CN110075865B - Four-corner biconical platinum-iron-copper ternary metal nano alloy and preparation method and application thereof - Google Patents
Four-corner biconical platinum-iron-copper ternary metal nano alloy and preparation method and application thereof Download PDFInfo
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- CN110075865B CN110075865B CN201910464132.2A CN201910464132A CN110075865B CN 110075865 B CN110075865 B CN 110075865B CN 201910464132 A CN201910464132 A CN 201910464132A CN 110075865 B CN110075865 B CN 110075865B
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- IUNUQZUNCWXDMP-UHFFFAOYSA-N copper iron platinum Chemical compound [Fe][Pt][Cu] IUNUQZUNCWXDMP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000956 alloy Substances 0.000 title claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 52
- 240000004282 Grewia occidentalis Species 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001879 copper Chemical class 0.000 claims description 23
- 150000003057 platinum Chemical class 0.000 claims description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 150000002505 iron Chemical class 0.000 claims description 18
- 239000011668 ascorbic acid Substances 0.000 claims description 15
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 26
- 239000003054 catalyst Substances 0.000 abstract description 20
- 229910052697 platinum Inorganic materials 0.000 abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- 239000000446 fuel Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 239000010949 copper Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910002549 Fe–Cu Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
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- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
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Abstract
The invention discloses a four-corner biconical platinum-iron-copper ternary metal nano alloy and a preparation method and application thereof. The nanometer alloy with the four-corner bipyramid structure has evenly distributed platinum, iron and copper atoms and can be used as a catalyst of a methanol fuel cell.
Description
Technical Field
The invention belongs to the technical field of nano alloy materials, and particularly relates to a four-corner biconical platinum-iron-copper ternary metal nano alloy as well as a preparation method and application thereof.
Background
Metal nanomaterials are widely noticed due to their unique properties, and have been widely used in many fields such as energy, biomedicine, security, information, etc. The noble metal, especially the platinum nano material has excellent catalytic performance and is widely applied to the aspects of fuel cell catalysts, organic synthesis and the like.
Although the platinum catalyst has excellent performance, it is expensive and scarce in reserves, and thus its large-scale application is limited. To solve these problems, researchers have developed a variety of platinum-containing alloy nanomaterials that reduce the cost of the catalyst by alloying platinum with abundant and inexpensive metals. Meanwhile, the introduced metal can generate a synergistic effect with platinum, so that the catalytic performance of the alloy is improved.
However, in the prior art, the steps for preparing the platinum alloy nano material are complicated, the method is complex, and strict reaction conditions are required.
Disclosure of Invention
In order to solve the technical problems, the invention provides the four-corner biconical platinum-iron-copper ternary metal nano alloy, and the preparation method and the application thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a four-corner biconical platinum-iron-copper ternary metal nano alloy comprises the following steps: dissolving a surfactant, ascorbic acid, platinum salt, copper salt and ferric salt in oleylamine, transferring the mixed solution into a high-pressure reaction kettle, reacting for 7-10 h at 180-200 ℃, cooling, centrifuging, washing and drying to obtain the four-corner biconical platinum-iron-copper ternary metal nano alloy.
The surfactant is one or more of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and polyvinylpyrrolidone.
The platinum salt is one or two of potassium chloroplatinate and chloroplatinic acid.
The iron salt is one or more of ferric chloride, ferrous chloride and ferrous sulfate.
The copper salt is one or more of copper chloride, copper sulfate, copper nitrate and copper acetylacetonate.
The concentrations of the surfactant, ascorbic acid, platinum salt, copper salt and iron salt in oleylamine are respectively 1-2 g 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 of the platinum salt, the copper salt and the iron salt is 1 (1-2): (1-2).
Further, the ratio of the amount of the platinum salt, the copper salt, and the iron salt is preferably 1:2:2 or 1:1:1 or 1:2: 1.
The invention also provides the four-corner biconical platinum-iron-copper ternary metal nano alloy prepared by the preparation method, the four-corner biconical platinum-iron-copper ternary metal nano alloy is uniform in shape, and platinum, iron and copper atoms in the alloy material are uniformly distributed. The four-corner biconical shape is provided with six vertexes, wherein four vertexes are positioned on the same plane to form a quadrangle, the other two vertexes are respectively positioned above and below the plane, and the six vertexes form a four-corner biconical shape together.
The invention also provides application of the four-corner biconical platinum-iron-copper ternary metal nano alloy in electrocatalytic oxidation of methanol. The four-corner biconical platinum-iron-copper ternary metal nano alloy provided by the invention has a unique morphology capable of exposing a large number of high-activity crystal faces, so that when the alloy is used as an anode catalyst of a catalyst such as a methanol fuel cell, higher catalytic performance than that of pure platinum can be obtained, and meanwhile, the cost is lower.
The invention utilizes a liquid phase chemical reduction method, adopts platinum salt, copper salt and ferric salt as raw materials, adopts ascorbic acid as a reducing agent, and synthesizes the four-corner biconical platinum-iron-copper ternary metal nano alloy in one step under the action of a surfactant. The nanometer alloy with the four-corner bipyramid structure has evenly distributed platinum, iron and copper atoms and can be used as a catalyst of a methanol fuel cell.
Compared with the prior art, the invention has the following advantages:
1. the invention prepares a four-corner biconical platinum-iron-copper ternary metal nano alloy, wherein platinum, iron and copper are jointly used as the components of the alloy;
2. the method has the advantages of simple operation, green raw materials, short experimental period, high synthesis efficiency, high repetition rate and easy preparation and popularization;
3. the method for synthesizing the four-corner biconical platinum-iron-copper ternary metal nano alloy by one step by using the simple liquid phase method has no report;
4. the platinum-iron-copper ternary metal nano alloy provided by the invention has remarkably superior catalytic performance compared with a commercial Pt/C catalyst when being used as a methanol fuel cell anode catalyst.
Drawings
Fig. 1 is an XRD pattern of a four-corner biconical platinum-iron-copper nano-alloy prepared in example 1;
fig. 2 is a TEM image of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 1;
FIG. 3 is an elemental area distribution plot of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 1;
FIG. 4 is an elemental EDS plot of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 1;
FIG. 5 is an XRD pattern of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 2;
FIG. 6 is a TEM image of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 2;
FIG. 7 is an EDS map of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 2;
FIG. 8 is a TEM image of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 3;
FIG. 9 is a TEM image of a four-corner biconical platinum-iron-copper nanoalloy prepared in example 4;
FIG. 10 shows the Pt-Fe-Cu alloy prepared in example 1 and Pt/C at 0.5mol L-1Sulfuric acid and 0.5mol L-1CV chart in a mixed aqueous solution of methanol;
FIG. 11 shows the Pt-Fe-Cu alloy prepared in example 1 and Pt/C at 0.5mol L–1Sulfuric acid and 0.5mol L–1Current-time plot in mixed aqueous solution of methanol;
FIG. 12 is a TEM image of the product prepared in comparative example 1;
FIG. 13 shows the results of comparative example 1 at 0.5mol L-1Sulfuric acid and 0.5mol L-1CV chart in a mixed aqueous solution of methanol.
Detailed Description
The invention is described in detail below with reference to the following examples and the accompanying drawings.
Example 1
A preparation method of a four-corner biconical platinum-iron-copper nano alloy comprises the following steps:
PVP is taken as a surfactant, ascorbic acid is taken as a reducing agent, chloroplatinic acid, ferric chloride and acetylacetoneCopper is respectively taken as a platinum salt, an iron salt and a copper salt, the materials are dissolved in 5mL of oleylamine together, and the concentration of each material in the oleylamine is as follows: PVP 1g L-1Ascorbic acid 0.01mol L-1Chloroplatinic acid 0.0004mol L-10.0008mol L of ferric chloride-10.0008mol L of copper acetylacetonate-1The ratio of the amount of the platinum salt, the copper salt and the iron salt in the raw materials is 1:2: 2. Putting the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a drying oven, reacting for 10 hours at 180 ℃, cooling to room temperature, centrifugally separating a product, washing the product for a plurality of times by using absolute ethyl alcohol, and drying the product for 2 hours in a vacuum drying oven at 60 ℃ to obtain the quadrangular biconical platinum-iron-copper nano alloy with the yield of 90%.
The samples were characterized by X-ray powder diffraction (XRD) as shown in figure 1. By analyzing and comparing standard cards of platinum, iron and copper (card numbers: Pt 04-0802; Fe 52-0513; Cu 04-0836 respectively), only one set of diffraction peaks of the product is found, and the product is shifted compared with the diffraction peaks of pure metal, so that the product can be concluded to be an alloy formed by the platinum, the iron and the copper.
The morphology of the product was characterized by Transmission Electron Microscopy (TEM). As shown in fig. 2, a large number of dispersed tetragonal biconical platinum-iron-copper nanoalloys with an average size of 50nm can be seen. The element area distribution diagram is shown in fig. 3, and it can be seen that the three elements of platinum, iron and copper are uniformly distributed in the alloy. The ratio of each element in the alloy was measured by an energy spectrometer (EDS) attached to a transmission electron microscope, and the results are shown in fig. 4, where the atomic ratio of platinum, iron, and copper in the platinum-iron-copper alloy was 25: 5: 70.
example 2
A preparation method of a four-corner biconical platinum-iron-copper nano alloy comprises the following steps:
CTAB is taken as a surfactant, ascorbic acid is taken as a reducing agent, potassium chloroplatinate, ferrous chloride and copper chloride are respectively taken as platinum salt, iron salt and copper salt, the substances are dissolved in 5mL of oleylamine together, and the concentration of each substance in the oleylamine is as follows in sequence: CTAB 1.5g L-1Ascorbic acid 0.012mol L-10.0004mol L of potassium chloroplatinate-10.0004mol L of ferrous chloride-10.0008mol L of copper chloride-1Platinum salt in raw materialThe ratio of the amount of the copper salt to the amount of the iron salt is 1:1: 2. And (3) putting the solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into a drying oven, reacting for 7 hours at the temperature of 200 ℃, centrifugally separating a product, washing the product for a plurality of times by using absolute ethyl alcohol, and drying the product for 2 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the quadrangular biconical platinum-iron-copper nano alloy with the yield of 90%.
The sample was characterized by XRD and the product was platinum, iron and copper alloyed as shown in FIG. 5 by analysis of a comparative standard card (card numbers: Pt 04-0802; Fe 52-0513; Cu 04-0836, respectively).
The morphology of the product was characterized by TEM, as shown in fig. 6, from which a large amount of dispersed four-corner biconical platinum-iron-copper ternary nano-alloy with an average size of about 50nm could be seen. The proportions of the elements in the alloy were measured by EDS, and the results are shown in fig. 7, where the atomic ratio of platinum, iron, and copper in the platinum-iron-copper alloy was 32: 4: 64. compared with the example 1, changing the ratio of the platinum salt, the iron salt and the copper salt in the raw materials has little influence on the atomic ratio of the platinum, the iron and the copper in the product.
Example 3
A preparation method of a four-corner biconical platinum-iron-copper nano alloy comprises the following steps:
CTAC is used as a surfactant, ascorbic acid is used as a reducing agent, chloroplatinic acid, ferrous sulfate and copper sulfate are respectively used as platinum salt, iron salt and copper salt, the substances are dissolved in 5mL of oleylamine together, and the concentration of each substance in the oleylamine is as follows in sequence: CTAC 2g L-1Ascorbic acid 0.015mol L-1Chloroplatinic acid 0.0012mol L-10.0012mol L of ferrous sulfate-10.0012mol L of copper sulfate-1The ratio of the amount of the platinum salt, the copper salt and the iron salt in the raw materials is 1:1: 1. Putting the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, reacting for 9 hours at 190 ℃, cooling to room temperature, centrifugally separating a product, washing the product for a plurality of times by using absolute ethyl alcohol, and drying in a vacuum drying oven for 2 hours at 60 ℃ to obtain the four-corner biconical platinum-iron-copper nano alloy, wherein the yield is 90%, the TEM picture of the product is shown in figure 8, and a large amount of dispersed four-corner biconical platinum-iron-copper ternary nano alloy can be seen from the TEM picture, and the average size is about 50 nm.
Example 4
A preparation method of a four-corner biconical platinum-iron-copper nano alloy comprises the following steps:
the method comprises the following steps of taking a mixture of PVP, CTAB and CTAC as a surfactant, ascorbic acid as a reducing agent, chloroplatinic acid and potassium chloroplatinate as platinum salts, ferric chloride, ferrous chloride and ferrous sulfate as iron salts, copper chloride, copper sulfate, copper nitrate and copper acetylacetonate as copper salts, dissolving the above substances in 5mL of oleylamine, wherein the concentration of each substance in the oleylamine is as follows in sequence: surfactant 1g L-1Ascorbic acid 0.012mol L-10.0005mol L of platinum salt-10.001mol L of iron salt-1Copper salt 0.0005mol L-1The ratio of the amount of the platinum salt, the copper salt and the iron salt in the raw materials is 1:2: 1. Putting the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, reacting for 8 hours at 180 ℃, cooling to room temperature, centrifugally separating a product, washing the product for a plurality of times by using absolute ethyl alcohol, and drying in a vacuum drying oven for 2 hours at 60 ℃ to obtain the four-corner biconical platinum-iron-copper nano alloy, wherein the yield is 90%, the TEM picture of the product is shown in FIG. 9, and a large amount of uniformly dispersed four-corner biconical platinum-iron-copper ternary nano alloy can be seen from the TEM picture, and the average size is about 30 nm.
Example 5
The application of the four-corner biconical platinum-iron-copper nano alloy as a methanol oxidation reaction catalyst.
The four-corner biconical platinum-iron-copper nano alloy obtained in example 1 is loaded on a glassy carbon electrode to serve as a working electrode, and a platinum sheet electrode and an Hg/HgO electrode are respectively used as a counter electrode and a reference electrode to form a three-electrode system for testing the oxidation performance of the electrocatalytic methanol.
FIG. 10 is a graph of a four-corner biconical Pt-Fe-Cu nanoalloy and commercial Pt/C catalyst at 0.5mol L-1Sulfuric acid and 0.5mol L-1In the mixed solution of methanol, the potential range is-0.2 to 1.0V (relative to a standard hydrogen electrode), and the scanning speed is 50mV s-1The cyclic voltammogram obtained is as follows. These cyclic voltammograms exhibited oxidation peaks on both the forward sweep and the flyback plots, which are due to oxidation of methanol at the catalyst surfaceThe peak formed. The mass activity of the catalyst can be calculated by dividing the peak current of the positive sweep by the platinum loading. The mass activity of the four-corner biconical platinum-iron-copper nano alloy is 648.8mA mg-1 PtMuch higher than the mass activity of commercial Pt/C catalyst (173.8mA mg-1 Pt)。
The catalytic stability of the catalyst was tested by chronoamperometry, as shown in fig. 11. The test is carried out at 0.5mol L-1Sulfuric acid and 0.5mol L-1The test was carried out in a mixed solution of methanol, with an applied potential of 0.65V and a test time of 3600 seconds. Both the platinum-iron-copper catalyst and the Pt/C catalyst showed a significant reduction in current density after the start of the test due to the reduction in the concentration step of methanol on the catalyst surface due to oxidation, and the poisoning effect of the oxidation intermediate carbon monoxide on the catalyst. In the test process, the current density of the platinum-iron-copper catalyst is always much higher than that of the Pt/C catalyst, and good catalytic stability is shown.
Comparative example 1
PVP is taken as a surfactant, ascorbic acid is taken as a reducing agent, chloroplatinic acid, ferric chloride and copper acetylacetonate are respectively taken as platinum salt, ferric salt and copper salt, the substances are dissolved in 5mL of oleylamine together, and the concentration of each substance in the oleylamine is as follows in sequence: PVP 1g L-1Ascorbic acid 0.01mol L-1Chloroplatinic acid 0.0008mol L-10.0004mol L of ferric chloride-10.0004mol L of copper acetylacetonate-1The ratio of the amount of the platinum salt, the copper salt and the iron salt in the raw materials is 2:1: 1. Putting the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a drying oven, reacting for 10h at 180 ℃, cooling to room temperature, centrifugally separating a product, washing the product for a plurality of times by using absolute ethyl alcohol, and drying in a vacuum drying oven for 2h at 60 ℃, wherein the obtained particles have the shape shown in figure 12, and the product is an aggregate consisting of small particles instead of a quadrangular bipyramid shape. The proportion of the platinum salt, the copper salt and the iron salt in the raw materials can influence the appearance of the product. The electrocatalytic properties of the product were tested by cyclic voltammetry. FIG. 13 is a graph showing that it is at 0.5mol L-1Sulfuric acid and 0.5mol L-1In the mixed solution of methanol, the potential range is-0.2 to 1.0V (relative to the standard hydrogen potential)Polar), scan rate of 50mV s-1The cyclic voltammogram obtained is as follows. The mass activity was found to be 265.5mA mg-1 PtMuch lower than the mass activity of the tetragonal biconical platinum-iron-copper nanoalloy of example 1.
The above detailed description of a quadrangular biconical platinum-iron-copper ternary metallic nano-alloy, its preparation method and use with reference to the embodiments is illustrative and not restrictive, several embodiments can be cited within the limits thereof, and thus, variations and modifications thereof without departing from the general inventive concept shall fall within the scope of the present invention.
Claims (9)
1. A preparation method of a four-corner biconical platinum-iron-copper ternary metal nano alloy is characterized by comprising the following steps: dissolving a surfactant, ascorbic acid, platinum salt, copper salt and ferric salt in oleylamine, transferring the mixed solution into a high-pressure reaction kettle, reacting for 7-10 h at 180-200 ℃, cooling, centrifuging, washing and drying to obtain the four-corner biconical platinum-iron-copper ternary metal nano alloy;
the ratio of the platinum salt, the copper salt and the iron salt is 1 (1-2): (1-2).
2. The method for preparing the quadrangular biconical platinum-iron-copper ternary metal nano alloy according to claim 1, wherein the surfactant is one or more of cetyltrimethyl ammonium bromide, cetyltrimethyl ammonium chloride and polyvinylpyrrolidone.
3. The method for preparing the quadrangular biconical platinum-iron-copper ternary metal nano alloy according to claim 1, wherein the platinum salt is one or two of potassium chloroplatinate and chloroplatinic acid.
4. The method for preparing the quadrangular biconical platinum-iron-copper ternary metal nano alloy according to claim 1, wherein the iron salt is one or more of ferric chloride, ferrous chloride and ferrous sulfate.
5. The method for preparing the quadrangular biconical platinum-iron-copper ternary metal nano alloy according to claim 1, wherein the copper salt is one or more of copper chloride, copper sulfate, copper nitrate and copper acetylacetonate.
6. The method for preparing the quadrangular biconical platinum-iron-copper ternary metal nano alloy according to claim 1, wherein the concentrations of the surfactant, the ascorbic acid, the platinum salt, the copper salt and the iron salt in the oleylamine are respectively 1-2 g 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. The method for preparing the quadrangular biconical platinum-iron-copper ternary metal nano alloy according to any one of claims 1 to 6, wherein the amount ratio of the platinum salt, the copper salt and the iron salt is 1:2:2, or 1:1:1, or 1:2: 1.
8. The four-corner biconical platinum-iron-copper ternary metal nano alloy prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the four-corner biconical platinum-iron-copper ternary metallic nanoalloy of claim 8 in the electrocatalytic oxidation of methanol.
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