CN110075865A - A kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy and its preparation method and application - Google Patents
A kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy and its preparation method and application Download PDFInfo
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- CN110075865A CN110075865A CN201910464132.2A CN201910464132A CN110075865A CN 110075865 A CN110075865 A CN 110075865A CN 201910464132 A CN201910464132 A CN 201910464132A CN 110075865 A CN110075865 A CN 110075865A
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- platinum
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- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010949 copper Substances 0.000 title claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 150000003057 platinum Chemical class 0.000 claims abstract description 25
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 16
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 16
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 239000000446 fuel Substances 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910002549 Fe–Cu Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- -1 acyl acetone copper Chemical compound 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B01J23/8926—Copper and noble metals
-
- 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
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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
- B01J37/16—Reducing
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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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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloys and its preparation method and application, utilize solution phase chemical reduction, using platinum salt, mantoquita and molysite are as raw material, ascorbic acid is as reducing agent, under the action of surfactant, one-step synthesis quadrangle biconial platinum-iron/copper ternary metal Nanoalloy.Platinum, iron, copper atom in the Nanoalloy of this quadrangle double cone structure are evenly distributed, and can be used as the catalyst of methanol fuel cell.
Description
Technical field
The invention belongs to Nanoalloy field of material technology, and in particular to a kind of quadrangle biconial platinum-iron/copper ternary metal
Nanoalloy and its preparation method and application.
Background technique
Metal nano material is widely noticed due to its unique performance, in crowds such as the energy, biomedicine, safety, information
It is multi-field to be all widely used.Noble metal especially platinum nano material has outstanding catalytic performance, in fuel cell catalyst
Agent, organic synthesis etc. are widely applied.
Although platinum catalyst is had excellent performance, but its is at high price, and reserves are rare, thus its large-scale application is limited
System.To solve these problems, researcher develops the alloy nano-material of a variety of platiniferous, by introducing rich reserves and price
Cheap metal forms alloy with platinum, to reduce the cost of catalyst.The metal introduced simultaneously can generate synergistic effect with platinum, from
And improve the catalytic performance of alloy.
But in the prior art, the step of preparing the alloy nano-material of platinum is cumbersome, and method is complicated, and needs strictly anti-
Answer condition.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloys
And its preparation method and application, method of the invention only needs single step reaction that can synthesize quadrangle biconial platinum-iron/copper ternary gold
Belong to Nanoalloy, this method is easy to operate, and raw material is green safe, and experimental period is short, and combined coefficient is high, reproducible.
The technical scheme adopted by the invention is as follows:
A kind of preparation method of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy, comprising the following steps: by surface
Activating agent, ascorbic acid, platinum salt, mantoquita and molysite are dissolved in oleyl amine, and mixed solution is transferred in autoclave, 180~
7~10h is reacted at 200 DEG C, through centrifugation, washing, drying, can be obtained the quadrangle biconial platinum-iron/copper ternary after cooling
Metal nano alloy.
The surfactant is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyvinyl pyrrole
One of alkanone is a variety of.
The platinum salt is one of potassium chloroplatinate, chloroplatinic acid or two kinds.
The molysite is one of iron chloride, frerrous chloride, ferrous sulfate or a variety of.
The mantoquita is one of copper chloride, copper sulphate, copper nitrate, acetylacetone copper or a variety of.
The concentration of the surfactant, ascorbic acid, platinum salt, mantoquita, molysite in oleyl amine is respectively 1~2g L-1、
0.01~0.015mol L-1, 0.0004~0.0012mol L-1, 0.0004~0.0012mol L-1, 0.0004~
0.0012mol L-1。
The ratio between the platinum salt, amount of substance of mantoquita, molysite are 1:(1~2): (1~2).
Further, the ratio between the platinum salt, amount of substance of mantoquita, molysite be preferably 1:2:2 or 1:1:2 or 1:1:1 or
1:2:1。
The present invention also provides a kind of quadrangle biconial platinum-iron/copper ternary metals being prepared such as above-mentioned preparation method
Nanoalloy, the quadrangle biconial platinum-iron/copper ternary metal Nanoalloy pattern is uniform, and platinum in alloy material,
Iron, copper atom are evenly distributed.There are six vertex for the quadrangle biconial tool, wherein four vertex are in the same plane, constitute
Quadrangle, other two vertex are located above and below plane, and six vertex collectively form quadrangle bipyramid.
The present invention also provides the quadrangle biconial platinum-iron/copper ternary metal Nanoalloys in electrocatalytic oxidation first
Application in alcohol.Biconial platinum in quadrangle provided by the invention-iron/copper ternary metal Nanoalloy, unique pattern can expose
The crystal face of a large amount of high activity, thus when the anode catalyst as catalyst such as methanol fuel cell, it can obtain than pure
The higher catalytic performance of platinum, while cost is lower.
The present invention utilizes solution phase chemical reduction, and using platinum salt, mantoquita and molysite are as raw material, and ascorbic acid is as reduction
Agent, under the action of surfactant, one-step synthesis quadrangle biconial platinum-iron/copper ternary metal Nanoalloy.This quadrangle
Platinum, iron, copper atom in the Nanoalloy of double cone structure are evenly distributed, and can be used as the catalyst of methanol fuel cell.
Compared with prior art, the invention has the following advantages that
1, the present invention is prepared for a kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy, in the alloy, platinum, iron
With copper collectively as the ingredient of alloy；
2, operation of the present invention is simple, and raw material green, experimental period is short, and combined coefficient is high, and repetitive rate is high, easily prepared and push away
Extensively；
3, provided by the invention to utilize simple liquid phase method one-step synthesis quadrangle biconial platinum-iron/copper ternary metal nanometer
The method of alloy there are no any report；
4, platinum provided by the invention-iron/copper ternary metal Nanoalloy is showed as methanol fuel cell anode catalyzer
Outstanding catalytic performance more significant than the Pt/C catalyst of business out.
Detailed description of the invention
Fig. 1 is quadrangle biconial platinum-iron/copper Nanoalloy XRD diagram prepared by embodiment 1；
Fig. 2 is the figure of quadrangle biconial platinum-iron/copper Nanoalloy TEM prepared by embodiment 1；
Fig. 3 is quadrangle biconial platinum-iron/copper Nanoalloy Element area profile prepared by embodiment 1；
Fig. 4 is the figure of quadrangle biconial platinum-iron/copper Nanoalloy element EDS prepared by embodiment 1；
Fig. 5 is quadrangle biconial platinum-iron/copper Nanoalloy XRD diagram prepared by embodiment 2；
Fig. 6 is the figure of quadrangle biconial platinum-iron/copper Nanoalloy TEM prepared by embodiment 2；
Fig. 7 is the figure of quadrangle biconial platinum-iron/copper Nanoalloy EDS prepared by embodiment 2；
Fig. 8 is the figure of quadrangle biconial platinum-iron/copper Nanoalloy TEM prepared by embodiment 3；
Fig. 9 is the figure of quadrangle biconial platinum-iron/copper Nanoalloy TEM prepared by embodiment 4；
Figure 10 is Pt-Fe-Cu alloy prepared by embodiment 1 and Pt/C in 0.5mol L-1Sulfuric acid and 0.5mol L-1First
CV figure in the mixed aqueous solution of alcohol；
Figure 11 is Pt-Fe-Cu alloy prepared by embodiment 1 and Pt/C in 0.5mol L–1Sulfuric acid and 0.5mol L–1First
Current-vs-time figure in the mixed aqueous solution of alcohol；
Figure 12 is the TEM figure of product prepared by comparative example 1；
Figure 13 is product prepared by comparative example 1 in 0.5mol L-1Sulfuric acid and 0.5mol L-1In the mixed aqueous solution of methanol
CV figure.
Specific embodiment
Below with reference to embodiment and Figure of description, the present invention is described in detail.
Embodiment 1
A kind of preparation method of quadrangle biconial platinum-iron/copper Nanoalloy, comprising the following steps:
Using PVP as surfactant, ascorbic acid makees reducing agent, and chloroplatinic acid, iron chloride and acetylacetone copper are made respectively
For platinum salt, molysite and mantoquita, above-mentioned substance is dissolved in 5mL oleyl amine together, concentration of each substance in oleyl amine is successively are as follows: PVP 1g
L-1, ascorbic acid 0.01mol L-1, chloroplatinic acid 0.0004mol L-1, iron chloride 0.0008mol L-1, acetylacetone copper
0.0008mol L-1, the ratio between platinum salt, amount of substance of mantoquita, molysite are 1:2:2 in raw material.Above-mentioned solution is packed into reaction under high pressure
It in kettle, is placed in baking oven, reacts 10h at 180 DEG C, after being cooled to room temperature, product is centrifugated, wash number with dehydrated alcohol
Secondary, dry 2h at 60 DEG C, can be obtained quadrangle biconial platinum-iron/copper Nanoalloy, yield 90% in vacuum oven.
Sample is characterized by X-ray powder diffraction (XRD), as shown in Figure 1.Pass through analysis, comparison platinum, iron and copper
Standard card (card number is respectively as follows: Pt 04-0802；Fe 52-0513；Cu 04-0836), find product only a set of diffraction
Peak, the diffraction maximum with pure metal is offset compared to having, and deducibility product is the alloy that platinum, iron and copper are formed.
The pattern of product is characterized by transmission electron microscope (TEM).As shown in Figure 2, it can be seen that a large amount of dispersions
Quadrangle biconial platinum-iron/copper Nanoalloy, average-size 50nm.Element area profile is as shown in Figure 3, it is seen that platinum, iron and
Three kinds of elements of copper are uniformly distributed in alloy.The ratio of each element is measured by the subsidiary energy disperse spectroscopy of transmission electron microscope (EDS) in alloy,
As a result as shown in figure 4, platinum, iron, copper atom ratio 25:5:70 in platinum-iron/copper alloy.
Embodiment 2
A kind of preparation method of quadrangle biconial platinum-iron/copper Nanoalloy, comprising the following steps:
Using CTAB as surfactant, ascorbic acid makees reducing agent, and potassium chloroplatinate, frerrous chloride and copper chloride are made respectively
For platinum salt, molysite and mantoquita, above-mentioned substance is dissolved in 5mL oleyl amine together, concentration of each substance in oleyl amine is successively are as follows: CTAB
1.5g L-1, ascorbic acid 0.012mol L-1, potassium chloroplatinate 0.0004mol L-1, frerrous chloride 0.0004mol L-1, copper chloride
0.0008mol L-1, the ratio between platinum salt, amount of substance of mantoquita, molysite are 1:1:2 in raw material.Above-mentioned solution is packed into reaction under high pressure
Kettle is placed in baking oven, reacts 7h at 200 DEG C, product is centrifugated, and is washed for several times with dehydrated alcohol, 60 in vacuum oven
Dry 2h, can be obtained quadrangle biconial platinum-iron/copper Nanoalloy, yield 90% at DEG C.
Sample is characterized by XRD, as shown in figure 5, (card number is respectively as follows: Pt by analysis contrast standard card
04-0802；Fe 52-0513；Cu 04-0836) know that product is platinum, the alloy that iron and copper are formed.
It is characterized by pattern of the TEM to product, as shown in fig. 6, the quadrangle bipyramid largely dispersed as can be seen from FIG.
Shape platinum-iron/copper ternary nano alloy, average-size are 50nm or so.The ratio of each element is measured by EDS in alloy, as a result such as
Shown in Fig. 7, platinum, iron, copper atom ratio 32:4:64 in platinum-iron/copper alloy.It is compared with embodiment 1, platinum salt, iron in feed change
The ratio of salt and mantoquita slightly influences platinum, iron, copper atom ratio in product.
Embodiment 3
A kind of preparation method of quadrangle biconial platinum-iron/copper Nanoalloy, comprising the following steps:
Using CTAC as surfactant, ascorbic acid makees reducing agent, chloroplatinic acid, ferrous sulfate and copper sulphate respectively as
Above-mentioned substance is dissolved in 5mL oleyl amine by platinum salt, molysite and mantoquita together, and concentration of each substance in oleyl amine is successively are as follows: CTAC 2g
L-1, ascorbic acid 0.015mol L-1, chloroplatinic acid 0.0012mol L-1, ferrous sulfate 0.0012mol L-1, copper sulphate
0.0012mol L-1, the ratio between platinum salt, amount of substance of mantoquita, molysite are 1:1:1 in raw material.Above-mentioned solution is packed into reaction under high pressure
Kettle is placed in baking oven, reacts 9h at 190 DEG C, and after being cooled to room temperature, product is centrifugated, and is washed for several times with dehydrated alcohol,
Dry 2h at 60 DEG C, can be obtained quadrangle biconial platinum-iron/copper Nanoalloy, yield 90%, product in vacuum oven
TEM figure as shown in figure 8, the quadrangle biconial platinum-iron/copper ternary nano alloy largely dispersed as can be seen from FIG., average ruler
Very little is 50nm or so.
Embodiment 4
A kind of preparation method of quadrangle biconial platinum-iron/copper Nanoalloy, comprising the following steps:
Using PVP, CTAB and CTAC mixture as surfactant, ascorbic acid makees reducing agent, chloroplatinic acid and chloroplatinic acid
Potassium is together as platinum salt, and iron chloride, frerrous chloride and ferrous sulfate are together as molysite, copper chloride, copper sulphate, copper nitrate and second
Above-mentioned substance is dissolved in 5mL oleyl amine, concentration of each substance in oleyl amine is successively are as follows: table together as mantoquita by acyl acetone copper together
Face activating agent 1g L-1, ascorbic acid 0.012mol L-1, platinum salt 0.0005mol L-1, molysite 0.001mol L-1, mantoquita
0.0005mol L-1, the ratio between platinum salt, amount of substance of mantoquita, molysite are 1:2:1 in raw material.Above-mentioned solution is packed into reaction under high pressure
Kettle is placed in baking oven, reacts 8h at 180 DEG C, and after being cooled to room temperature, product is centrifugated, and is washed for several times with dehydrated alcohol,
Dry 2h at 60 DEG C, can be obtained quadrangle biconial platinum-iron/copper Nanoalloy, yield 90%, product in vacuum oven
TEM figure as shown in figure 9, a large amount of finely dispersed quadrangle biconial platinum-iron/copper ternary nano alloys as can be seen from FIG., put down
Having a size of 30nm or so.
Embodiment 5
Quadrangle biconial platinum-application of the iron/copper Nanoalloy as methanol oxidation catalyst.
Quadrangle biconial platinum-iron/copper Nanoalloy that embodiment 1 obtains is loaded on glass-carbon electrode, as work electricity
Pole constitutes three-electrode system, carries out electro-catalysis first respectively using platinum plate electrode and Hg/HgO electrode as to electrode and reference electrode
The test of alcohol oxidation susceptibility.
Figure 10 is quadrangle biconial platinum-iron/copper Nanoalloy and business Pt/C catalyst in 0.5mol L-1Sulfuric acid and
0.5mol L-1In the mixed solution of methanol, potential range is -0.2~1.0V (relative to standard hydrogen electrode), and sweep speed is
50mV s-1The cyclic voltammetry curve of lower acquisition.These cyclic voltammetry curves have oxidation peak to go out on just sweeping the curve with flyback
Existing, these oxidation peaks are since methanol is at the peak that catalyst surface aoxidizes and is formed.The mass activity of catalyst can be by just
The peak current swept is calculated divided by the load capacity of platinum.Quadrangle biconial platinum-iron/copper Nanoalloy mass activity is
648.8mA mg-1 Pt, much higher than mass activity (the 173.8mA mg of business Pt/C catalyst-1 Pt)。
The catalytic stability of catalyst is tested by chronoamperometry, as shown in figure 11.Test is in 0.5mol L-1Sulfuric acid and
0.5mol L-1It is carried out in the mixed solution of methanol, the potential of application is 0.65V, and the testing time is 3600 seconds.Platinum-iron/copper catalysis
Agent and Pt/C catalyst have the phenomenon that apparent current density reduction after test starts, this is because catalyst surface methanol
The concentration ladder occurred due to oxidation reduces and intermediate oxidation product carbon monoxide causes catalyst poisoning effect jointly
's.During the test, platinum-iron/copper catalyst current density is higher by much than Pt/C catalyst always, is shown good
Catalytic stability.
Comparative example 1
Using PVP as surfactant, ascorbic acid makees reducing agent, and chloroplatinic acid, iron chloride and acetylacetone copper are made respectively
For platinum salt, molysite and mantoquita, above-mentioned substance is dissolved in 5mL oleyl amine together, concentration of each substance in oleyl amine is successively are as follows: PVP 1g
L-1, ascorbic acid 0.01mol L-1, chloroplatinic acid 0.0008mol L-1, iron chloride 0.0004mol L-1, acetylacetone copper
0.0004mol L-1, the ratio between platinum salt, amount of substance of mantoquita, molysite are 2:1:1 in raw material.Above-mentioned solution is packed into reaction under high pressure
It in kettle, is placed in baking oven, reacts 10h at 180 DEG C, after being cooled to room temperature, product is centrifugated, wash number with dehydrated alcohol
Secondary, dry 2h at 60 DEG C in vacuum oven, obtained granule-morphology is as shown in figure 12, the aggregation that product is made of little particle
Body, rather than quadrangle biconial.Illustrate that the ratio regular meeting of platinum salt in raw material, mantoquita, molysite has an impact the pattern of product.The production
The electrocatalysis characteristic of object is tested by cyclic voltammetry.Figure 13 is it in 0.5mol L-1Sulfuric acid and 0.5mol L-1First
In the mixed solution of alcohol, potential range is -0.2~1.0V (relative to standard hydrogen electrode), and sweep speed is 50mV s-1Lower acquisition
Cyclic voltammetry curve.Know that its mass activity is 265.5mA mg-1 Pt, far below the quadrangle biconial platinum-in embodiment 1
The mass activity of iron/copper Nanoalloy.
It is above-mentioned referring to embodiment to a kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy and preparation method thereof and
It is illustrative without being restrictive using the detailed description of progress, several implementations can be enumerated according to limited range
Example, therefore the change and modification in the case where not departing from present general inventive concept, should belong within protection scope of the present invention.
Claims (10)
1. a kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy preparation method, which is characterized in that the preparation side
Method shifts mixed solution the following steps are included: surfactant, ascorbic acid, platinum salt, mantoquita and molysite are dissolved in oleyl amine
Into autoclave, 7~10h is reacted at 180~200 DEG C, through centrifugation, washing, drying, can be obtained described four after cooling
Angle biconial platinum-iron/copper ternary metal Nanoalloy.
2. biconial platinum in quadrangle according to claim 1-iron/copper ternary metal Nanoalloy preparation method, feature
It is, the surfactant is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyvinylpyrrolidone
One of or it is a variety of.
3. biconial platinum in quadrangle according to claim 1-iron/copper ternary metal Nanoalloy preparation method, feature
It is, the platinum salt is one of potassium chloroplatinate, chloroplatinic acid or two kinds.
4. biconial platinum in quadrangle according to claim 1-iron/copper ternary metal Nanoalloy preparation method, feature
It is, stating molysite is one of iron chloride, frerrous chloride, ferrous sulfate or a variety of.
5. biconial platinum in quadrangle according to claim 1-iron/copper ternary metal Nanoalloy preparation method, feature
It is, the mantoquita is one of copper chloride, copper sulphate, copper nitrate, acetylacetone copper or a variety of.
6. biconial platinum in quadrangle according to claim 1-iron/copper ternary metal Nanoalloy preparation method, feature
It is, the concentration of the surfactant, ascorbic acid, platinum salt, mantoquita, molysite in oleyl amine is respectively 1~2g L-1、0.01
~0.015mol L-1, 0.0004~0.0012mol L-1, 0.0004~0.0012mol L-1, 0.0004~0.0012mol L-1。
7. quadrangle biconial platinum-iron/copper ternary metal Nanoalloy preparation side described in -6 any one according to claim 1
Method, which is characterized in that the ratio between the platinum salt, amount of substance of mantoquita, molysite are 1:(1~2): (1~2).
8. quadrangle biconial platinum-iron/copper ternary metal Nanoalloy preparation side described in -6 any one according to claim 1
Method, which is characterized in that the ratio between the platinum salt, amount of substance of mantoquita, molysite are 1:2:2 or 1:1:2 or 1:1:1 or 1:2:1.
9. a kind of quadrangle biconial platinum-iron/copper ternary that the preparation method as described in claim 1-8 any one is prepared
Metal nano alloy.
10. biconial platinum in quadrangle according to claim 9-iron/copper ternary metal Nanoalloy is in Electrocatalytic Oxidation of Methanol
In application.
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