CN110814362A - Preparation method of nano material with carbon-coated metal particle anchoring structure - Google Patents
Preparation method of nano material with carbon-coated metal particle anchoring structure Download PDFInfo
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- CN110814362A CN110814362A CN201911132399.8A CN201911132399A CN110814362A CN 110814362 A CN110814362 A CN 110814362A CN 201911132399 A CN201911132399 A CN 201911132399A CN 110814362 A CN110814362 A CN 110814362A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
The invention discloses a preparation method of a nano material with a carbon-coated metal particle anchoring structure, which comprises the following operation steps: (1) preparing a metal salt solution A, adding a substrate material B, uniformly mixing, reducing, filtering, cleaning, drying and calcining at high temperature to obtain a primary sample C; (2) and mixing the organic carbon source D with the sample C, carrying out hydrothermal reaction, filtering, cleaning, drying and calcining at high temperature to obtain the nano material with the carbon-coated metal particle anchoring structure. The metal particles in the nano material with the carbon-coated metal particle anchoring structure prepared by the invention are uniformly coated by the thin carbon layer, the preparation method is simple and controllable, and the nano material can be used as an electro-catalytic material with low cost, high efficiency and high stability and has great potential to be applied to practical production.
Description
Technical Field
The invention relates to a preparation method of a nano material, in particular to a preparation method of a nano material with a carbon-coated metal particle anchoring structure.
Background
In order to solve the problems of energy crisis, environmental pollution and the like caused by excessive consumption of the traditional fossil fuel, the development of efficient and environment-friendly energy conversion and storage technologies (such as fuel cells, hydrogen production by water electrolysis, super capacitors and the like) becomes a research hotspot. The carbon coating technology has great development potential in the energy field, and the electrocatalytic material with the anchoring structure is controllably synthesized by applying the carbon coating material preparation technology, so that the stability and the catalytic activity of the catalyst are greatly improved, and the cost of the catalyst is reduced. However, most processes for obtaining stable catalysts in the existing preparation technology of electrocatalysts are complex, long in time consumption and high in cost, so that a method for obtaining stable catalysts with simple and convenient processes and low cost is needed.
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 the preparation method of the nano material with the carbon-coated metal particle anchoring structure, and the simple, controllable, stable, cheap and efficient nano material can be obtained by the method.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following operation steps:
(1) preparing a metal salt solution A, adding a base material B into the metal salt solution A, mixing, dropwise adding a reducing agent for reduction, filtering, cleaning, drying, and calcining at high temperature in a mixed atmosphere to obtain a primary sample C, wherein the reduction reaction mode is a liquid phase reaction or a solvothermal reaction;
(2) and (2) mixing an organic carbon source D with the primary sample C obtained in the step (1), carrying out solvothermal reaction, filtering, cleaning, drying, and calcining at high temperature in a mixed atmosphere to obtain the nano material with the carbon-coated metal particle anchoring structure.
Preferably, the metal salt solution A in the step (1) is a metal salt solution obtained by dissolving the metal salt A in water; the metal salt A is at least one of iron salt, cobalt salt, nickel salt, tungsten salt, molybdenum salt, vanadium salt, platinum salt, rhodium salt, palladium salt, gold salt, ruthenium salt and iridium salt, the mixing proportion of two or more of the metal salt A and the palladium salt is arbitrary, wherein the mixing proportion of any one of the iron salt, the cobalt salt or the nickel salt is not zero when the iron salt, the cobalt salt or the nickel salt participates in the mixing; the ferric salt is one of 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, ethyl ferrocene, ferroferric dodecacarbonyl, ferric acetate or ferrous acetate; the cobalt salt is one of 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 or cobalt acetylacetonate; the nickel salt is one of 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 salt is one of tungsten hexacarbonyl, tungsten isopropoxide, ammonium metatungstate, ammonium tungstate, potassium tungstate, sodium tungstate, phosphotungstic acid, sodium phosphotungstate, tungstosilicic acid, tungsten hexachloride, tungsten hexacarbonyl, tungsten isopropoxide or ammonium metatungstate; the molybdenum salt is one of molybdenum hexacarbonyl, molybdenum acetylacetonate, molybdenum isopropoxide, ammonium tetramolybdate, ammonium heptamolybdate, ammonium dimolybdate, sodium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, molybdenum chloride, lithium molybdate or potassium molybdate; the vanadium salt is triisopropoxytriovanadium oxide, acetylacetonatovanadium oxide, triisopropoxytriovanadium oxide, vanadium diacetylacetonate oxide, ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadium chloride, vanadium oxide, vanadium tetrachloride or sodium vanadate; the platinum salt is one of ammonium hexachloroplatinate, potassium chloroplatinate, platinum dichloride, potassium hexachloroplatinate, platinum tetrachloride, platinum tetraammine chloride, platinum dichloride, platinum tetraiodide, platinum tetraammine nitrate, dinitrosoplatinum, (1, 2-diaminocyclohexane) platinum dichloride, platinum chloride, potassium tetracyanoplatinate, sodium hexachloroplatinate, cis-diaminedichloroplatinum, hydrogenated hexachloroplatinate, bis (2, 4-pentanedionato acid) platinum, acetylacetone platinum, ethylenediamine platinum chloride, (1, 5-cyclooctadiene) dichloro or ammonium chloroplatinate; the rhodium salt is one of rhodium acetylacetonate, rhodium chloride, rhodium acetate, rhodium iodide, rhodium octanoate, ammonium chlororhodate, dicarbonyl rhodium acetylacetonate, tetrakis (triphenylphosphine) rhodium hydride, bis (1, 5-cyclooctadiene) rhodium tetrafluoroborate, (1, 5-cyclooctadiene) rhodium chlororhodate dicarbonyl rhodium dichloride, rhodium octanoate dimer, rhodium triacetylacetonate, bicyclo octene rhodium chloride dimer, potassium hexachlororhodate, bis- Μ -chloro-tetracarbonylrhodium, ammonium pentachlororhodate hydrate, rhodium acetate dimer, sodium hexachlororhodate, ammonium hexachlororhodate hydrate, bis (triphenylphosphine) carbonyl rhodium chloride or rhodium heptafluorobutyrate dimer; the palladium salt is one of palladium acetate, palladium iodide, palladium acetate, palladium nitrate, palladium sulfate, palladium dibromide, ammonium chloropalladite, palladium acetylacetonate, sodium tetrachloropalladate, potassium chloropalladite, dichlorodiammine palladium, potassium tetrabromocapalladate, palladium hexafluoroacetylacetonate, palladium nitrate dihydrate, dichlorotetraammine palladium, palladium bromide, sodium chloropalladate, palladium trifluoroacetate, 1, 2-bis (dicyclohexyl) ethane palladium chloride or bis (ethylenediamine) palladium chloride; the gold salt is one of gold acetate, gold iodide, potassium tetrachloroplatinate, (triphenylphosphine) gold chloride, aurous chloride, sodium tetrachloroaurate, gold bromide, ammonium tetrachloroaurate hydrate, potassium chloroaurate, gold chloride, chloroauric acid, gold hydroxide, gold oxide, dichloro [ (+/-) -BINAP ] gold (I) or bis (chloroauric (I)) bis (diphenylphosphino) methane; the ruthenium salt is one of ruthenium acetylacetonate, ruthenium acetate, ruthenium trichloride, ammonium chlororuthenate, ammonium hexachlororuthenate, ruthenium oxide, carbonyl (dihydro) tris (diphenylphosphino) ruthenium, dichlorophenyl ruthenium (II) dimer, isopropylphenyl ruthenium dichloride, hexaammine ruthenium chloride, ruthenium nitrosyl nitrate, (1, 5-cyclooctadiene) ruthenium dichloride, tris (2, 2' -bipyridine) chloride, potassium homoruthenium (VII) or potassium hexachlororuthenate; the iridium salt is one of iridium acetate, iridium acetylacetonate, iridium bromide, iridium chloride, ammonium chloroiridate, iridium 2, 4-pentanedionate, iridium carbonylchloride bis (triphenylphosphine), iridium acetylacetonate bis (2-phenylpyridine) and potassium hexachloroiridium (IV).
Preferably, the metal salt A and the reducing agent in the step (1) are in a molar ratio of 1: 10.
Preferably, the base material B in step (1) is one of carbon black, carbon fiber, activated carbon, carbon nanotube, graphene, carbon felt, tungsten carbide, molybdenum carbide, vanadium carbide, tungsten nitride, molybdenum nitride, vanadium nitride, carbon cloth, nickel mesh, copper mesh, or titanium mesh.
Preferably, the liquid phase reaction in the step (1) is performed by dropping a reducing agent into a mixed solution of the base material B and the metal salt solution a at room temperature, and then stirring for 2 to 12 hours.
Preferably, the solvothermal reaction in the step (1) is to drop a reducing agent into a mixed solution of the carbon substrate material B and the metal salt solution A, stir the mixture uniformly, transfer the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave, place the autoclave in a forced air drying oven, react at 100-180 ℃ for 6-12 hours, cool the autoclave to room temperature, and take out the obtained substance.
Preferably, the reducing agent in step (1) is one of sodium borohydride, hydrazine hydrate, potassium borohydride, ethylene glycol, polyvinylpyrrolidone, N-propanol, N-butanol, ethanol, triethylene glycol, tetraethylene glycol, 1, 2-hexadecanediol, 1, 4-butanediol, 1, 4-pentanediol, hydroquinone, formaldehyde, benzaldehyde, acetic acid, oxalic acid, malic acid, ascorbic acid, vitamins, citric acid, formic acid, hydrazine, hydroxylamine, aniline, pyridine, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), or the like.
Preferably, the organic carbon source D in the step (2) is ethylene glycol, methanol, ethanol, isopropanol, glycerol, N-butanol, N-dimethylformamide, oleylamine, oleic acid, polyethylene glycol, toluene, acetonitrile, N-dimethylacetamide, dimethyl sulfoxide, pyridine, pyrrole, urea, aniline, N-methylaniline, N-dimethylaniline, N-ethylaniline, N-diethylaniline, diphenylamine, aniline hydrochloride, dioxodimethylpurine, phenylalanine, 2-hydroxypyridine, 2-aminopyridine, 2, 6-diaminopyridine, 2-methylpyridine, 3-aminopyridine, 4-methylpyridine, pentachloropyridine, 3-chloropyridine, 3-fluoropyridine, 3-bromopyridine, 2, 3-diaminopyridine, ethanol, N-dimethylformamide, N-methylaniline, oleic acid, polyethylene glycol, toluene, N-dimethylacetamide, dimethyl sulfoxide, pyridine, pyrrole, urea, aniline, N-methyla, 2-amino-3-chloropyridine, 2-pyrrolidone, 2-pyrrole carboxylic acid, 3-acetyl-2, 4-dimethylpyrrole, hydroxyethylpyrrolidone, 2-acetylpyrrole, 1-methylpyrrole, tetrahydropyrrole, ethyl pyrrole-2-carboxylate, 2, 4-dimethylpyrrole, 4-acetylpyridine, 2-acetylpyrrole, N-methylpyrrole, ion exchange resin, or the like.
Preferably, the molar ratio of the primary sample C to the organic carbon source D in the step (2) is 1-5: 1.
Preferably, the solvothermal reaction in the step (2) is to mix the organic carbon source D and the primary sample C, stir the mixture uniformly, transfer the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, place the autoclave in a forced air drying oven, react the mixture for 6 to 12 hours at 100 to 180 ℃, cool the mixture to room temperature, and take out the obtained substance.
Preferably, the high-temperature calcination in the steps (1) and (2) is carried out at a temperature rise speed of 5-20 ℃ per minute, a calcination temperature of 300-1000 ℃ and a heat preservation time of 1-6 hours; the mixed atmosphere is obtained by mixing hydrogen and inert gas according to any volume ratio, and the hydrogen content is not zero; the inert gas is one or a mixture of several of nitrogen, argon or helium.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nano material with the carbon-coated metal particle anchoring structure, which is prepared by the invention, has the advantages of stable structure, uniform size distribution of metal particles, low cost and simple preparation process, can be used as a high-performance electro-catalytic material, and has better electro-catalytic activity and electrochemical stability;
(2) the nano material prepared by the invention fully utilizes the anchoring effect of the carrier material on the metal particles, effectively relieves the phenomenon of catalyst inactivation caused by migration and falling of the metal particles in the electrochemical acceleration process, improves the stability of the catalyst and prolongs the service life of the catalyst;
(3) the nano material prepared by the method can be widely applied to the fields of fuel cells, metal-air batteries, electrolyzed water, electrolyzed wastewater and the like, and can be produced in a large scale.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention.
Fig. 2 is a schematic diagram of a nanomaterial product with an anchoring structure of carbon-coated metal particles prepared according to the present invention.
Fig. 3 is an oxygen reduction (ORR) polarization plot (LSV) of the nanomaterial with carbon-coated metal particle anchoring structure prepared according to the present invention in a 0.1 mole/perchloric acid solution.
Fig. 4 is a graph of Oxygen Evolution (OER) polarization curve (LSV) of nanomaterials with carbon-coated metal particle anchoring structures prepared according to the present invention in 1.0 mol/l potassium hydroxide 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. In the following examples, all the starting materials used were those obtained commercially unless otherwise specified.
Example 1
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) 2.378g (0.01mol) of nickel chloride hexahydrate and 4.44g (0.01mol) of ammonium hexachloroplatinate are dissolved in 100ml of deionized water and then are magnetically stirred, the mixed solution of the nickel chloride and the ammonium hexachloroplatinate which is obtained after uniform stirring is a metal salt solution A, 50g of carbon fiber is added into the metal salt solution A for mixing, then 7.566g (0.2mol) of reducing agent sodium borohydride is slowly dropped to carry out reduction reaction, the stirring is continued for 8 hours, then carrying out suction filtration, washing with deionized water, carrying out vacuum drying on filter residue obtained after suction filtration for 12 hours, transferring the dried substance into a tubular furnace for high-temperature calcination, namely, after introducing mixed gas (5% hydrogen and 95% argon) at a rate of 0.2ml/min for 30 minutes, then heating to 300 ℃ at the speed of 5 ℃/min, preserving the heat for 5 hours, and naturally cooling to obtain a primary sample C;
(2) mixing 35ml of ethylene glycol with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing into a blast drying oven, reacting at 180 ℃ for 12 hours, cooling to room temperature, taking out the obtained substance, carrying out suction filtration, washing with deionized water, carrying out vacuum drying on filter residues obtained after suction filtration for 12 hours, transferring the dried substance into a tubular furnace, carrying out high-temperature calcination, namely introducing mixed gas (5% hydrogen and 95% argon) at the speed of 0.2ml/min for 30 minutes, then heating to 650 ℃ at the speed of 10 ℃ per minute, carrying out heat preservation for 2 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 2
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) dissolving 1.9g (0.008mol) of nickel chloride hexahydrate, 1.904g (0.008mol) of cobalt chloride hexahydrate and 1.08g (0.004mol) of ferric chloride hexahydrate in 100ml of deionized water, then carrying out magnetic stirring, uniformly stirring to obtain a nickel chloride solution, a cobalt chloride solution and a ferric chloride solution which are metal salt solutions A, adding 50g of carbon fibers into the metal salt solutions A for mixing, then slowly dropwise adding 7.566g (0.20mol) of reducing agent sodium borohydride for reduction reaction, continuously stirring for 12 hours, then carrying out suction filtration, cleaning with deionized water, carrying out vacuum drying on filter residues obtained after suction filtration for 12 hours, transferring the dried substances into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% hydrogen and 95% argon) at a speed of 0.2ml/min for 30 minutes, then heating to 600 ℃ at a speed of 10 ℃/min, carrying out heat preservation for 3 hours, then naturally cooling, obtaining a primary sample C;
(2) mixing 35ml of ethylene glycol with the primary sample C obtained in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying oven, reacting at 100 ℃ for 12 hours, cooling to room temperature, taking out the obtained substance, carrying out suction filtration, washing with deionized water, and carrying out vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 300 ℃ at the speed of 5 ℃ per minute, preserving heat for 6 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 3
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) 2.57g (0.01mol) of nickel acetylacetonate and 3.984g (0.01mol) of ruthenium acetylacetonate are dissolved in 100ml of deionized water and then are magnetically stirred, the mixed solution of the nickel acetylacetonate and the ruthenium acetylacetonate which is obtained after uniform stirring is the metal salt solution A, 50g of carbon fiber is added into the metal salt solution A for mixing, then 7.566g (0.2mol) of reducing agent sodium borohydride is slowly dropped to carry out reduction reaction, the mixture is continuously stirred for 6 hours, then carrying out suction filtration, washing with deionized water, carrying out vacuum drying on filter residue obtained after suction filtration for 12 hours, transferring the dried substance into a tubular furnace for high-temperature calcination, namely, after introducing mixed gas (5% hydrogen and 95% argon) at a rate of 0.2ml/min for 30 minutes, then heating to 1000 ℃ at the speed of 5 ℃/min, preserving the heat for 1 hour, and naturally cooling to obtain a primary sample C;
(2) mixing 35ml of isopropanol with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying oven, reacting for 6 hours at 160 ℃, cooling to room temperature, taking out the obtained substance, performing suction filtration, washing with deionized water, and performing vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 1000 ℃ at the speed of 20 ℃ per minute, preserving heat for 1 hour, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 4
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1)1.189g (0.005mol) of nickel chloride hexahydrate is dissolved in 35ml of deionized water and then is magnetically stirred, the nickel chloride solution obtained after uniform stirring is a metal salt solution A, 10g of carbon fiber is added into the metal salt solution A for mixing, then 1.892g (0.05mol) of reducing agent sodium borohydride is slowly dripped for reduction reaction, the mixture is uniformly stirred, then the obtained substance after stirring is moved into a 50ml of polytetrafluoroethylene lining stainless steel autoclave, then the stainless steel autoclave is placed in a blast drying box and reacts for 8 hours at 100 ℃, the substance obtained after cooling to room temperature is taken out for suction filtration, filter residue is washed by deionized water, the obtained filter residue after suction filtration is dried for 12 hours in vacuum, the obtained substance after drying is calcined at high temperature in a tubular furnace, namely mixed gas (5% hydrogen and 95% argon) is introduced at the speed of 0.2ml/min for 30 minutes, then the temperature is raised to 650 ℃ at the speed of 10 ℃/min, preserving the heat for 2 hours, and naturally cooling to obtain a primary sample C;
(2) mixing 35ml of isopropanol with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying oven, reacting for 8 hours at 160 ℃, cooling to room temperature, taking out the obtained substance, performing suction filtration, washing with deionized water, and performing vacuum drying on the filter residue obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 850 ℃ at the speed of 15 ℃ per minute, preserving heat for 3 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 5
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) 4.756g (0.02mol) of nickel chloride hexahydrate is dissolved in 35ml of deionized water and then is magnetically stirred, the nickel chloride solution obtained after uniform stirring is a metal salt solution A, 10g of carbon nano tube is added into the metal salt solution A for mixing, then 10ml (0.1mol) of reducing agent hydrazine hydrate is slowly dripped for reduction reaction, the mixture is uniformly stirred, then the obtained substance after stirring is moved into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then the stainless steel autoclave is placed in a blast drying box and reacts for 8 hours at 160 ℃, the obtained substance is taken out after cooling to room temperature for suction filtration, the obtained substance is cleaned by deionized water, the filter residue obtained after suction filtration is dried for 12 hours in vacuum, the obtained substance after drying is moved into a tubular furnace for high-temperature calcination, namely mixed gas (5 percent hydrogen and 95 percent argon) is introduced for 30 minutes at the speed of 0.2ml/min, then the temperature is raised to 650 ℃ at the speed of 8 ℃/min, preserving the heat for 2 hours, and naturally cooling to obtain a primary sample C;
(2) mixing 30ml of ethylene glycol and 0.5ml of pyridine with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying box, reacting for 10 hours at 120 ℃, cooling to room temperature, taking out the obtained substance, performing suction filtration, washing with deionized water, and performing vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 1000 ℃ at the speed of 15 ℃ per minute, preserving heat for 2 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 6
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) 0.5962g (0.024mol) of nickel acetate tetrahydrate is dissolved in 35ml of deionized water and then is magnetically stirred, the nickel acetate solution obtained after even stirring is a metal salt solution A, 10g of tungsten carbide is added into the metal salt solution A for mixing, then 2.5ml (0.05mol) of reducing agent hydrazine hydrate is slowly dripped for reduction reaction, the mixture is evenly stirred, then the obtained substance after stirring is moved into a 50ml of polytetrafluoroethylene lining stainless steel autoclave, then the stainless steel autoclave is placed in a blowing drying box and reacts for 6 hours at 180 ℃, the substance obtained after cooling to room temperature is taken out for suction filtration, the filter residue obtained after suction filtration is cleaned by deionized water, the filter residue obtained after suction filtration is dried for 12 hours in vacuum, the substance obtained after drying is moved into a tubular furnace for high-temperature calcination, namely mixed gas (5% hydrogen and 95% argon) is introduced for 30 minutes at the speed of 0.2ml/min, then the temperature is increased to 1000 ℃ at the speed of 15 ℃/min, preserving the heat for 1 hour, and naturally cooling to obtain a primary sample C;
(2) mixing 30ml of ethylene glycol and 0.5ml of pyridine with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying oven, reacting for 10 hours at 140 ℃, cooling to room temperature, taking out the obtained substance, performing suction filtration, washing with deionized water, and performing vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 800 ℃ at the speed of 20 ℃ per minute, preserving heat for 3 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 7
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) dissolving 1.64g (0.005mol) of molybdenum acetylacetonate, 0.5623g (0.002mol) of cobalt sulfate heptahydrate and 0.27g (0.001mol) of ferric chloride hexahydrate in 35ml of deionized water, magnetically stirring, uniformly stirring to obtain a mixed solution of molybdenum acetylacetonate, cobalt sulfate and ferric chloride, namely a metal salt solution A, adding 10g of tungsten carbide into the metal salt solution A, mixing, slowly dropwise adding 4ml (0.08mol) of reducing agent hydrazine hydrate for reduction reaction, uniformly stirring, transferring the stirred substance into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, placing the substance into a blowing drying oven, reacting for 12 hours at 100 ℃, cooling to room temperature, taking out the substance, carrying out suction filtration, washing with deionized water, carrying out vacuum drying on filter residue for 12 hours, transferring the dried substance into a tubular furnace, carrying out high-temperature calcination, namely introducing mixed gas (5% hydrogen and 95% argon) at the speed of 0.2ml/min for 30 minutes, then heating to 450 ℃ at the speed of 5 ℃/min, preserving the temperature for 2 hours, and naturally cooling to obtain a primary sample C;
(2) mixing 30ml of ethylene glycol and 0.5ml of pyridine with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying box, reacting for 6 hours at 180 ℃, cooling to room temperature, taking out the obtained substance, performing suction filtration, washing with deionized water, and performing vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 450 ℃ at the speed of 5 ℃ per minute, preserving heat for 2 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 8
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) dissolving 0.475g (0.002mol) of nickel chloride hexahydrate, 0.66g (0.002mol) of sodium tungstate dihydrate and 0.117g (0.001mol) of ammonium metavanadate in 35ml of deionized water, then carrying out magnetic stirring, uniformly stirring to obtain a mixed solution of nickel chloride, sodium tungstate and ammonium metavanadate, namely a metal salt solution A, adding 10g of tungsten carbide into the metal salt solution A for mixing, then slowly dropwise adding 0.5ml (0.05mol) of 1, 4-butanediol serving as a reducing agent for reduction reaction, uniformly stirring, then transferring the stirred substance into a 50ml polytetrafluoroethylene-lined stainless steel autoclave, then placing the substance into a blast drying box, reacting for 8 hours at 140 ℃, cooling to room temperature, taking out the substance for suction filtration, washing with deionized water, carrying out vacuum drying on filter residue for 12 hours after suction filtration, transferring the dried substance into a tubular furnace for high-temperature calcination, introducing mixed gas (5% hydrogen and 95% argon) at the speed of 0.2ml/min for 30 minutes, then heating to 350 ℃ at the speed of 15 ℃ per minute, preserving heat for 6 hours, and naturally cooling to obtain a primary sample C;
(2) mixing 30ml of ethylene glycol and 0.5ml of pyridine with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying oven, reacting for 6 hours at 150 ℃, cooling to room temperature, taking out the obtained substance, carrying out suction filtration, washing with deionized water, and carrying out vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 450 ℃ at the speed of 10 ℃ per minute, preserving heat for 4 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 9
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) dissolving 0.412g (0.002mol) of sodium molybdate, 0.66g (0.002mol) of sodium tungstate dihydrate and 0.117g (0.001mol) of ammonium metavanadate in 100ml of deionized water, then carrying out magnetic stirring, uniformly stirring to obtain a mixed solution of sodium molybdate, sodium tungstate and ammonium metavanadate, namely a metal salt solution A, adding 50g of tungsten carbide into the metal salt solution A for mixing, then slowly dropwise adding 0.25ml (0.05mol) of reducing agent hydrazine hydrate for reduction reaction, continuously stirring for 2 hours, then carrying out suction filtration, washing with deionized water, carrying out vacuum drying on filter residues obtained after suction filtration for 12 hours, transferring the dried substances into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 450 ℃ at the speed of 5 ℃ per minute, preserving heat for 2 hours, then naturally cooling, obtaining a primary sample C;
(2) mixing 30ml of ethylene glycol and 0.5ml of pyridine with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying oven, reacting for 10 hours at 180 ℃, cooling to room temperature, taking out the obtained substance, performing suction filtration, washing with deionized water, and performing vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 550 ℃ at the speed of 5 ℃ per minute, preserving heat for 5 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
Example 10
The preparation method of the nano material with the carbon-coated metal particle anchoring structure comprises the following specific operation steps:
(1) dissolving 0.412g (0.002mol) of sodium molybdate, 0.66g (0.002mol) of sodium tungstate dihydrate and 0.117g (0.001mol) of ammonium metavanadate in 35ml of deionized water, then carrying out magnetic stirring, uniformly stirring to obtain a mixed solution of sodium molybdate, sodium tungstate and ammonium metavanadate, namely a metal salt solution A, adding 10g of carbon black into the metal salt solution A for mixing, then slowly dropwise adding 0.25ml (0.05mol) of hydrazine hydrate for reduction reaction, uniformly stirring, then transferring the stirred substance into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the substance into a blast drying oven, reacting for 10 hours at 150 ℃, cooling to room temperature, taking out the substance for suction filtration, washing with deionized water, carrying out vacuum drying on filter residue for 12 hours after suction filtration, transferring the dried substance into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 450 ℃ at the speed of 5 ℃/min, preserving the heat for 4 hours, and naturally cooling to obtain a primary sample C;
(2) mixing 30ml of ethylene glycol and 0.5ml of pyridine with the primary sample C in the step (1), uniformly stirring, transferring the solution obtained after stirring into a 50ml stainless steel autoclave with a polytetrafluoroethylene lining, then placing the autoclave in a forced air drying oven, reacting for 12 hours at 180 ℃, cooling to room temperature, taking out the obtained substance, performing suction filtration, washing with deionized water, and performing vacuum drying on filter residues obtained after suction filtration for 12 hours; and (3) transferring the dried sample into a tubular furnace for high-temperature calcination, namely introducing mixed gas (5% of hydrogen and 95% of argon) at the speed of 0.2ml/min for 30 minutes, then heating to 450 ℃ at the speed of 5 ℃ per minute, preserving heat for 4 hours, and then naturally cooling to obtain the nano material with the carbon-coated metal particle anchoring structure.
As can be seen from fig. 2, the product prepared by the present invention has a carbon-coated structure, and the metal particles are stably anchored on the carbon substrate; wherein the metal salt A-1, the metal salt A-2 and the metal salt A-3 respectively represent different metals.
As can be seen from FIG. 3, the oxygen reduction (ORR) activity of the nanomaterial with carbon-coated metal particle anchoring structure prepared by the present invention is still maintained above 98% after ten thousand cycles of stability test in 0.1 mol/perchloric acid solution.
As can be seen from FIG. 4, the nanomaterial with carbon-coated metal particle anchoring structure prepared by the invention has an Oxygen Evolution (OER) performance ratio of 40% IrO in 1.0 mol/L potassium hydroxide solution2the/C commercial catalyst was also superior at 50mA/cm2At a current density of (2), the overpotential ratio of the product is 40% IrO2the/C is about 80mV lower.
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 (10)
1. The preparation method of the nano material with the carbon-coated metal particle anchoring structure is characterized by comprising the following operation steps of:
(1) preparing a metal salt solution A, adding a base material B into the metal salt solution A, mixing, dropwise adding a reducing agent for reduction, filtering, cleaning, drying, and calcining at high temperature in a mixed atmosphere to obtain a primary sample C, wherein the reduction reaction mode is a liquid phase reaction or a solvothermal reaction;
(2) and (2) mixing an organic carbon source D with the primary sample C obtained in the step (1), carrying out solvothermal reaction, filtering, cleaning, drying, and calcining at high temperature in a mixed atmosphere to obtain the nano material with the carbon-coated metal particle anchoring structure.
2. The method of claim 1, wherein: the metal salt solution A in the step (1) is obtained by dissolving metal salt A in water; the metal salt A is at least one of iron salt, cobalt salt, nickel salt, tungsten salt, molybdenum salt, vanadium salt, platinum salt, rhodium salt, palladium salt, gold salt, ruthenium salt and iridium salt, the mixing proportion of two or more of the metal salt A and the palladium salt is arbitrary, wherein the mixing proportion of any one of the iron salt, the cobalt salt or the nickel salt is not zero when the iron salt, the cobalt salt or the nickel salt participates in the mixing; the ferric salt is one of 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, ethyl ferrocene, ferroferric dodecacarbonyl, ferric acetate or ferrous acetate; the cobalt salt is one of 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 or cobalt acetylacetonate; the nickel salt is one of 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 salt is one of tungsten hexacarbonyl, tungsten isopropoxide, ammonium metatungstate, ammonium tungstate, potassium tungstate, sodium tungstate, phosphotungstic acid, sodium phosphotungstate, tungstosilicic acid, tungsten hexachloride, tungsten hexacarbonyl, tungsten isopropoxide or ammonium metatungstate; the molybdenum salt is one of molybdenum hexacarbonyl, molybdenum acetylacetonate, molybdenum isopropoxide, ammonium tetramolybdate, ammonium heptamolybdate, ammonium dimolybdate, sodium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, molybdenum chloride, lithium molybdate or potassium molybdate; the vanadium salt is triisopropoxytriovanadium oxide, acetylacetonatovanadium oxide, triisopropoxytriovanadium oxide, vanadium diacetylacetonate oxide, ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadium chloride, vanadium oxide, vanadium tetrachloride or sodium vanadate; the platinum salt is one of ammonium hexachloroplatinate, potassium chloroplatinate, platinum dichloride, potassium hexachloroplatinate, platinum tetrachloride, platinum tetraammine chloride, platinum dichloride, platinum tetraiodide, platinum tetraammine nitrate, dinitrosoplatinum, (1, 2-diaminocyclohexane) platinum dichloride, platinum chloride, potassium tetracyanoplatinate, sodium hexachloroplatinate, cis-diaminedichloroplatinum, hydrogenated hexachloroplatinate, bis (2, 4-pentanedionato acid) platinum, acetylacetone platinum, ethylenediamine platinum chloride, (1, 5-cyclooctadiene) dichloro or ammonium chloroplatinate; the rhodium salt is one of rhodium acetylacetonate, rhodium chloride, rhodium acetate, rhodium iodide, rhodium octanoate, ammonium chlororhodate, dicarbonyl rhodium acetylacetonate, tetrakis (triphenylphosphine) rhodium hydride, bis (1, 5-cyclooctadiene) rhodium tetrafluoroborate, (1, 5-cyclooctadiene) rhodium chlororhodate dicarbonyl rhodium dichloride, rhodium octanoate dimer, rhodium triacetylacetonate, bicyclo octene rhodium chloride dimer, potassium hexachlororhodate, bis- Μ -chloro-tetracarbonylrhodium, ammonium pentachlororhodate hydrate, rhodium acetate dimer, sodium hexachlororhodate, ammonium hexachlororhodate hydrate, bis (triphenylphosphine) carbonyl rhodium chloride or rhodium heptafluorobutyrate dimer; the palladium salt is one of palladium acetate, palladium iodide, palladium acetate, palladium nitrate, palladium sulfate, palladium dibromide, ammonium chloropalladite, palladium acetylacetonate, sodium tetrachloropalladate, potassium chloropalladite, dichlorodiammine palladium, potassium tetrabromocapalladate, palladium hexafluoroacetylacetonate, palladium nitrate dihydrate, dichlorotetraammine palladium, palladium bromide, sodium chloropalladate, palladium trifluoroacetate, 1, 2-bis (dicyclohexyl) ethane palladium chloride or bis (ethylenediamine) palladium chloride; the gold salt is one of gold acetate, gold iodide, potassium tetrachloroplatinate, (triphenylphosphine) gold chloride, aurous chloride, sodium tetrachloroaurate, gold bromide, ammonium tetrachloroaurate hydrate, potassium chloroaurate, gold chloride, chloroauric acid, gold hydroxide, gold oxide, dichloro [ (+/-) -BINAP ] gold (I) or bis (chloroauric (I)) bis (diphenylphosphino) methane; the ruthenium salt is one of ruthenium acetylacetonate, ruthenium acetate, ruthenium trichloride, ammonium chlororuthenate, ammonium hexachlororuthenate, ruthenium oxide, carbonyl (dihydro) tris (diphenylphosphino) ruthenium, dichlorophenyl ruthenium (II) dimer, isopropylphenyl ruthenium dichloride, hexaammine ruthenium chloride, ruthenium nitrosyl nitrate, (1, 5-cyclooctadiene) ruthenium dichloride, tris (2, 2' -bipyridine) chloride, potassium homoruthenium (VII) or potassium hexachlororuthenate; the iridium salt is one of iridium acetate, iridium acetylacetonate, iridium bromide, iridium chloride, ammonium chloroiridate, iridium 2, 4-pentanedionate, iridium carbonylchloride bis (triphenylphosphine), iridium acetylacetonate bis (2-phenylpyridine) and potassium hexachloroiridium (IV).
3. The method of claim 1, wherein: the metal salt A and the reducing agent in the step (1) are in a molar ratio of 1: 10.
4. The method of claim 1, wherein: the substrate material B in the step (1) is one of carbon black, carbon fiber, activated carbon, carbon nano tubes, graphene, carbon felt, tungsten carbide, molybdenum carbide, vanadium carbide, tungsten nitride, molybdenum nitride, vanadium nitride, carbon cloth, nickel mesh, copper mesh or titanium mesh.
5. The method of claim 1, wherein: the liquid phase reaction in the step (1) is that at room temperature, a reducing agent is dripped into a mixed solution of a base material B and a metal salt solution A, and then the mixture is stirred for 2-12 hours; the solvothermal reaction is to drop a reducing agent into a mixed solution of a base material B and a metal salt solution A, uniformly stir, transfer the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave, place the autoclave in a forced air drying oven, react for 6-12 hours at 100-180 ℃, and cool the autoclave to room temperature and take out the obtained substance.
6. The method of claim 1, wherein: the reducing agent in the step (1) is one of sodium borohydride, hydrazine hydrate, potassium borohydride, ethylene glycol, polyvinylpyrrolidone, N-propanol, N-butanol, ethanol, triethylene glycol, tetraethylene glycol, 1, 2-hexadecanediol, 1, 4-butanediol, 1, 4-pentanediol, hydroquinone, formaldehyde, benzaldehyde, acetic acid, oxalic acid, malic acid, ascorbic acid, vitamin, citric acid, formic acid, hydrazine, hydroxylamine, aniline, pyridine, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC).
7. The method of claim 1, wherein: the organic carbon source D in the step (2) is ethylene glycol, methanol, ethanol, isopropanol, glycerol, N-butanol, N-dimethylformamide, oleylamine, oleic acid, polyethylene glycol, toluene, acetonitrile, N-dimethylacetamide, dimethyl sulfoxide, pyridine, pyrrole, urea, aniline, N-methylaniline, N-dimethylaniline, N-ethylaniline, N-diethylaniline, diphenylamine, aniline hydrochloride, dioxodimethylpurine, phenylalanine, 2-hydroxypyridine, 2-aminopyridine, 2, 6-diaminopyridine, 2-methylpyridine, 3-aminopyridine, 4-methylpyridine, pentachloropyridine, 3-chloropyridine, 3-fluoropyridine, 3-bromopyridine, 2, 3-diaminopyridine, isopropanol, glycerol, N-butanol, N-dimethylformamide, oleylamine, oleic acid, polyethylene glycol, toluene, acetonitrile, N-dimethylacetamide, dimethyl sulfoxide, pyridine, pyrrole, urea, aniline, N-methylaniline, 2-amino-3-chloropyridine, 2-pyrrolidone, 2-pyrrole carboxylic acid, 3-acetyl-2, 4-dimethylpyrrole, hydroxyethyl pyrrolidone, 2-acetylpyrrole, 1-methylpyrrole, tetrahydropyrrole, pyrrole-2-carboxylic acid ethyl ester, 2, 4-dimethylpyrrole, 4-acetylpyridine, 2-acetylpyrrole, N-methylpyrrole, fludarabine monophosphate, 1-butyl-3-methylimidazole hexafluorophosphate or an ion exchange resin.
8. The method of claim 1, wherein: the molar ratio of the primary sample C to the organic carbon source D in the step (2) is 1-5: 1.
9. The method of claim 1, wherein: and (3) carrying out the solvothermal reaction in the step (2) by mixing and uniformly stirring an organic carbon source D and a primary sample C, transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave, then placing the autoclave in a forced air drying oven, reacting for 6-12 hours at 100-180 ℃, cooling to room temperature, and taking out the obtained substance.
10. The method of claim 1, wherein: the high-temperature calcination in the steps (1) and (2) is carried out at the temperature rising speed of 2-20 ℃ per minute, the calcination temperature of 300-1000 ℃ and the heat preservation time of 1-6 hours; the mixed atmosphere is obtained by mixing hydrogen and inert gas according to any volume ratio, and the hydrogen content is not zero; the inert gas is one or a mixture of several of nitrogen, argon or helium.
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| CN114188517B (en) * | 2021-11-29 | 2023-12-29 | 万华化学(四川)有限公司 | Preparation method of ternary positive electrode material, lithium battery prepared from positive electrode material and application of lithium battery |
| CN116219477A (en) * | 2023-05-09 | 2023-06-06 | 四川大学 | Nano hybrid material and preparation method and application thereof |
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