CN111804313A - Fe2O3@Co9S8Preparation method and application of double-hollow core-shell structure nano composite material - Google Patents
Fe2O3@Co9S8Preparation method and application of double-hollow core-shell structure nano composite material Download PDFInfo
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011258 core-shell material Substances 0.000 title claims abstract description 99
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- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 28
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 28
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
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- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 6
- MYPQMIXEQWTNHO-UHFFFAOYSA-N CO.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound CO.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] MYPQMIXEQWTNHO-UHFFFAOYSA-N 0.000 description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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Abstract
The invention discloses Fe2O3@Co9S8The double hollow core-shell structure nano composite material and the preparation method and the application thereof, the method comprises the following steps: mixing and diluting ferric chloride solution and ammonium dihydrogen phosphate solution, and synthesizing Fe by a hydrothermal method2O3A hollow nanotube; then adding Fe2O3Dispersing the nanotube in an organic solvent, adding polyvinylpyrrolidone, mixing with a soluble cobalt salt solution and a 2-methylimidazole solution, stirring, separating, washing and drying to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite; then adding Fe2O3Dissolving the @ ZIF-67 composite material in an organic solvent, adding thioacetamide for etching, stirring, separating, washing, drying, and annealing to obtain Fe2O3@Co9S8A double hollow core-shell structure nano composite material. The method is convenient, reliable, low in cost, simple in equipment and easy to observe and control, and realizes the shape regulation of the double-hollow core-shell structure.
Description
Technical Field
The invention belongs to the technical field of functional nano material synthesis, and particularly relates to a method for preparing Fe2O3@Co9S8The general method of the double hollow core-shell structure nano composite material is applied to the electrolytic water oxygen evolution catalytic reaction process.
Background
With the rapid development of the world economy, human beings face a great challenge that fossil fuel is consumed, and in the development of a plurality of renewable energy sources, hydrogen energy is taken as non-intermittent clean energy and is paid much attention due to clean and effective cyclic conversion between chemical energy and electric energy, and electrochemical water decomposition hydrogen production is gradually becoming a high-prospect approach for industrial hydrogen production. Therefore, the development of excellent electrocatalysts to reduce the consumption of excessive electric energy in the electrolysis of water and accelerate the reaction rate is the current research hotspot.
The metal organic framework frame compounds (MOFs) are novel coordination polymers and have the advantages of high design flexibility, adjustable pore channels, large specific surface area, unique photoelectric and catalytic properties and the like. In the application of the precursor MOFs as an electrocatalyst, the MOFs derivative material obtained by chemical treatment keeps the morphology, the pore channel and the specific surface area of the precursor MOFs to a certain extent.
Transition Metal Chalcogenides (TMC) have unique physicochemical properties and are widely studied for use in electrochemical water splitting. With the development of the electrolytic water catalyst, the transition metal chalcogenide is modified by methods of surface engineering, structure control, component adjustment and the like, so that the number of active sites of the catalyst is increased, the conductivity is improved, and the catalytic activity of certain TMC is close to that of a noble metal catalyst.
Disclosure of Invention
To solve the problems of the prior art, the invention aims to overcome the defects of the prior artThe technology has the defects that Fe is provided2O3@Co9S8The preparation method is convenient and reliable, low in cost, simple in equipment, easy to control the process and convenient to realize the shape regulation and control of the double-hollow core-shell structure. Due to the Fe2O3@Co9S8The synergistic effect of the nano composite material multi-component compound improves the electrochemical catalytic performance, so that the nano composite material is applied to the electrolytic water oxygen evolution catalytic reaction.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
fe2O3@Co9S8The double-hollow core-shell structure nano composite material is characterized in that a double-hollow core-shell structure is formed by a core and a shell coated outside the core, wherein the core is Fe2O3Hollow nanotubes, the shell being Co9S8Hollow nanocage polyhedral material.
One kind of Fe of the invention2O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
mixing ferric chloride solution and ammonium dihydrogen phosphate solution in proportion, diluting the mixed solution, and synthesizing to obtain Fe through hydrothermal reaction2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
subjecting the Fe obtained in step a to2O3Dispersing hollow nanotubes in an organic solvent, adding polyvinylpyrrolidone, mixing with an organic solution of soluble cobalt salt and an organic solution of 2-methylimidazole, stirring for reaction, and then separating, washing and drying a solid product to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8double hollow core-shell structure nano compositeThe preparation process of the material comprises the following steps:
subjecting the Fe obtained in step b to2O3The @ ZIF-67 core-shell structure nano composite material is dissolved in an organic solvent, thioacetamide is added for etching, and after stirring, solid product separation, washing and drying are carried out to obtain Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
In a preferred embodiment of the present invention, in the step a, the Fe is2O3The preparation method of the hollow nanotube comprises the following steps:
a-1. preparation of hydrothermal reaction mixture:
the ferric chloride solution adopts a mixed solution of ferric chloride and ultrapure water, and the molar concentration of the ferric chloride in the ferric chloride solution is 0.5-1 mol/L; the ammonium dihydrogen phosphate solution adopts a mixed solution of ammonium dihydrogen phosphate and ultrapure water, and the molar concentration of the ammonium dihydrogen phosphate in the ammonium dihydrogen phosphate solution is 0.01-0.05 mol/L; the volume usage ratio of the ferric chloride solution to the ammonium dihydrogen phosphate solution is (3-4) to (2.5-6), and 70-85mL of ultrapure water is added into the mixed solution of the ferric chloride solution and the ammonium dihydrogen phosphate solution for dilution to obtain a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
the hydrothermal synthesis conditions are as follows: b, putting the hydrothermal reactant mixed solution prepared in the step a-1 into a polytetrafluoroethylene reaction kettle, heating to a temperature not lower than 220 ℃, carrying out hydrothermal reaction for at least 48 hours to obtain a product, removing a supernatant, carrying out centrifugal separation, and then washing with deionized water and ethanol in sequence to obtain a solution of a purified product;
a-3, separating solid product and post-processing:
the specific steps for separating the solid product are as follows: centrifuging the solution of the product purified in the step a-2 at the rotation speed of 8000-;
a-4. repeating the operation in the step a-3Making for 6-8 times, collecting solid product, drying in oven at 50-70 deg.C for 10-20 hr to obtain Fe2O3Hollow nanotubes.
In a preferred embodiment of the present invention, in the step b, the Fe is2O3The preparation method of the @ ZIF-67 core-shell structure nano composite material comprises the following steps:
b-1. Fe to be prepared in said step a2O3Dispersing the hollow nano-tube in an anhydrous methanol solvent to form a mixed solution A1Setting Fe2O3The concentration of the hollow nano-tube is 0.5-3 g/L;
b-2, dispersing polyvinylpyrrolidone in the mixed solution A1Stirring at room temperature for 5-15min, and standing for 10-20min to obtain mixed solution A2The polyvinylpyrrolidone is in A2The concentration of the mixed solution is 20-24 g/L;
b-3, dispersing cobalt nitrate hexahydrate in an anhydrous methanol solvent to form a uniform mixed solution B when preparing an organic solution of soluble cobalt salt, wherein the molar concentration of the cobalt nitrate hexahydrate is 0.5-1 mmol/L;
b-4, dispersing 2-methylimidazole in an anhydrous methanol solvent to form a uniform mixed solution C when preparing the organic solution of 2-methylimidazole, wherein the molar concentration of 2-methylimidazole is 30-50 mmol/L;
b-5, simultaneously mixing the mixed solution B and the mixed solution C with the mixed solution A2Mixing, and performing coordination reaction, wherein the mixed solution B, the mixed solution C and the mixed solution A2The volume ratio of the dosage of the components is 1:2:1, and the components are magnetically stirred and mixed at room temperature for 2-3 h;
b-6, separating a solid product, comprising the following steps: centrifuging the solid product at the speed of 8000-; repeating the centrifugation for 3-5 times; then washing the solid product with methanol; then collecting the solid product, and drying the solid product in an oven at 50-70 deg.C for a drying time10-20h to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite.
As a preferred embodiment of the present invention, the step c includes the steps of:
c-1. Fe to be prepared in said step b2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in organic solvent isopropanol and subjected to ultrasonic oscillation to form uniform Fe2O3@ ZIF-67 solution of said Fe2O3The dosage ratio of the @ ZIF-67 core-shell structure nano composite material to isopropanol is (10-15) mg, (16-20) mL;
c-2. in said Fe2O33.5-12g thioacetamide is added into the @ ZIF-67 solution, and the mixture is magnetically stirred for 10-15h for etching to obtain a product solution;
c-3, separating a solid product, comprising the following steps: centrifuging the solid product at 8000-; then collecting solid product, drying the solid product in a vacuum oven at 50-70 ℃ for 10-20h, and finally annealing the obtained product at not lower than 300 ℃ for at least 2h to obtain Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
As a preferred technical scheme of the invention, in the step a, the prepared Fe2O3The overall length of the hollow nanotube is 200-400 nm, the outer diameter of the nanotube is 90-110 nm, and the inner diameter of the nanotube is 40-80 nm.
As a preferable technical scheme of the invention, in the step b, ZIF-67 is uniformly grown on Fe through coordination reaction2O3Outside the hollow nanotube, Fe is obtained2O3The @ ZIF-67 core-shell structure nano composite material particles have the average particle size of 400-600 nm.
One kind of Fe of the invention2O3@Co9S8The application of the nano composite material with the double hollow core-shell structure is characterized in that: said Fe2O3@Co9S8The double-hollow core-shell structure nano composite material is used as an electrocatalyst in an electrolytic water oxygen evolution catalytic reaction.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. fe of the invention2O3@Co9S8Preparation method of nano composite material with double hollow core-shell structure, using Fe2O3The hollow nano tube is taken as a substrate, the unique organic-inorganic hybrid functional nano material is successfully constructed by coating ZIF-67 on the outside of the substrate, and Fe is further coated2O3@ ZIF-67 is chemically etched and annealed to convert it into Fe assembled by hollow nanotubes and hollow nanocages2O3@Co9S8The double-hollow core-shell structure nano composite material realizes the structural design, the morphology control and the synergistic effect of a multi-component compound;
2. the preparation method adopted by the invention has the advantages of convenient operation, low cost, simple equipment, less requirements on raw materials and equipment types, and easy observation and control of the process; fe of the invention2O3@Co9S8Preparation method of double-hollow core-shell structure nano composite material, not only in Fe2O3The hollow nanotube is successfully applied as a substrate, and provides a new idea for substrates with other shapes and sizes;
3. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
FIG. 1 is Fe prepared in example 12O3Scanning Electron Microscope (SEM) images of (a).
FIG. 2 is Fe prepared in example 12O3@ ZIF-67 Transmission Electron Microscope (TEM) image.
FIG. 3 is Fe prepared in example 12O3@Co9S8Transmission Electron Microscope (TEM) images of (a).
FIG. 4 is Fe prepared in example 12O3@Co9S8X-ray diffraction (XRD) pattern of (a).
FIG. 5 is Fe prepared in example 52O3@Co9S8Transmission Electron Microscope (TEM) images of (a).
FIG. 6 is Fe prepared in example 62O3@Co9S8Transmission Electron Microscope (TEM) images of (a).
FIG. 7 is Fe prepared in example 7 versus example 12O3@Co9S8The electrochemical test performance diagram of the double hollow core-shell structure nano composite material comprises a diagram a which is a linear scanning voltammetry curve chart; b is a tafel slope diagram; c is a cyclic voltammogram; and d is electrochemical double layer capacitance.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1:
in this example, one kind of Fe2O3@Co9S8The double-hollow core-shell structure nano composite material is characterized in that a double-hollow core-shell structure is formed by a core and a shell coated outside the core, wherein the core is Fe2O3Hollow nanotubes, the shell being Co9S8Hollow nanocage polyhedral material.
In this example, Fe2O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
a-1. preparation of hydrothermal reaction mixture:
preparing anhydrous ferric chloride solution with the molar concentration of 0.5mol/L and ammonium dihydrogen phosphate solution with the molar concentration of 0.02 mol/L; mixing 3.2mL of ferric chloride solution and 2.88mL of ammonium dihydrogen phosphate solution, adding deionized water until the volume reaches 80mL, diluting, and stirring to form uniform solution; obtaining a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
transferring the mixed solution to a containerPlacing the high-pressure reaction kettle in a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, placing the high-pressure reaction kettle in a 220 ℃ drying oven for reaction for 48 hours, and cooling to room temperature after the reaction is finished; removing supernatant of the product, centrifuging, adding deionized water for resuspension, centrifuging and washing for 3 times, adding ethanol for resuspension, centrifuging and washing for 3 times, drying in an oven at 60 ℃ for 12h to obtain Fe2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe2O3Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10 min; then 50mL of cobalt nitrate hexahydrate methanol solution with the molar concentration of 0.69mmol/L and 100mL of 2-methylimidazole methanol solution with the molar concentration of 36mmol/L are poured into the above solutions at the same time for mixing, and magnetic stirring is carried out at room temperature for 2 hours of coordination reaction; after the completion, the product is centrifugally separated, added with methanol for heavy suspension, centrifugally washed for 3 times, and dried in an oven at 60 ℃ for 12 hours to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in 200mL of isopropanol and ultrasonically vibrated to form a uniform solution; adding 7.48g of thioacetamide, magnetically stirring for 12h at room temperature for chemical etching, performing centrifugal separation, adding ethanol for resuspension, performing centrifugal washing for 3 times, and drying in a vacuum oven at 60 ℃ for 12 h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
Experimental test analysis:
the intermediate products and final products prepared in this example were used as test samples to perform the examination, and FIG. 1 shows Fe prepared in this example2O3The Scanning Electron Microscope (SEM) picture of the hollow nanotube shows that the nanotube has complete structure, smooth surface, uniform dispersion and large and small sizeThe nano tube has uniform length of 200-400 nm, the outer diameter of the nano tube is 90-110 nm, and the inner diameter is 40-80 nm. FIG. 2 shows Fe prepared in this example2O3In a Transmission Electron Microscope (TEM) picture of the @ ZIF-67 core-shell structure nanocomposite, it can be seen that the ZIF-67 grows uniformly in Fe2O3The average particle size of the hollow nano-tube is 400-600 nm. FIG. 3 shows Fe prepared in this example2O3@Co9S8In the Transmission Electron Microscope (TEM) image of the double hollow core-shell structure nanocomposite, Fe can be seen2O3@ ZIF-67 after normal temperature vulcanization of thioacetamide, the material retained the overall morphology. Fe2O3The hollow nano-tube is not obviously changed, and ZIF-67 is vulcanized into Co with a hollow structure9S8Nanocage, and Co9S8The surface of the hollow nanocages is no longer smooth and flat, thus exposing a large number of active sites. FIG. 4 shows Fe prepared in this example2O3@Co9S8The X-ray diffraction (XRD) pattern of the double-hollow core-shell structure nano composite material can be seen, and the pattern is Fe corresponding to JCPDS standard card No.33-0664 and JCPDS standard card No.19-03642O3Diffraction peaks and Co9S8Diffraction peaks are completely coincided, and the obtained product is well proved to be Fe2O3@Co9S8A composite material.
Example 2:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
in this example, Fe2O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
a-1. preparation of hydrothermal reaction mixture:
preparing anhydrous ferric chloride solution with the molar concentration of 0.5mol/L and ammonium dihydrogen phosphate solution with the molar concentration of 0.02 mol/L; mixing 3.2mL of ferric chloride solution and 5.76mL of ammonium dihydrogen phosphate solution, adding deionized water until the volume reaches 80mL, diluting, and stirring to form uniform solution; obtaining a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, placing the high-pressure autoclave in a drying oven at 220 ℃ for reacting for 48 hours, and cooling to room temperature after the reaction is finished; removing supernatant of the product, centrifuging, adding deionized water for resuspension, centrifuging and washing for 3 times, adding ethanol for resuspension, centrifuging and washing for 3 times, drying in an oven at 60 ℃ for 12h to obtain Fe2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe2O3Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10 min; then 50mL of cobalt nitrate hexahydrate methanol solution with the molar concentration of 0.69mmol/L and 100mL of 2-methylimidazole methanol solution with the molar concentration of 36mmol/L are poured into the above solutions at the same time for mixing, and magnetic stirring is carried out at room temperature for 2 hours of coordination reaction; after the completion, the product is centrifugally separated, added with methanol for heavy suspension, centrifugally washed for 3 times, and dried in an oven at 60 ℃ for 12 hours to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in 200mL of isopropanol and ultrasonically vibrated to form a uniform solution; adding 7.48g of thioacetamide, magnetically stirring for 12h at room temperature for chemical etching, performing centrifugal separation, adding ethanol for resuspension, performing centrifugal washing for 3 times, and drying in a vacuum oven at 60 ℃ for 12 h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
Example 3:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, Fe2O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
a-1. preparation of hydrothermal reaction mixture:
preparing anhydrous ferric chloride solution with the molar concentration of 0.5mol/L and ammonium dihydrogen phosphate solution with the molar concentration of 0.02 mol/L; mixing 3.2mL of ferric chloride solution and 2.88mL of ammonium dihydrogen phosphate solution, adding deionized water until the volume reaches 80mL, diluting, and stirring to form uniform solution; obtaining a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, placing the high-pressure autoclave in a drying oven at 220 ℃ for reacting for 48 hours, and cooling to room temperature after the reaction is finished; removing supernatant of the product, centrifuging, adding deionized water for resuspension, centrifuging and washing for 3 times, adding ethanol for resuspension, centrifuging and washing for 3 times, drying in an oven at 60 ℃ for 12h to obtain Fe2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 0.5g/L Fe2O3Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10 min; then 50mL of cobalt nitrate hexahydrate methanol solution with the molar concentration of 0.69mmol/L and 100mL of 2-methylimidazole methanol solution with the molar concentration of 36mmol/L are poured into the above solutions at the same time for mixing, and magnetic stirring is carried out at room temperature for 2 hours of coordination reaction; after the completion, the product is centrifugally separated, added with methanol for heavy suspension, centrifugally washed for 3 times, and dried in an oven at 60 ℃ for 12 hours to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in 200mL of isopropanol and ultrasonically vibrated to form a uniform solution; adding 7.48g of thioacetamide, magnetically stirring for 12h at room temperature for chemical etching, performing centrifugal separation, adding ethanol for resuspension, performing centrifugal washing for 3 times, and drying in a vacuum oven at 60 ℃ for 12 h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
Example 4:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, Fe2O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
a-1. preparation of hydrothermal reaction mixture:
preparing anhydrous ferric chloride solution with the molar concentration of 0.5mol/L and ammonium dihydrogen phosphate solution with the molar concentration of 0.02 mol/L; mixing 3.2mL of ferric chloride solution and 2.88mL of ammonium dihydrogen phosphate solution, adding deionized water until the volume reaches 80mL, diluting, and stirring to form uniform solution; obtaining a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, placing the high-pressure autoclave in a drying oven at 220 ℃ for reacting for 48 hours, and cooling to room temperature after the reaction is finished; removing supernatant of the product, centrifuging, adding deionized water for resuspension, centrifuging and washing for 3 times, adding ethanol for resuspension, centrifuging and washing for 3 times, drying in an oven at 60 ℃ for 12h to obtain Fe2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 2g/L Fe2O3Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10 min; then 50mL of cobalt nitrate hexahydrate methanol solution with the molar concentration of 0.69mmol/L and 100mL of 2-methylimidazole methanol solution with the molar concentration of 36mmol/L are poured into the above solutions at the same time for mixing, and magnetic stirring is carried out at room temperature for 2 hours of coordination reaction; after the completion, the product is centrifugally separated, added with methanol for heavy suspension, centrifugally washed for 3 times, and dried in an oven at 60 ℃ for 12 hours to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in 200mL of isopropanol and ultrasonically vibrated to form a uniform solution; adding 7.48g of thioacetamide, magnetically stirring for 12h at room temperature for chemical etching, performing centrifugal separation, adding ethanol for resuspension, performing centrifugal washing for 3 times, and drying in a vacuum oven at 60 ℃ for 12 h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
Example 5:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, Fe2O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
a-1. preparation of hydrothermal reaction mixture:
preparing anhydrous ferric chloride solution with the molar concentration of 0.5mol/L and ammonium dihydrogen phosphate solution with the molar concentration of 0.02 mol/L; mixing 3.2mL of ferric chloride solution and 2.88mL of ammonium dihydrogen phosphate solution, adding deionized water until the volume reaches 80mL, diluting, and stirring to form uniform solution; obtaining a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, placing the high-pressure autoclave in a drying oven at 220 ℃ for reacting for 48 hours, and cooling to room temperature after the reaction is finished; removing supernatant of the product, centrifuging, adding deionized water for resuspension, centrifuging and washing for 3 times, adding ethanol for resuspension, centrifuging and washing for 3 times, drying in an oven at 60 ℃ for 12h to obtain Fe2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe2O3Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10 min; then 50mL of cobalt nitrate hexahydrate methanol solution with the molar concentration of 0.69mmol/L and 100mL of 2-methylimidazole methanol solution with the molar concentration of 36mmol/L are poured into the above solutions at the same time for mixing, and magnetic stirring is carried out at room temperature for 2 hours of coordination reaction; after the completion, the product is centrifugally separated, added with methanol for heavy suspension, centrifugally washed for 3 times, and dried in an oven at 60 ℃ for 12 hours to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in 200mL of isopropanol and ultrasonically vibrated to form a uniform solution; adding 7.48g of thioacetamide, magnetically stirring for 12h at room temperature for chemical etching, performing centrifugal separation, adding ethanol for resuspension, performing centrifugal washing for 3 times, and drying in a vacuum oven at 60 ℃ for 12 h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
Experimental test analysis:
FIG. 5 shows Fe prepared in this example2O3@Co9S8A double hollow core-shell structure nano composite material. As can be seen, the product is Fe2O3External to the hollow nanotubesCo9S8The nanocage was less open than the product prepared in example 1, indicating that reducing the amount of thioacetamide reduced the degree of vulcanization.
Example 6:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, Fe2O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
a-1. preparation of hydrothermal reaction mixture:
preparing anhydrous ferric chloride solution with the molar concentration of 0.5mol/L and ammonium dihydrogen phosphate solution with the molar concentration of 0.02 mol/L; mixing 3.2mL of ferric chloride solution and 2.88mL of ammonium dihydrogen phosphate solution, adding deionized water until the volume reaches 80mL, diluting, and stirring to form uniform solution; obtaining a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, placing the high-pressure autoclave in a drying oven at 220 ℃ for reacting for 48 hours, and cooling to room temperature after the reaction is finished; removing supernatant of the product, centrifuging, adding deionized water for resuspension, centrifuging and washing for 3 times, adding ethanol for resuspension, centrifuging and washing for 3 times, drying in an oven at 60 ℃ for 12h to obtain Fe2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe2O3Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10 min; then 50mL of cobalt nitrate hexahydrate methanol solution with the molar concentration of 0.69mmol/L and 100mL of 2-methylimidazole methanol solution with the molar concentration of 36mmol/L are poured into the above solutions at the same time for mixing, and magnetic stirring is carried out at room temperature for 2 hours of coordination reaction; centrifuging the product after finishing, adding methanol for resuspension, and centrifugingWashing for 3 times, drying in an oven at 60 ℃ for 12h to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in 200mL of isopropanol and ultrasonically vibrated to form a uniform solution; adding 11.22g thioacetamide, magnetically stirring at room temperature for 12h for chemical etching, performing centrifugal separation, adding ethanol for resuspension, performing centrifugal washing for 3 times, and drying in a vacuum oven at 60 ℃ for 12 h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
Experimental test analysis:
FIG. 6 shows Fe prepared in this example2O3@Co9S8A double hollow core-shell structure nano composite material. As can be seen, the product is Fe2O3Co outside of hollow nanotubes9S8The nanocages were partially fragmented and the morphology and structure of ZIF-67 could not be fully maintained, indicating that increasing the amount of thioacetamide exacerbates the degree of vulcanization leading to morphology collapse.
Example 7:
in this example, performance testing was performed as follows:
1) preparing a working electrode: the catalyst ink was prepared from 3mg of the prepared material by mixing 55 μ L ethanol, 165 μ L deionized water and 20 μ L of the Afion solution and sonicating for 30 min. Dripping 80 mu L of catalyst ink on the surface of the foamed nickel electrode, and drying to prepare a working electrode;
2) assembling a three-electrode system: taking an Hg/HgO electrode as a reference electrode, a graphite rod electrode as a counter electrode, a foam nickel electrode loaded with a catalyst as a working electrode, and taking a 1.0M KOH solution as an electrolyte at room temperature for testing;
3) the polarization curve test scan rate was 5mV/s and 90% iR compensation was performed. Electrochemical double layer capacitance (C)dl) By different scan rates (10mVs, 20mV/s, 40mV/s, 60mV/s, 80mV/s, 100 mV/s). The tafel slope is obtained by calculating and converting a linear scanning voltammogram.
FIG. 7 shows Fe prepared in this example for example 12O3@Co9S8And (3) performing an electrochemical test performance diagram on the double-hollow core-shell structure nano composite material. It can be seen that in a 1.0M KOH electrolyte, Fe2O3@Co9S8The catalyst has excellent catalytic efficiency. a linear sweep voltammogram at 10mAcm-2The overpotential is only 205mV at 100mAcm-2Under the current density, the overpotential reaches 281mV, and the graph b shows that the Tafel slope of the material is 69mVdec-1Calculating electrochemical double layer capacitance according to cyclic voltammogram of the graph c, and as shown in the graph d, the electrochemical double layer capacitance of the material reaches 15.47mF cm-2. This indicates that Fe2O3@Co9S8The double-hollow core-shell structure nano composite material is convenient in charge transfer, has rich active sites, and has strong synergistic effect of the components, so that the catalytic efficiency in electrochemical decomposition of water is excellent.
In summary, the above embodiments prepare the TMC nanocomposite by doping the substrate and using the MOFs material as the precursor. The unique structure and morphology of the catalyst and the synergistic effect of the multi-component compound can further reduce the charge transfer resistance, enrich the active sites and achieve the purpose of improving the performance of the catalyst. Examples Fe above2O3@Co9S8The preparation method and the application of the double-hollow core-shell structure nano composite material comprise the following steps: 1) mixing and diluting ferric chloride solution and ammonium dihydrogen phosphate solution in proportion, and synthesizing Fe by a hydrothermal method2O3A hollow nanotube; 2) mixing Fe2O3Dispersing the nanotube in an organic solvent, adding polyvinylpyrrolidone, mixing with a soluble cobalt salt solution and a 2-methylimidazole solution, stirring, separating, washing and drying to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite; 3) mixing Fe2O3Dissolving the @ ZIF-67 composite material in an organic solvent, adding thioacetamide for etching, stirring, separating, washing, drying, and annealing to obtain Fe2O3@Co9S8A double hollow core-shell structure nano composite material. The preparation method provided by the invention is convenient and reliable, low in cost, simple in equipment and easy to observe and control in process, successfully realizes the shape regulation and control of the double-hollow core-shell structure, and simultaneously the Fe2O3@Co9S8The nano composite material has excellent electrochemical performance, so that the nano composite material is applied to electrolytic water oxygen evolution catalytic reaction.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, but various changes, modifications, substitutions, combinations or simplifications may be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the present invention should be made in an equivalent manner to the purpose of the invention without departing from the invention2O3@Co9S8The double hollow core-shell structure nano composite material, the preparation method thereof, the technical principle of the application and the inventive concept belong to the protection scope of the invention.
Claims (8)
1. Fe2O3@Co9S8The double-hollow core-shell structure nano composite material is characterized in that: the double-hollow core-shell structure consists of a core and a shell coated outside the core, wherein the core is Fe2O3Hollow nanotubes, the shell being Co9S8Hollow nanocage polyhedral material.
2. Fe as defined in claim 12O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material is characterized by comprising the following steps:
a. synthesis of Fe2O3The process of hollow nanotube:
mixing ferric chloride solution and ammonium dihydrogen phosphate solution in proportion, and diluting the mixed solutionAfter release, Fe is obtained by hydrothermal reaction and synthesis2O3A hollow nanotube;
b. preparation of Fe2O3The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
subjecting the Fe obtained in step a to2O3Dispersing hollow nanotubes in an organic solvent, adding polyvinylpyrrolidone, mixing with an organic solution of soluble cobalt salt and an organic solution of 2-methylimidazole, stirring for reaction, and then separating, washing and drying a solid product to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite;
c.Fe2O3@Co9S8the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
subjecting the Fe obtained in step b to2O3The @ ZIF-67 core-shell structure nano composite material is dissolved in an organic solvent, thioacetamide is added for etching, and after stirring, solid product separation, washing and drying are carried out to obtain Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
3. Fe according to claim 22O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step a, Fe is used2O3The preparation method of the hollow nanotube comprises the following steps:
a-1. preparation of hydrothermal reaction mixture:
the ferric chloride solution adopts a mixed solution of ferric chloride and ultrapure water, and the molar concentration of the ferric chloride in the ferric chloride solution is 0.5-1 mol/L; the ammonium dihydrogen phosphate solution adopts a mixed solution of ammonium dihydrogen phosphate and ultrapure water, and the molar concentration of the ammonium dihydrogen phosphate in the ammonium dihydrogen phosphate solution is 0.01-0.05 mol/L; the volume usage ratio of the ferric chloride solution to the ammonium dihydrogen phosphate solution is (3-4) to (2.5-6), and 70-85mL of ultrapure water is added into the mixed solution of the ferric chloride solution and the ammonium dihydrogen phosphate solution for dilution to obtain a hydrothermal reactant mixed solution for later use;
a-2, hydrothermal synthesis reaction process and primary separation treatment:
the hydrothermal synthesis conditions are as follows: b, putting the hydrothermal reactant mixed solution prepared in the step a-1 into a polytetrafluoroethylene reaction kettle, heating to a temperature not lower than 220 ℃, carrying out hydrothermal reaction for at least 48 hours to obtain a product, removing a supernatant, carrying out centrifugal separation, and then washing with deionized water and ethanol in sequence to obtain a solution of a purified product;
a-3, separating solid product and post-processing:
the specific steps for separating the solid product are as follows: centrifuging the solution of the product purified in the step a-2 at the rotation speed of 8000-;
a-4, repeating the operation in the step a-3 for 6-8 times, then collecting the solid product, drying in an oven, controlling the drying temperature to be 50-70 ℃ and the drying time to be 10-20h, and obtaining Fe2O3Hollow nanotubes.
4. Fe according to claim 22O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step b, Fe is used2O3The preparation method of the @ ZIF-67 core-shell structure nano composite material comprises the following steps:
b-1. Fe to be prepared in said step a2O3Dispersing the hollow nano-tube in an anhydrous methanol solvent to form a mixed solution A1Setting Fe2O3The concentration of the hollow nano-tube is 0.5-3 g/L;
b-2, dispersing polyvinylpyrrolidone in the mixed solution A1Stirring at room temperature for 5-15min, and standing for 10-20min to obtain mixed solution A2The polyvinylpyrrolidone is in A2The concentration of the mixed solution is 20-24 g/L;
b-3, dispersing cobalt nitrate hexahydrate in an anhydrous methanol solvent to form a uniform mixed solution B when preparing an organic solution of soluble cobalt salt, wherein the molar concentration of the cobalt nitrate hexahydrate is 0.5-1 mmol/L;
b-4, dispersing 2-methylimidazole in an anhydrous methanol solvent to form a uniform mixed solution C when preparing the organic solution of 2-methylimidazole, wherein the molar concentration of 2-methylimidazole is 30-50 mmol/L;
b-5, simultaneously mixing the mixed solution B and the mixed solution C with the mixed solution A2Mixing, and performing coordination reaction, wherein the mixed solution B, the mixed solution C and the mixed solution A2The volume ratio of the dosage of the components is 1:2:1, and the components are magnetically stirred and mixed at room temperature for 2-3 h;
b-6, separating a solid product, comprising the following steps: centrifuging the solid product at the speed of 8000-; repeating the centrifugation for 3-5 times; then washing the solid product with methanol; then collecting the solid product, drying the solid product in an oven at 50-70 ℃ for 10-20h to obtain Fe2O3@ ZIF-67 core-shell structure nanocomposite.
5. Fe according to claim 22O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step c, the method comprises the following steps:
c-1. Fe to be prepared in said step b2O3The @ ZIF-67 core-shell structure nano composite material is dispersed in organic solvent isopropanol and subjected to ultrasonic oscillation to form uniform Fe2O3@ ZIF-67 solution of said Fe2O3The dosage ratio of the @ ZIF-67 core-shell structure nano composite material to isopropanol is (10-15) mg, (16-20) mL;
c-2. in said Fe2O33.5-12g thioacetamide is added into the @ ZIF-67 solution, and the mixture is magnetically stirred for 10-15h for etching to obtain a product solution;
c-3, separating a solid product, comprising the following steps: the solid product was transferred at a rate of 8000-Centrifuging for 5-10min, discarding supernatant, adding ethanol, resuspending, centrifuging again, repeating the above centrifuging operation for 3-5 times, and washing solid product with ethanol; then collecting solid product, drying the solid product in a vacuum oven at 50-70 ℃ for 10-20h, and finally annealing the obtained product at not lower than 300 ℃ for at least 2h to obtain Fe2O3@Co9S8A double hollow core-shell structure nano composite material.
6. Fe according to any one of claims 1 to 52O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step a, the prepared Fe2O3The overall length of the hollow nanotube is 200-400 nm, the outer diameter of the nanotube is 90-110 nm, and the inner diameter of the nanotube is 40-80 nm.
7. Fe according to any one of claims 1 to 52O3@Co9S8The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step b, ZIF-67 uniformly grows on Fe through coordination reaction2O3Outside the hollow nanotube, Fe is obtained2O3The @ ZIF-67 core-shell structure nano composite material particles have the average particle size of 400-600 nm.
8. Fe as defined in claim 12O3@Co9S8The application of the nano composite material with the double hollow core-shell structure is characterized in that: said Fe2O3@Co9S8The double-hollow core-shell structure nano composite material is used as an electrocatalyst in an electrolytic water oxygen evolution catalytic reaction.
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| CN113477253A (en) * | 2021-07-21 | 2021-10-08 | 电子科技大学 | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material |
| CN113860381A (en) * | 2021-10-09 | 2021-12-31 | 国家能源集团科学技术研究院有限公司 | Magnetic heteroplasmon nano material and preparation method thereof |
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| CN101259401A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball and hollow ball with complex structure by template method |
| CN108301017A (en) * | 2018-03-12 | 2018-07-20 | 郑州大学 | A kind of water electrolysis hydrogen production catalyst Co9S8@CNT and preparation method thereof |
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| CN113477253A (en) * | 2021-07-21 | 2021-10-08 | 电子科技大学 | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material |
| CN113860381A (en) * | 2021-10-09 | 2021-12-31 | 国家能源集团科学技术研究院有限公司 | Magnetic heteroplasmon nano material and preparation method thereof |
| CN113860381B (en) * | 2021-10-09 | 2024-01-26 | 国家能源集团科学技术研究院有限公司 | Magnetic heteroplasmon nanometer material and preparation method thereof |
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