CN113070059A - Preparation method of platinum-based composite nano electrode catalyst - Google Patents
Preparation method of platinum-based composite nano electrode catalyst Download PDFInfo
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- CN113070059A CN113070059A CN202110320853.3A CN202110320853A CN113070059A CN 113070059 A CN113070059 A CN 113070059A CN 202110320853 A CN202110320853 A CN 202110320853A CN 113070059 A CN113070059 A CN 113070059A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 21
- 150000003057 platinum Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000000593 microemulsion method Methods 0.000 abstract description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 22
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a platinum-based composite nano electrode catalyst, which comprises the following steps: (1) preparing reverse microemulsion: respectively preparing reversed-phase microemulsion containing platinum salt or platinic acid, a reducing agent and other metal salts, wherein the reducing agent is used for reducing the platinum salt or the platinic acid and the other metal salts into metal simple substances; (2) liquid-phase reduction reaction: simultaneously or sequentially mixing the reverse microemulsion containing the platinum salt or the platinic acid and the reverse microemulsion containing other metal salts with the reverse microemulsion containing the reducing agent for reaction for a preset time until the platinum and other metals in the platinum salt or the platinic acid and the other metal salts are completely reduced; (3) and (5) cleaning and separating. The invention adopts the inverse microemulsion method to prepare the platinum-based composite nano-electrode catalyst, which can not only reduce the usage amount of metal platinum, but also control the structural form and the particle size between composite metals, fully play the synergistic effect between the two metals, improve the electrolytic reaction effect and overcome the defect that the platinum electrode is easy to cause excessive oxidation.
Description
Technical Field
The invention relates to the technical field of membrane preparation, in particular to a preparation method of an antioxidant polyamide reverse osmosis membrane.
Background
Fuel cell technology and electrochemical reaction technology are attracting more and more attention as key methods for mutual conversion of chemical energy and electric energy due to good conversion efficiency, simple operation conditions and environmental friendliness.
Currently, platinum electrode catalysts exhibit the highest electrocatalytic activity and excellent electrocatalytic efficiency, both from the viewpoint of catalytic activity and from the viewpoint of service life. However, the cost of platinum electrode is high, it is easy to poison in fuel cell, and it has not been able to meet the requirement of large-scale commercial application, especially in electrochemical reaction, the platinum electrode is easy to cause excessive oxidation of free radicals so as to reduce the selectivity of product.
In summary, it is highly desirable to provide a method for preparing a platinum-based composite nanoelectrode catalyst, which can reduce the usage amount of platinum metal, reduce the cost, fully exert the synergistic effect between two metals, improve the electrolytic reaction effect, and overcome the defect that the platinum electrode is prone to cause excessive oxidation.
Disclosure of Invention
The invention aims to develop a preparation method of a platinum-based composite nano electrode catalyst, which can reduce the usage amount of metal platinum, reduce the cost, fully play the synergistic effect between double metals, improve the electrolytic reaction effect and overcome the defect that a platinum electrode is easy to cause excessive oxidation.
The above purpose is realized by the following technical scheme: a preparation method of a platinum-based composite nano electrode catalyst comprises the following steps:
(1) preparing reverse microemulsion: respectively preparing reversed-phase microemulsion containing platinum salt or platinic acid, a reducing agent and other metal salts, wherein the reducing agent is used for reducing the platinum salt or the platinic acid and the other metal salts into metal simple substances;
(2) liquid-phase reduction reaction: simultaneously or sequentially mixing the reverse microemulsion containing the platinum salt or the platinic acid and the reverse microemulsion containing other metal salts with the reverse microemulsion containing the reducing agent for reaction for a preset time until the platinum and other metals in the platinum salt or the platinic acid and the other metal salts are completely reduced;
(3) cleaning and separating: and adding a demulsifier, performing solid-liquid separation, and then washing and drying the solid to obtain the platinum-based composite nano electrode catalyst.
The invention adopts the reverse microemulsion method to prepare the platinum-based composite nano electrode catalyst, the reverse microemulsion solubilized with platinum salt and other metal salts can exchange the sequence or simultaneously reduce the platinum salt and the other metal salts into metal, and the electrode catalysts with different configurations can be obtained by different reduction sequences, so that the performance of the product can be easily controlled, the usage amount of the metal platinum can be reduced, the cost is reduced, the structural form and the particle size of the composite metal can be controlled, the synergistic effect of the two metals can be fully exerted, the electrolytic reaction effect is improved, and the defect that the platinum electrode is easy to cause over oxidation is overcome.
Preferably, a further technical scheme is that in the step (2), the reverse microemulsion containing the platinum salt or the platinic acid is stirred for a predetermined time, then the excessive reverse microemulsion containing the reducing agent is added, the stirring reaction is continued until the platinum is completely reduced into the simple substance platinum, then a proper amount of reverse microemulsion containing other metal salts is added, the mixture is stirred for a predetermined time, finally the excessive reverse microemulsion containing the reducing agent is added again, and the stirring is continued for a predetermined time until other metal salts are completely reduced into the simple substance.
Preferably, a further technical scheme is that in the step (2), the reverse-phase microemulsion containing other metal salts is stirred for a predetermined time, then the excessive reverse-phase microemulsion containing the reducing agent is added, the stirring reaction is continued until the metal salts are reduced to the metal simple substance, then the added reverse-phase microemulsion containing the platinum salt or the platinic acid is mixed and stirred for a predetermined time, finally the excessive reverse-phase microemulsion containing the reducing agent is added again, and the stirring is continued for a predetermined time until the platinum is completely reduced to the simple substance.
Preferably, a further technical proposal is that the concentration of the reducing agent in the reversed-phase microemulsion solubilized with the reducing agent added for the second time in the step (2) is greater than that in the reversed-phase microemulsion solubilized with the reducing agent added for the first time.
Preferably, a further technical scheme is that a catalyst carrier prepared from a conductive material is added to the mixed microemulsion after the reduction reaction in the step (2) is completed, and the prepared platinum-based composite nanoelectrode catalyst is adsorbed on the catalyst carrier after the stirring is continued for a predetermined time.
Preferably, the carrier is carbon black, carbon nanotubes, carbon fiber powder or tungsten carbide.
Preferably, the platinum salt or the platinic acid includes hexachloroplatinate ions, and the other metal salt is a platinum salt.
Preferably, the reverse microemulsion comprises an aqueous phase, an oil phase, a surfactant and an auxiliary agent, wherein the oil phase comprises one or more of normal alkane, isoparaffin, cycloparaffin, aromatic hydrocarbon and halogenated hydrocarbon, the surfactant comprises one of cationic surfactant, anionic surfactant and nonionic surfactant, and the auxiliary agent comprises small molecular alcohol. The oil phase can be octane, heptane, cyclohexane, toluene, o-xylene, kerosene, etc
Preferably, the reducing agent is hydrazine hydrate or the like.
Preferably, the further technical scheme is that a demulsifier is added in the step (3) and stirred for a predetermined time to perform demulsification, then vacuum filtration is performed, then the solid is washed by using ethanol and deionized water for three times respectively, and finally vacuum drying is performed.
The invention adopts a reverse microemulsion method to prepare the platinum-based composite nano electrode catalyst, the metal particles of the electrode catalyst have good dispersibility, and the particle size and the structure can be regulated and controlled by optimizing synthesis conditions, thereby being beneficial to improving the catalytic activity and the stability of the electrode catalyst in electrocatalysis reaction. The invention can not only reduce the usage amount of noble metal platinum and gold and realize the high-efficiency reaction in the electrolytic process, but also introduce the composite metal to exert the intermetallic synergistic effect by adjusting the parameters of the structural form, the particle size and the like of the composite metal, promote the dissociation of the electrolytic solution, improve the conductivity of the solution and reduce the energy consumption of electrolysis. In addition, the method has the advantages of simple technical operation, low energy consumption, high yield of the applied electrolysis product, stable quality and good popularization and application prospect.
Detailed Description
The invention will be further described with reference to specific examples to assist a better understanding of the invention, but the scope of the invention is not limited to these examples.
Example 1
(1) Respectively preparing different reverse microemulsions:
the reverse microemulsion (a) comprises the following components: polyethylene glycol octyl phenyl ether: n-octanol:
palladium chloride aqueous solution 20 mL: 20mL of: 20mL of: 15 mL; the reverse microemulsion (b) comprises the following components: polyethylene glycol octyl phenyl ether: n-octanol: aqueous hexachloroplatinic acid solution 20 mL:
20mL of: 20mL of: 15 mL; the reverse microemulsion (c) comprises the following components: polyethylene glycol octyl phenyl ether: n-octanol: hydrazine hydrate solution: deionized water 10 mL: 10mL of: 10mL of:
0.4 g: 7.5 mL; the reverse microemulsion (d) comprises the following components: polyethylene glycol octyl phenyl ether: n-octanol: hydrazine hydrate solution: deionized water 10 mL: 10mL of: 10mL of: 0.6 g: 7.5
mL。
(2) Liquid-phase reduction reaction:
firstly, stirring the reverse microemulsion (a) for 20-40 min at normal temperature, then adding the reverse microemulsion (d), continuously stirring for 60-120min, mixing the reverse microemulsion (b), then stirring for 20-40 min, adding the reverse microemulsion (c) again, and continuously stirring for 60-120min to completely reduce the metal. After the metal was completely reduced, the addition of carbon black powder to the microemulsion was continued and stirring was continued for 60 min.
(3) Cleaning and separating:
and after the reduction reaction is finished, adding a demulsifier (ethanol) into the microemulsion, continuously stirring for 60min for demulsification, then carrying out vacuum filtration, respectively washing the solid by using ethanol and deionized water for three times, and finally carrying out vacuum drying (at the temperature of 150 ℃ and the pressure of-0.1 MPa) for 2h to prepare the platinum-palladium composite metal catalyst, and carrying out analysis and detection.
Example 2
(1) Respectively preparing different reverse microemulsions:
the reverse microemulsion (a) comprises the following components: cetyl trimethylammonium bromide: n-octanol: palladium chloride aqueous solution 20 mL: 21 g: 20mL of: 15 mL; the reverse microemulsion (b) comprises the following components: cetyl trimethylammonium bromide: n-octanol: aqueous hexachloroplatinic acid solution 20 mL: 21 g: 20mL of: 15 mL; the reverse microemulsion (c) comprises the following components: cetyl trimethylammonium bromide: n-octanol: hydrazine hydrate solution: deionized water 10 mL: 10 g: 10mL of: 0.4 g: 7.5 mL; the reverse microemulsion (d) comprises the following components: cetyl trimethylammonium bromide: n-octanol: hydrazine hydrate solution: deionized water 10 mL: 10 g: 10mL of: 0.6 g: 7.5 mL.
(2) Liquid-phase reduction reaction:
firstly, stirring the reverse microemulsion (b) for 20-40 min at normal temperature, then adding the reverse microemulsion (c), continuously stirring for 60-120min, mixing the reverse microemulsion (a), then stirring for 20-40 min, adding the reverse microemulsion (d) again, and continuously stirring for 60-120min to completely reduce the metal. After the metal was completely reduced, tungsten carbide powder was continuously added to the microemulsion and stirring was continued for 60 min.
(3) Cleaning and separating:
and after the reduction reaction is finished, adding a demulsifier (ethanol) into the microemulsion, continuously stirring for 60min for demulsification, then carrying out vacuum filtration, respectively washing the solid by using ethanol and deionized water for three times, and finally carrying out vacuum drying (at the temperature of 150 ℃ and the pressure of-0.1 MPa) for 2h to prepare the platinum-palladium composite metal catalyst, and carrying out analysis and detection.
Example 3
(1) Respectively preparing different reverse microemulsions:
the reverse microemulsion (a) comprises the following components: cetyl trimethylammonium bromide: n-octanol: palladium chloride aqueous solution 20 mL: 21 g: 20mL of: 15 mL; the reverse microemulsion (b) comprises the following components: cetyl trimethylammonium bromide: n-octanol: aqueous hexachloroplatinic acid solution 20 mL: 21 g: 20mL of: 15 mL; the reverse microemulsion (c) comprises the following components: cetyl trimethylammonium bromide: n-octanol: hydrazine hydrate solution: deionized water 10 mL: 10 g: 10mL of: 0.6 g: 7.5 mL.
(2) Liquid-phase reduction reaction:
firstly, stirring the reverse microemulsion (a) and the reverse microemulsion (b) for 20-40 min at normal temperature, then adding the excessive reverse microemulsion (c), and continuing stirring for 60-120min to completely reduce the metal. After the metal was completely reduced, the addition of carbon nanotubes to the microemulsion was continued and stirring was continued for 60 min.
(3) Cleaning and separating:
and after the reduction reaction is finished, adding a demulsifier (acetone) into the microemulsion, continuously stirring for 60min for demulsification, then carrying out vacuum filtration, respectively washing the solid by using ethanol and deionized water for three times, and finally carrying out vacuum drying (at the temperature of 150 ℃ and the pressure of-0.1 MPa) for 2h to prepare the platinum-palladium composite metal catalyst, and carrying out analysis and detection.
Through detection, the particle sizes of the composite metal catalysts prepared in the embodiments are all nano-scale sizes, and the composite metal catalysts have good electrochemical catalytic performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a platinum-based composite nano electrode catalyst is characterized by comprising the following steps:
(1) preparing reverse microemulsion: respectively preparing reversed-phase microemulsion containing platinum salt or platinic acid, a reducing agent and other metal salts, wherein the reducing agent is used for reducing the platinum salt or the platinic acid and the other metal salts into metal simple substances;
(2) liquid-phase reduction reaction: simultaneously or sequentially mixing the reverse microemulsion containing the platinum salt or the platinic acid and the reverse microemulsion containing other metal salts with the reverse microemulsion containing the reducing agent for reaction for a preset time until the platinum and other metals in the platinum salt or the platinic acid and the other metal salts are completely reduced;
(3) cleaning and separating: and adding a demulsifier, performing solid-liquid separation, and then washing and drying the solid to obtain the platinum-based composite nano electrode catalyst.
2. The method for preparing a platinum-based composite nano-electrode catalyst according to claim 1, wherein in the step (2), the inverse microemulsion containing platinum salt or platinic acid is stirred for a predetermined time, then an excessive amount of inverse microemulsion solubilized with a reducing agent is added, the stirring reaction is continued until platinum is completely reduced to simple substance platinum, then an appropriate amount of inverse microemulsion containing other metal salts is added, the mixture is stirred for a predetermined time, finally an excessive amount of inverse microemulsion solubilized with a reducing agent is added again, and the stirring is continued for a predetermined time until other metal salts are completely reduced to simple substances.
3. The method for preparing a platinum-based composite nano-electrode catalyst according to claim 1, wherein in the step (2), the reverse microemulsion containing other metal salts is stirred for a predetermined time, then an excessive reverse microemulsion solubilized with a reducing agent is added, the stirring reaction is continued until the metal salts are reduced to a metal simple substance, the added reverse microemulsion containing platinum salts or platinic acid is mixed and stirred for a predetermined time, finally, the excessive reverse microemulsion solubilized with the reducing agent is added again, and the stirring is continued for a predetermined time until platinum is completely reduced to the simple substance.
4. The method of preparing a platinum-based composite nanoelectrode catalyst according to claim 2 or 3, wherein the concentration of the reducing agent in the second addition of the reducing agent-solubilized reverse microemulsion in the step (2) is greater than the concentration of the reducing agent in the first addition of the reducing agent-solubilized reverse microemulsion.
5. The method of preparing a platinum-based composite nanoelectrode catalyst according to claim 2 or 3, wherein a catalyst support made of a conductive material is added to the mixed microemulsion after the reduction reaction is completed in the step (2), and the prepared platinum-based composite nanoelectrode catalyst is adsorbed on the catalyst support after the stirring is continued for a predetermined time.
6. The method of preparing a platinum-based composite nanoelectrode catalyst according to claim 5, wherein the carrier is carbon black, carbon nanotubes, carbon fiber powder or tungsten carbide.
7. The method for preparing a platinum-based composite nano-electrode catalyst according to claim 5, wherein the platinum salt or the platinic acid comprises hexachloroplatinate ions, and the other metal salt is a platinum salt.
8. The method for preparing the platinum-based composite nano-electrode catalyst according to claim 5, wherein the reverse microemulsion comprises an aqueous phase, an oil phase, a surfactant and an auxiliary agent, wherein the oil phase comprises one or more of normal alkane, isoparaffin, cycloparaffin, aromatic hydrocarbon and halogenated hydrocarbon, the surfactant comprises one of cationic surfactant, anionic surfactant and nonionic surfactant, and the auxiliary agent comprises small molecular alcohol.
9. The method for preparing a platinum-based composite nanoelectrode catalyst according to claim 8, wherein the reducing agent is hydrazine hydrate or the like.
10. The method for preparing the platinum-based composite nanoelectrode catalyst according to claim 9, wherein the demulsifying agent is added in the step (3) and stirred for a predetermined time to perform demulsification, then vacuum filtration is performed, the solid is washed with ethanol and deionized water for three times respectively, and finally vacuum drying is performed.
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Citations (8)
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