and it is highly popular in the field of catalysis because it can not only improve the dispersibility of metal particles, but also improve the mass transfer rate.
However, most of the preparation of platinum-based alloy/graphene electrocatalysts involves hydrothermal/solvothermal reactions, the long-term hydrothermal reaction causes severe accumulation of graphene, which is very unfavorable for the material conductivity of the catalyst, and the use of chemical reducing agents is involved, which causes a certain burden to the environment.
Disclosure of Invention
In order to solve the above-mentioned drawbacks of the background art, the present invention aims to provide a method for preparing a platinum-nickel alloy nanoparticle/graphene composite catalyst.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a platinum-nickel alloy nanoparticle/graphene composite catalyst comprises the following steps:
a: dispersing graphene oxide in deionized water to form a uniform graphene oxide solution, and adjusting the solution to be alkaline by using ammonia water;
b: dissolving nickel salt in excessive ammonia water, shaking up, and performing reaction according to Pt: ni ═ 1: adding chloroplatinic acid hexahydrate in a proportion of 1, oscillating and shaking up, centrifugally cleaning for a plurality of times by using ethanol, putting the mixture into an oven for drying to obtain a PtNi alloy precursor, dissolving the PtNi alloy precursor into a graphene oxide solution, and oscillating and ultrasonically dispersing the precursor uniformly to obtain a catalyst precursor;
c: freeze-drying the catalyst precursor to obtain catalyst precursor powder;
d: uniformly placing the catalyst precursor powder in a porcelain boat, placing the porcelain boat in an IC-PECVD device, vacuumizing to 3Pa, and introducing N2/H2The mixed gas is 1/2-3 in proportion, then the mixed gas is heated to 700 ℃ for heat preservation for 1-2h, the discharge power is 200W with 100 ℃ and the heating rate is 5-20 ℃/min, after the end, the glow discharge equipment is closed, and the platinum-nickel alloy nano-particle/graphene composite catalyst is obtained after natural cooling to the room temperature.
Further, the graphene oxide in the step A is thermal expansion graphene oxide, and is dispersed in deionized water through ultrasonic dispersion for 1-2 h.
Further, the nickel salt is dissolved in the excess ammonia water in the step B to form stable [ Ni (NH)3)6]2+The complex solution was shaken and then a fixed amount of chloroplatinic acid hexahydrate was added to immediately produce a pale yellow-green [ Ni (NH) ]3)6]2+[PtCl6]2-And (4) precipitating a complex, centrifuging the complex precipitate, and washing the complex precipitate for 3-5 times by using ethanol to obtain the PtNi alloy precursor.
Further, in the step C, the freeze-drying time is 24-48h, and the freeze-drying temperature is-78 ℃.
The invention has the beneficial effects that:
1. the method has the advantages that the ammonia water is firstly utilized to complex the platinum-nickel alloy precursor, the operation is simple, the time consumption is short, and the batch preparation is easy;
2. the plasma-assisted high-temperature reduction is used, so that the complexity and the environmental problems of hydrothermal reduction are avoided, a chemical reducing agent is not used for synthesizing an efficient methanol oxidation catalyst, and compared with the traditional high-temperature thermal reduction, the plasma-assisted high-temperature reduction greatly shortens the synthesis time.
3. The high dispersibility of the platinum-nickel nanoparticles on the graphene carrier is realized, the platinum content is reduced, the cost is saved, and the catalytic activity and the stability of methanol oxidation are greatly improved.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 shows the composite catalysts GPN-TE, GPN-T, GPN-E and commercial Pt/C1M H prepared in examples one, two and three, respectively2SO4The sweep rate is 50 mV/s;
FIG. 2 shows that the composite catalysts GPN-TE, GPN-T, GPN-E and commercial Pt/C catalyst 0.5M H were prepared in example one, two and three2SO4+1M CH3CV plot in OH with sweep rate of 50 mV/s;
FIG. 3 shows the composite catalysts GPN-TE, GPN-T, GPN-E and commercial products prepared in examples one, two and three, respectivelyPt/C ratio of 0.5M H2SO4+1M CH3IT plot in OH;
FIG. 4 shows that the GPN-TE composite catalyst prepared in example one is 0.5M H2SO4+1M CH3CV curve diagram in OH, the cycle number is 2000 circles, and the sweep rate is 200 mV/s;
FIG. 5 shows that the commercial Pt/C ratio is 0.5M H2SO4+1M CH3CV plot in OH with cycle number of 2000 cycles at a sweep rate of 200 mV/s.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A preparation method of a platinum-nickel alloy nanoparticle/graphene composite catalyst comprises the following steps:
a: weighing 30mg of graphene oxide, dissolving the graphene oxide in 15ml of deionized water, and carrying out ultrasonic treatment for 1 hour to prepare 2mg/ml graphene oxide dispersion liquid; and adjusting the pH value to about 11 by using ammonia water for later use.
B: 25mg of nickel chloride hexahydrate is weighed, dissolved in excessive ammonia water and shaken up, according to the Pt: ni ═ 1: adding a certain amount of chloroplatinic acid hexahydrate according to the proportion of 1, shaking up, centrifugally cleaning with ethanol (10000rmp,10min) for 3-5 times, and putting into an oven for drying to obtain the PtNi alloy precursor. Weighing 10mgPtNi alloy precursor, dispersing in the graphene oxide solution, stirring for 2h, performing ultrasonic treatment for 0.5h, and placing in a freezing box for later use.
C: and (3) putting the frozen catalyst precursor into a freeze dryer, and freeze-drying for 30h at-78 ℃ to obtain the catalyst precursor powder.
D: uniformly placing 10mg of the precursor powder in a porcelain boat, placing the porcelain boat in the middle of a first temperature zone of an IC-PECVD device, vacuumizing to about 3Pa, and introducing N2/H2The ratio of the mixed gas is 1/2.5, the pressure is about 110Pa, then the mixed gas is heated to 700 ℃, the temperature is kept for 1.5h, meanwhile, the discharge power is 130W, after the discharge is finished, the glow discharge equipment is closed, the mixed gas is naturally cooled to the room temperature, and the platinum-nickel alloy nanoparticle/graphene composite electrocatalyst is obtained and marked as GPN-TE, wherein G represents graphene, P represents Pt, N represents Ni, T represents high-temperature action, and E represents plasma action.
Example two
The invention provides a preparation method and application of a high-performance platinum-nickel alloy nanoparticle/graphene composite catalyst, which are characterized by comprising the following steps of:
in this embodiment, A, B, C is the same as that in the first embodiment, and in the step D, 10mg of precursor powder is uniformly placed in a porcelain boat, the porcelain boat is placed in the middle of the first temperature zone of the IC-PECVD device, the vacuum is pumped to about 3Pa, and N is introduced2/H2The ratio of the mixed gas is 1/2.5, the pressure is about 110Pa, then the mixture is heated to 700 ℃, the temperature is kept for 1.5h, then the mixture is naturally cooled to the room temperature, and the platinum-nickel alloy nanoparticle/graphene composite catalyst is prepared under the condition of no discharge and is marked as GPN-T, wherein G represents graphene, P represents Pt, N represents Ni, and T represents high-temperature action.
EXAMPLE III
The invention provides a preparation method and application of a high-performance platinum-nickel alloy nanoparticle/graphene composite catalyst, which are characterized by comprising the following steps of:
in this embodiment, A, B, C is the same as that in the first embodiment, and in the step D, 10mg of precursor powder is uniformly placed in a porcelain boat, the porcelain boat is placed in a radio frequency coil, vacuum pumping is performed to about 3Pa, and N is introduced2/H2And (3) the mixed gas ratio is 1/2.5, the pressure is about 110Pa, the discharge power is 130W, glow discharge is closed after 1.5h, and the platinum-nickel alloy nanoparticle/graphene composite catalyst is obtained and marked as GPN-E, wherein G represents graphene, P represents Pt, N represents Ni, and E represents plasma action.
As can be seen from fig. 1, the graphene platinum nickel composite treated by plasma-assisted high-temperature annealing (GPN-TE) in example one has the largest active specific surface area, which is significantly better than the same material treated by only high temperature (GPN-T) in example two or only plasma (GPN-E) in example three, and is better than commercial Pt/C, which indicates that the plasma-assisted high-temperature annealing environment provides a higher and more active energy field, which promotes the graphene platinum nickel composite to be reduced to a higher degree; and the activity specific surface area of GPN-P is larger than that of GPN-T, and the GPN-P is superior to that of commercial Pt/C, which shows that the plasma has strong activation and etching effects and is beneficial to the ordered alloying of the platinum-nickel precursor.
As can be seen from FIG. 2, GPN-TE in example one exhibited the highest specific mass activity of 1650mA/mgPtGPN-T (675 mA/mg) in example twoPt) GPN-E (600 mA/mg) in EXAMPLE IIIPt) And commercial Pt/C (355 mA/mg)Pt) 2.44 times, 2.75 times and 4.65 times of the total amount of the components, has very high catalytic activity, and shows that the plasma-assisted high-temperature treatment exerts 1+1>2, synthesizing the high-efficiency platinum-nickel alloy nanoparticle/graphene composite electrocatalyst.
As can be seen from FIG. 3, after 4000s, the GPN-TE current density in example one was 352mA/mgPtOn the left and right sides, GPN-T (100 mA/mg) in example twoPt) Example III GPN-E (10 mA/mg)Pt) And commercial Pt/C (44 mA/mg)Pt) 3.52 times, 35.2 times and 8 times of the GPN-TE show that the GPN-TE has high catalytic stability, and a stable platinum-nickel alloy structure is formed possibly due to the double-effect synergistic effect of the plasma and the high temperature, so that high quality specific activity is kept in a long-time test, however, in the third example, the GPN-E is reduced quickly, and the morphology structure of the catalyst is damaged probably due to long-time plasma etching, so that the current density is reduced quickly.
As can be seen from FIG. 4, the GPN-TE in example one is at 0.5M H2SO4+1M CH3After 2000 cycles of OH electrolyte, 75% of the initial current density is reserved; compared with the commercial Pt/C in FIG. 5, which only retains 35% of the initial current density after being cycled for 2000 cycles under the same conditions, the method has very obvious advantages, thereby indicating that GPN-TE has very high cycling stability and is far superior to the commercial Pt/C.
In a word, ammonia water is firstly utilized to complex a platinum-nickel alloy precursor, and a high-efficiency platinum-nickel alloy nanoparticle/graphene composite catalyst is prepared in a short time through plasma-assisted high-temperature annealing.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (4)
1. A preparation method of a platinum-nickel alloy nanoparticle/graphene composite catalyst is characterized by comprising the following steps:
a: dispersing graphene oxide in deionized water to form a uniform graphene oxide solution, and adjusting the solution to be alkaline by using ammonia water;
b: dissolving nickel salt in excessive ammonia water, shaking up, and performing reaction according to Pt: ni ═ 1: adding chloroplatinic acid hexahydrate in a proportion of 1, oscillating and shaking up, centrifugally cleaning for a plurality of times by using ethanol, putting the mixture into an oven for drying to obtain a PtNi alloy precursor, dissolving the PtNi alloy precursor into a graphene oxide solution, and oscillating and ultrasonically dispersing the precursor uniformly to obtain a catalyst precursor;
c: freeze-drying the catalyst precursor to obtain catalyst precursor powder;
d: uniformly placing the catalyst precursor powder in a porcelain boat, placing the porcelain boat in an IC-PECVD device, vacuumizing to 3Pa, and introducing N2/H2The mixed gas is 1/2-3 in proportion, then the mixed gas is heated to 700 ℃ for heat preservation for 1-2h, the discharge power is 200W with 100 ℃ and the heating rate is 5-20 ℃/min, after the end, the glow discharge equipment is closed, and the platinum-nickel alloy nano-particle/graphene composite catalyst is obtained after natural cooling to the room temperature.
2. The method for preparing the platinum-nickel alloy nanoparticle/graphene composite catalyst according to claim 1, wherein the graphene oxide in the step A is thermally expanded graphene oxide, and is ultrasonically dispersed in deionized water for 1-2 hours.
3. The method for preparing the platinum-nickel alloy nanoparticle/graphene composite catalyst as claimed in claim 1, wherein the nickel salt is dissolved in excessive ammonia water in the step B to form stable [ Ni (NH)3)6]2+The complex solution was shaken and then a fixed amount of chloroplatinic acid hexahydrate was added to immediately produce a pale yellow-green [ Ni (NH) ]3)6]2+[PtCl6]2-And (4) precipitating a complex, centrifuging the complex precipitate, and washing the complex precipitate for 3-5 times by using ethanol to obtain the PtNi alloy precursor.
4. The method for preparing the platinum-nickel alloy nanoparticle/graphene composite catalyst according to claim 1, wherein the freeze-drying time in the step C is 24-48 hours, and the freeze-drying temperature is-78 ℃.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012088681A1 (en) * | 2010-12-29 | 2012-07-05 | 海洋王照明科技股份有限公司 | Pt/graphene catalyst, preparation method and use thereof |
WO2014009835A2 (en) * | 2012-07-07 | 2014-01-16 | Indian Institute Of Technology Madras | Metal nanoparticle-graphene composites and methods for their preparation and use |
CN104959134A (en) * | 2015-06-30 | 2015-10-07 | 华南理工大学 | Heteroatom-doped porous graphite electro-catalyst and preparation and application thereof as well as device |
CN104973596A (en) * | 2015-06-30 | 2015-10-14 | 华南理工大学 | Hetero atom-doped hollow spherical grapheme composite material, and preparation method and applications thereof |
CN105032461A (en) * | 2015-06-30 | 2015-11-11 | 华南理工大学 | Heteroatom-doped graphene material with hole in surface and preparation and application thereof, as well as device |
CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
CN111342060A (en) * | 2020-03-03 | 2020-06-26 | 中科院合肥技术创新工程院 | Preparation method of platinum-nickel/nitrogen-doped reduced graphene oxide |
-
2021
- 2021-09-27 CN CN202111132392.3A patent/CN113769760A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012088681A1 (en) * | 2010-12-29 | 2012-07-05 | 海洋王照明科技股份有限公司 | Pt/graphene catalyst, preparation method and use thereof |
WO2014009835A2 (en) * | 2012-07-07 | 2014-01-16 | Indian Institute Of Technology Madras | Metal nanoparticle-graphene composites and methods for their preparation and use |
CN104959134A (en) * | 2015-06-30 | 2015-10-07 | 华南理工大学 | Heteroatom-doped porous graphite electro-catalyst and preparation and application thereof as well as device |
CN104973596A (en) * | 2015-06-30 | 2015-10-14 | 华南理工大学 | Hetero atom-doped hollow spherical grapheme composite material, and preparation method and applications thereof |
CN105032461A (en) * | 2015-06-30 | 2015-11-11 | 华南理工大学 | Heteroatom-doped graphene material with hole in surface and preparation and application thereof, as well as device |
CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
CN111342060A (en) * | 2020-03-03 | 2020-06-26 | 中科院合肥技术创新工程院 | Preparation method of platinum-nickel/nitrogen-doped reduced graphene oxide |
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