CN106910899B - Preparation method of nitrogen-doped double-shell structure nano catalyst - Google Patents
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Abstract
The invention discloses a preparation method of a nitrogen-doped double-shell structure nano catalyst, which comprises the following operation steps: (1) adding a carrier and a metal precursor into a solvent, stirring, adding a reducing agent for reduction, filtering, cleaning and drying to obtain a primary product; (2) placing the mixture in a high-temperature reaction furnace, introducing gas and calcining to obtain a nitrogen-doped nano alloy catalyst; (3) and performing dealloying treatment to obtain the nitrogen-doped double-shell structure nano catalyst. The catalyst has 5-19 times of activity of commercial 20 wt% Pt/C catalyst in oxygen reduction mass at 0.9V, has higher oxygen reduction catalytic performance, and lays a technical foundation for large-scale application of proton exchange membrane fuel cells.
Description
Technical Field
The invention relates to a preparation method of a nano catalyst, in particular to a preparation method of a nitrogen-doped double-shell structure nano catalyst.
Background
At present, with the increasing demand for energy and the increasing awareness of environmental protection, the development of clean energy conversion technology is urgently needed. Proton exchange membrane fuel cells offer a promising approach to clean energy conversion, but commercialization has problems of high cost and poor stability. Platinum is a high efficiency catalyst for proton exchange membrane fuel cells, however, due to its very low content in the earth's crust and the growing demand in the automotive industry, researchers have been working on developing high efficiency non-noble metal catalysts and low content noble metal catalysts.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a nitrogen-doped double-shell structure nano catalyst, and aims to obtain the nitrogen-doped double-shell structure nano catalyst with simple process, low cost and good catalytic performance.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a nitrogen-doped double-shell structure nano catalyst comprises the following operation steps:
(1) and (3) reduction of the catalyst: adding a carrier and a metal precursor into a solvent, then carrying out ultrasonic stirring, adding a reducing agent, heating for reduction, filtering, cleaning and drying a mixture obtained by reduction to obtain a primary product;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a high-temperature reaction furnace, controlling the temperature of the high-temperature reaction furnace by a program, and introducing gas for high-temperature calcination to obtain a nitrogen-doped nano alloy catalyst;
(3) dealloying treatment: and (3) carrying out dealloying treatment on the nitrogen-doped nano alloy catalyst obtained in the step (2) to obtain the nitrogen-doped nano catalyst with a double-shell structure.
The carrier in the step (1) is any one or a combination of several of carbon black, carbon nano tubes, carbon fibers, carbon nano rods, graphene oxide, reduced graphene oxide, activated carbon and porous carbon; the solvent is any one or combination of several of deionized water, ethanol, isopropanol and ethylene glycol.
The metal precursor in the step (1) is composed of I-type and II-type metal precursors, wherein the I-type metal precursor is platinum salt and/or palladium salt, and the II-type metal precursor is one or a mixture of two of iron salt, cobalt salt, nickel salt, tungsten salt, molybdenum salt and vanadium salt.
Wherein, the metal precursor combination mode comprises the following steps: platinum iron tungsten, platinum iron molybdenum, platinum iron vanadium, platinum cobalt tungsten, platinum cobalt molybdenum, platinum cobalt vanadium, platinum nickel tungsten, platinum nickel molybdenum, platinum nickel vanadium, palladium iron tungsten, palladium iron molybdenum, palladium iron vanadium, palladium cobalt tungsten, palladium cobalt molybdenum, palladium cobalt vanadium, palladium nickel tungsten, palladium nickel molybdenum, palladium nickel vanadium, platinum iron cobalt, platinum iron nickel, platinum cobalt nickel, platinum tungsten molybdenum, platinum tungsten vanadium, platinum molybdenum vanadium, palladium iron cobalt, palladium iron nickel, palladium cobalt nickel, palladium tungsten molybdenum, palladium tungsten vanadium, palladium molybdenum vanadium, platinum palladium iron, platinum palladium cobalt, platinum palladium nickel, platinum palladium tungsten, platinum palladium molybdenum, platinum palladium vanadium; the molar ratio of the three elements in the combination is 1-10: 1-20.
Wherein the platinum salt is chloroplatinic acid, acetylacetone platinum, ammonium hexachloroplatinate, potassium hexachloroplatinate, sodium hexachloroplatinate, potassium tetrachloroplatinate, sodium chloroplatinate, platinum tetrachloride, platinum nitrate, platinum tetraammine nitrate, and platinum tetraammine chloride; the palladium salt is palladium chloride, palladium acetate, ammonium chloropalladite, potassium chloropalladite, palladium sulfate, palladium nitrate, sodium tetrachloropalladate, potassium tetrabromopaalladite, palladium dibromide, palladium trifluoroacetate, palladium acetylacetonate, dichlorodiammine palladium, tetraaminopalladium nitrate, palladium hexafluoroacetylacetonate, palladium triphenylphosphine acetate, tetrakis (triphenylphosphine) palladium, bis (benzonitrile) palladium dichloride, bis (triphenylphosphine) palladium chloride, tris (benzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, (1, 5-cyclooctadiene) palladium dichloride, (1, 3-bis (diphenylphosphino) propane) palladium chloride, 1, 2-bis (diphenylphosphino) ethane palladium dichloride; the ferric salt is ferric chloride, ferrous chloride, ferric acetylacetonate, potassium ferricyanide, sodium ferrocyanide, sodium nitrosoferrocyanide, ferrocene, ferric nitrate, ferric citrate, ferric ammonium oxalate, ferrous oxalate, potassium hexacyanoferrate, ferric sulfate, ferrous ammonium sulfate, ferric ammonium sulfate; the cobalt salt is cobalt chloride, cobalt acetate, cobalt phosphate, cobalt phthalocyanine, potassium cobalt cyanide, potassium hexacyanocobaltate, hexaaminocobalide chloride, cobalt perchlorate, cobalt nitrate, cobalt fluoride, cobalt iodide, cobalt bromide, cobalt sodium nitrite, cobalt oxalate, cobalt sulfate, cobaltous sulfate, cobalt ammonium sulfate, cobalt naphthenate and cobalt acetylacetonate; the nickel salt is nickel chloride, nickel acetylacetonate, nickel acetate, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel ammonium sulfate, nickel hypophosphite, nickel ammonium nitrate, nickel sulfamate, basic nickel carbonate, nickel formate, nickelocene, bis (triphenylphosphine) nickel bromide and bis (triphenylphosphine) nickel chloride; the tungsten salt is ammonium metatungstate, ammonium tungstate, potassium tungstate, sodium tungstate, phosphotungstic acid, sodium phosphotungstate, tungstosilicic acid, tungsten hexachloride, tungsten hexacarbonyl and tungsten isopropoxide; the molybdenum salt is molybdic acid, ammonium tetramolybdate, ammonium heptamolybdate, ammonium dimolybdate, sodium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, molybdenum chloride, lithium molybdate, potassium molybdate, molybdenum hexacarbonyl, molybdenum acetylacetonate and molybdenum isopropoxide; the vanadium salt is ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadium chloride, vanadium oxide, vanadium tetrachloride, sodium vanadate, vanadium acetylacetonate, triisopropoxytriovanadyl, vanadyl acetylacetonate, triisopropoxytriovanadyl oxide or vanadyl diacetonealkoxide.
Wherein the mass ratio of the carrier in the step (1) to the metal contained in the metal precursor is 0.25-99: 1.
Wherein the heating reduction temperature in the step (1) is 40-200 ℃, and the reduction time is 0.1-100 hours; the heating mode is any one of water bath heating, oil bath heating, sand bath heating or high-temperature reaction kettles.
Wherein, the reducing agent in the step (1) is any one or a combination of several of sodium borohydride, potassium borohydride, hydrazine hydrate, formic acid and acetic acid; the drying is carried out by heating to 50-120 ℃ under vacuum or inert gas protection for 12 hours; the inert gas is any one or combination of several of nitrogen, helium and argon.
Wherein, the high-temperature calcination procedure in the step (2) is divided into two steps: the first step is that reducing gas is introduced at the temperature of 20-350 ℃, the calcining temperature is 250-350 ℃, and the calcining time is 0.1-10 hours; secondly, introducing a mixed gas of ammonia and inert gas at 350-1000 ℃, wherein the calcining temperature is 500-1000 ℃, the calcining time is 0.1-10 hours, and the proportion of the ammonia in the mixed gas is arbitrary and is not zero; the reducing gas is a mixed gas of hydrogen and inert gas, wherein the proportion of the hydrogen is arbitrary and is not zero; the inert gas is any one or combination of several of nitrogen, helium and argon.
Wherein, the dealloying in the step (3) is realized by means of electrochemistry and acid washing.
Compared with the prior art, the invention has the following beneficial effects:
according to the technical scheme, the nitrogen content in the catalyst is regulated and controlled and the shell thickness is controlled by adjusting the proportion of the metal precursor and the high-temperature calcination process, the obtained catalyst is uniform in shape, has good catalytic activity and electrochemical stability, and can greatly reduce the cost of the proton exchange membrane fuel cell. In 0.1 mol/L saturated oxygen perchloric acid solution, the catalyst has 5-19 times of oxygen reduction mass activity at 0.9V as that of a commercial 20 wt% Pt/C catalyst, and the catalyst prepared by the method has higher oxygen reduction catalytic performance, thereby laying a technical foundation for large-scale application of proton exchange membrane fuel cells.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention.
FIG. 2 is an X-ray diffraction pattern of the Pt-Fe-Mo system catalyst prepared in example 1, example 2 and example 3 of this invention.
FIG. 3 is a graph comparing the mass activity of oxygen reduction at 0.9V for the Pt-Fe-Mo system catalysts prepared in examples 1,2, and 3 according to the present invention and a commercial 20 wt% Pt/C catalyst in a 0.1 mol/L saturated oxygen perchloric acid solution.
Detailed Description
The following detailed description is to be read in connection with the accompanying drawings, but it is to be understood that the scope of the invention is not limited to the specific embodiments.
Example 1
A preparation method of a nitrogen-doped double-shell structure nano catalyst comprises the following operation steps:
(1) and (3) reduction of the catalyst: dissolving 2 ml of chloroplatinic acid water solution with the concentration of 42 mg/ml, 19 mg of ferric trichloride and 12 mg of ammonium heptamolybdate in 50 ml of deionized water to obtain a metal precursor solution, adding 200 mg of carbon black into the metal precursor solution, performing ultrasonic stirring and dispersion to obtain a suspension, transferring the suspension into a constant-temperature oil bath kettle at 50 ℃, performing magnetic stirring, adding 27 mg of sodium borohydride, reducing for 24 hours, filtering, washing with deionized water, and performing vacuum drying on the obtained filter residue at 60 ℃ for 12 hours to obtain solid powder, namely a primary product;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a crucible, placing the crucible in a high-temperature reaction tube furnace, firstly introducing hydrogen/argon mixed gas with the volume fraction of 5% of hydrogen, heating the crucible to 300 ℃ from room temperature at the speed of 5 ℃ per minute, and then carrying out heat preservation and calcination for 1 hour; then introducing ammonia gas, heating the mixture from 300 ℃ to 600 ℃ at the speed of 5 ℃ per minute, then carrying out heat preservation and calcination for 1 hour, and naturally cooling the mixture to room temperature to obtain the nitrogen-doped nano alloy catalyst;
(3) dealloying treatment: placing the nitrogen-doped nano alloy catalyst obtained in the step (2) into a 0.5 mol/L sulfuric acid solution, stirring for 4 hours, and then filtering, cleaning and drying in the step (1) to obtain the nitrogen-doped MoN @ Fe with a double-shell structure1@Pt3a/C nano catalyst.
Example 2
A preparation method of a nitrogen-doped double-shell structure nano catalyst comprises the following operation steps:
(1) and (3) reduction of the catalyst: dissolving 1.7 ml of chloroplatinic acid water solution with the concentration of 42 mg/ml, 48 mg of ferric trichloride and 11 mg of ammonium heptamolybdate in 50 ml of deionized water to obtain a metal precursor solution, adding 200 mg of carbon black into the metal precursor solution, performing ultrasonic stirring and dispersion to obtain a suspension, transferring the suspension into a constant-temperature oil bath kettle at 50 ℃, performing magnetic stirring, adding 32 mg of sodium borohydride, reducing for 24 hours, filtering, washing with deionized water, and performing vacuum drying on the obtained filter residue at 60 ℃ for 12 hours to obtain solid powder, namely a primary product;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a crucible, placing the crucible in a high-temperature reaction tube furnace, firstly introducing hydrogen/argon mixed gas with the volume fraction of 5% of hydrogen, heating the crucible to 300 ℃ from room temperature at the speed of 5 ℃ per minute, and then carrying out heat preservation and calcination for 1 hour; then introducing ammonia gas, heating the mixture from 300 ℃ to 600 ℃ at the speed of 5 ℃ per minute, then carrying out heat preservation and calcination for 1 hour, and naturally cooling the mixture to room temperature to obtain the nitrogen-doped nano alloy catalyst;
(3) dealloying treatment: placing the nitrogen-doped nano alloy catalyst obtained in the step (2) into a 0.5 mol/L sulfuric acid solution, stirring for 4 hours, and then filtering, cleaning and drying in the step (1) to obtain the nitrogen-doped MoN @ Fe with a double-shell structure3@Pt3a/C nano catalyst.
Example 3
A preparation method of a nitrogen-doped double-shell structure nano catalyst comprises the following operation steps:
(1) and (3) reduction of the catalyst: dissolving 1.5 ml of chloroplatinic acid water solution with the concentration of 42 mg/ml, 71 mg of ferric trichloride and 9 mg of ammonium heptamolybdate in 50 ml of deionized water to obtain a metal precursor solution, adding 200 mg of carbon black into the metal precursor solution, performing ultrasonic stirring and dispersion to obtain a suspension, transferring the suspension into a constant-temperature oil bath kettle at 50 ℃, performing magnetic stirring, adding 37 mg of sodium borohydride, reducing for 24 hours, filtering, washing with deionized water, and performing vacuum drying on the obtained filter residue at 60 ℃ for 12 hours to obtain solid powder, namely a primary product;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a crucible, placing the crucible in a high-temperature reaction tube furnace, firstly introducing hydrogen/argon mixed gas with the volume fraction of 5% of hydrogen, heating the crucible to 300 ℃ from room temperature at the speed of 5 ℃ per minute, and then carrying out heat preservation and calcination for 1 hour; then introducing ammonia gas, heating the mixture from 300 ℃ to 600 ℃ at the speed of 5 ℃ per minute, then carrying out heat preservation and calcination for 1 hour, and naturally cooling the mixture to room temperature to obtain the nitrogen-doped nano alloy catalyst;
(3) dealloying treatment: placing the nitrogen-doped nano alloy catalyst obtained in the step (2) into a sulfuric acid solution of 0.5 mol/L, stirring for 4 hours, and then stirringFiltering, cleaning and drying in the step (1) to obtain the nitrogen-doped MoN @ Fe with double-shell structure5@Pt3a/C nano catalyst.
Example 4
A preparation method of a nitrogen-doped double-shell structure nano catalyst comprises the following operation steps:
(1) and (3) reduction of the catalyst: dissolving 16.4 ml of 20 mg/ml platinum tetrachloride aqueous solution with the concentration of 20 mg/ml, 23 mg of cobalt chloride and 11 mg of ammonium metavanadate in 50 ml of deionized water to obtain a metal precursor solution, adding 50 mg of graphene oxide into the metal precursor solution, performing ultrasonic stirring and dispersion to obtain a suspension, transferring the suspension into a constant-temperature water bath kettle at 40 ℃, performing magnetic stirring, adding 131 mg of potassium borohydride, reducing for 100 hours, filtering, washing with deionized water, and performing vacuum drying on the obtained filter residue at 80 ℃ for 12 hours to obtain solid powder, namely a primary product;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a crucible, placing the crucible in a high-temperature reaction tube furnace, firstly introducing hydrogen/argon mixed gas with the volume fraction of 5% of hydrogen, heating the crucible to 250 ℃ from room temperature at the speed of 5 ℃ per minute, and then carrying out heat preservation and calcination for 10 hours; then introducing ammonia gas, heating the mixture from 250 ℃ to 500 ℃ at the speed of 5 ℃ per minute, then carrying out heat preservation and calcination for 10 hours, and naturally cooling the mixture to room temperature to obtain the nitrogen-doped nano alloy catalyst;
(3) dealloying treatment: placing the nitrogen-doped nano alloy catalyst obtained in the step (2) into a sulfuric acid solution with the molar ratio of 0.5 liter, stirring for 6 hours, and then filtering, cleaning and drying in the step (1) to obtain the nitrogen-doped double-shell structure VN @ Co1@Pt10a/Graphene nano-catalyst.
Example 5
A preparation method of a nitrogen-doped double-shell structure nano catalyst comprises the following operation steps:
(1) and (3) reduction of the catalyst: taking 0.8 ml of 2.5 mg/ml palladium chloride aqueous solution with concentration, 63 mg of ferric chloride and 20 mg of ammonium heptamolybdate, dissolving in 50 ml of deionized water to obtain a metal precursor solution, then adding 225 mg of carbon nano tube into the metal precursor solution, performing ultrasonic stirring and dispersion to obtain a suspension, then moving the suspension into a 200 ℃ constant temperature sand bath kettle for magnetic stirring, then adding 40 mg of potassium borohydride for reduction for 0.1 hour, filtering and washing with deionized water, and performing vacuum drying on the obtained filter residue at 120 ℃ for 12 hours to obtain solid powder, namely a primary product;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a crucible, placing the crucible in a high-temperature reaction tube furnace, firstly introducing hydrogen/argon mixed gas with the volume fraction of 5% of hydrogen, heating the mixture from room temperature to 350 ℃ at the speed of 5 ℃ per minute, and then carrying out heat preservation and calcination for 0.1 hour; then introducing ammonia gas, heating from 350 ℃ to 1000 ℃ at the speed of 5 ℃ per minute, then carrying out heat preservation and calcination for 0.1 hour, and naturally cooling to room temperature to obtain the nitrogen-doped nano alloy catalyst;
(3) dealloying treatment: placing the nitrogen-doped nano alloy catalyst obtained in the step (2) into a 0.5 mol/L sulfuric acid solution, stirring for 12 hours, and then filtering, cleaning and drying in the step (1) to obtain the nitrogen-doped MoN @ Fe with a double-shell structure20@Pd1/CNTs nano catalyst.
Example 6
A preparation method of a nitrogen-doped double-shell structure nano catalyst comprises the following operation steps:
(1) and (3) reduction of the catalyst: taking 1.3 ml of palladium sulfate aqueous solution with the concentration of 2.5 mg/ml, 7 mg of nickel acetate and 15 mg of ammonium tungstate to dissolve in 50 ml of deionized water to obtain metal precursor solution, then adding 237 mg of activated carbon into the metal precursor solution, ultrasonically stirring and dispersing to obtain suspension, then moving the suspension into a water bath kettle at 90 ℃ for magnetic stirring, then adding 6 mg of sodium borohydride for reduction for 2 hours, filtering and washing with deionized water, and carrying out vacuum drying on obtained filter residues at 50 ℃ for 12 hours to obtain solid powder, namely a primary product;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a crucible, placing the crucible in a high-temperature reaction tube furnace, firstly introducing hydrogen/argon mixed gas with the volume fraction of 5% of hydrogen, heating the crucible to 300 ℃ from room temperature at the speed of 5 ℃ per minute, and then carrying out heat preservation and calcination for 1 hour; then introducing ammonia gas, heating the mixture from 300 ℃ to 800 ℃ at the speed of 5 ℃ per minute, then carrying out heat preservation and calcination for 5 hours, and naturally cooling the mixture to room temperature to obtain the nitrogen-doped nano alloy catalyst;
(3) dealloying treatment: placing the nitrogen-doped nano alloy catalyst obtained in the step (2) into a 0.5 mol/L sulfuric acid solution, stirring for 24 hours, and then filtering, cleaning and drying in the step (1) to obtain the W with the nitrogen-doped double-shell structure20N@Ni1@Pd1Active carbon nano catalyst.
And (3) testing the electrochemical performance of the obtained nitrogen-doped double-shell structure nano catalyst:
(1) 5 mg of the catalyst prepared in examples 1 to 3 of the present invention and 5 mg of a commercial 20 wt% Pt/C catalyst were weighed, respectively, and placed in 1 ml of Nafion solution prepared by mixing 20. mu.l of a 5 wt% Nafion solution available from DuPont with 980. mu.l of ethanol, sonicated for 15 minutes, 10. mu.l of the slurry was dropped on a rotating disk electrode using a syringe, and after drying, an electrochemical test was performed using a PINE electrochemical workstation.
(2) The test conditions were as follows: the carbon rod is used as a counter electrode, the silver/silver chloride electrode is used as a reference electrode, the disc electrode is used as a working electrode to form a three-electrode testing system, and 0.1 mol/L perchloric acid aqueous solution is used as electrolyte.
FIG. 2 is an X-ray diffraction pattern of the platinum-iron-molybdenum system catalysts prepared in examples 1 to 3 of the present invention.
FIG. 3 is a graph comparing the mass activity of oxygen reduction at 0.9 volts for the Pt-Fe-Mo system catalysts prepared in examples 1-3 of this invention and a commercial 20 wt% Pt/C catalyst; as can be seen from FIG. 3, the catalyst prepared by the invention has excellent oxygen reduction catalytic activity, and in a 0.1 mol/L saturated oxygen perchloric acid solution, the mass activity of the catalyst in 0.9V oxygen reduction is 5-19 times that of a commercial 20 wt% Pt/C catalyst, so that the cost of a proton exchange membrane fuel cell can be greatly reduced.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (6)
1. A preparation method of a nitrogen-doped double-shell structure nano catalyst is characterized by comprising the following operation steps:
(1) and (3) reduction of the catalyst: adding a carrier and a metal precursor into a solvent, stirring, adding a reducing agent, heating to 40-200 ℃, reducing for 0.1-100 hours, filtering, cleaning and drying a mixture obtained by reduction to obtain a primary product; the carrier is any one or combination of a plurality of carbon black, carbon nano tubes, carbon fibers, carbon nano rods, graphene oxide, reduced graphene oxide, activated carbon and porous carbon; wherein, the metal precursor combination mode comprises the following steps: platinum iron tungsten, platinum iron molybdenum, platinum iron vanadium, platinum cobalt tungsten, platinum cobalt molybdenum, platinum cobalt vanadium, platinum nickel tungsten, platinum nickel molybdenum, platinum nickel vanadium, palladium iron tungsten, palladium iron molybdenum, palladium iron vanadium, palladium cobalt tungsten, palladium cobalt molybdenum, palladium cobalt vanadium, palladium nickel tungsten, palladium nickel molybdenum, palladium nickel vanadium, platinum iron cobalt, platinum iron nickel, platinum cobalt nickel, platinum tungsten molybdenum, platinum tungsten vanadium, platinum molybdenum vanadium, palladium iron cobalt, palladium iron nickel, palladium cobalt nickel, palladium tungsten molybdenum, palladium tungsten vanadium, palladium molybdenum vanadium, platinum palladium iron, platinum palladium cobalt, platinum palladium nickel, platinum palladium tungsten, platinum palladium molybdenum or platinum palladium vanadium; the molar ratio of the three elements in the combination is 1-10: 1-20; the platinum is a platinum salt, and the platinum salt is acetylacetone platinum, ammonium hexachloroplatinate, potassium hexachloroplatinate, sodium hexachloroplatinate, potassium tetrachloroplatinate, sodium chloroplatinate, platinum tetrachloride, platinum nitrate, platinum tetraammine nitrate or platinum tetraammine chloride; the palladium is a palladium salt which is palladium chloride, palladium acetate, ammonium chloropalladite, potassium chloropalladite, palladium sulfate, palladium nitrate, sodium tetrachloropalladate, potassium tetrabromopaalladite, palladium dibromide, palladium trifluoroacetate, palladium acetylacetonate, dichlorodiammine palladium, tetraaminopalladium nitrate, palladium hexafluoroacetylacetonate, palladium triphenylphosphine acetate, tetrakis (triphenylphosphine) palladium, bis (benzonitrile) palladium dichloride, bis (triphenylphosphine) palladium chloride, tris (benzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, (1, 5-cyclooctadiene) palladium dichloride, (1, 3-bis (diphenylphosphino) propane) palladium chloride or 1, 2-bis (diphenylphosphino) ethane palladium dichloride; the iron is ferric salt, and the ferric salt is ferric chloride, ferrous chloride, ferric acetylacetonate, potassium ferricyanide, sodium ferrocyanide, sodium nitrosoferrocyanide, ferrocene, ferric nitrate, ferric citrate, ferric ammonium oxalate, ferrous oxalate, potassium hexacyanoferrate, ferric sulfate, ferrous ammonium sulfate or ferric ammonium sulfate; the cobalt is a cobalt salt, and the cobalt salt is cobalt chloride, cobalt acetate, cobalt phosphate, cobalt phthalocyanine, potassium cobalt cyanide, potassium hexacyanocobaltate, hexaaminocobalt chloride, cobalt perchlorate, cobalt nitrate, cobalt fluoride, cobalt iodide, cobalt bromide, cobalt sodium nitrite, cobalt oxalate, cobalt sulfate, cobaltous sulfate, cobalt ammonium sulfate, cobalt naphthenate or cobalt acetylacetonate; the nickel is nickel salt, and the nickel salt is nickel chloride, nickel acetylacetonate, nickel acetate, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel ammonium sulfate, nickel hypophosphite, nickel ammonium nitrate, nickel sulfamate, basic nickel carbonate, nickel formate, nickelocene, bis (triphenylphosphine) nickel bromide or bis (triphenylphosphine) nickel chloride; the tungsten is tungsten salt, and the tungsten salt is ammonium metatungstate, ammonium tungstate, potassium tungstate, sodium phosphotungstate, tungsten hexachloride, tungsten hexacarbonyl and tungsten isopropoxide; the molybdenum is molybdenum salt, and the molybdenum salt is ammonium tetramolybdate, ammonium heptamolybdate, ammonium dimolybdate, sodium molybdate, ammonium phosphomolybdate, sodium phosphomolybdate, molybdenum chloride, lithium molybdate, potassium molybdate, molybdenum hexacarbonyl, molybdenum acetylacetonate or molybdenum isopropoxide; the vanadium is a vanadium salt, and the vanadium salt is ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadium chloride, vanadium tetrachloride, sodium vanadate, vanadium acetylacetonate, triisopropoxvanadyl, vanadyl acetylacetonate, triisopropoxytriantioxide or vanadyl diacetoneate oxide;
(2) high-temperature calcination of the catalyst: placing the primary product obtained in the step (1) in a high-temperature reaction furnace, and introducing gas for high-temperature calcination to obtain a nitrogen-doped nano alloy catalyst;
the high-temperature calcination procedure is divided into two steps: the first step is that reducing gas is introduced at the temperature of 20-350 ℃, the calcining temperature is 250-350 ℃, and the calcining time is 0.1-10 hours; secondly, introducing a mixed gas of ammonia and inert gas at 350-1000 ℃, wherein the calcining temperature is 500-1000 ℃, the calcining time is 0.1-10 hours, and the proportion of the ammonia in the mixed gas is arbitrary and is not zero; the reducing gas is a mixed gas of hydrogen and inert gas, wherein the proportion of the hydrogen is arbitrary and is not zero; the inert gas is any one or combination of several of nitrogen, helium and argon;
(3) dealloying treatment: and (3) carrying out dealloying treatment on the nitrogen-doped nano alloy catalyst obtained in the step (2) to obtain the nitrogen-doped nano catalyst with a double-shell structure.
2. The method of claim 1, wherein: the solvent in the step (1) is any one or a combination of several of deionized water, ethanol, isopropanol and ethylene glycol.
3. The method of claim 1, wherein: the mass ratio of the carrier in the step (1) to the metal contained in the metal precursor is 0.25-99: 1.
4. The method of claim 1, wherein: the heating mode in the step (1) is any one of water bath heating, oil bath heating, sand bath heating or high-temperature reaction kettle heating.
5. The method of claim 1, wherein: the reducing agent in the step (1) is any one or a combination of several of sodium borohydride, potassium borohydride, hydrazine hydrate, formic acid and acetic acid; the drying is carried out by heating to 50-120 ℃ under vacuum or inert gas protection for 12 hours; the inert gas is any one or combination of several of nitrogen, helium and argon.
6. The method of claim 1, wherein: the dealloying in the step (3) is realized by means of electrochemistry and acid washing.
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