CN111804313B - Fe 2 O 3 @Co 9 S 8 Preparation method and application of double-hollow core-shell structure nano composite material - Google Patents
Fe 2 O 3 @Co 9 S 8 Preparation method and application of double-hollow core-shell structure nano composite material Download PDFInfo
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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
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses Fe 2 O 3 @Co 9 S 8 The 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 method 2 O 3 A hollow nanotube; then adding Fe 2 O 3 Dispersing 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite; then adding Fe 2 O 3 Dissolving the @ ZIF-67 composite material in an organic solvent, adding thioacetamide for etching, stirring, separating, washing, drying, and annealing to obtain Fe 2 O 3 @Co 9 S 8 A nano composite material with double hollow core-shell structure. The method is convenient and reliable, low in cost, simple in equipment and easy to observe and control in the process, and realizes the shape regulation and control of the double-hollow core-shell structure.
Description
Technical Field
The invention belongs to the technical field of synthesis of functional nano materials, and particularly relates to a method for preparing Fe 2 O 3 @Co 9 S 8 A 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 world economy, human beings face a huge challenge of depletion of fossil fuel, and in the development of a plurality of renewable energy sources, hydrogen energy is paid much attention as a non-intermittent clean energy source because the hydrogen energy can be subjected to clean and effective cyclic conversion between chemical energy and electric energy, and electrochemical water decomposition hydrogen production gradually becomes a high-prospect approach for industrial hydrogen production. Therefore, the development of excellent electrocatalysts to reduce the consumption of excessive electric energy in the electrolyzed water and to accelerate the reaction rate is the current research focus.
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 maintains the morphology, the pore channel and the specific surface area of the precursor MOFs material 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 such as 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 some TMC is close to that of a noble metal catalyst.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide Fe 2 O 3 @Co 9 S 8 The 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 Fe 2 O 3 @Co 9 S 8 The 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:
fe 2 O 3 @Co 9 S 8 The 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 Fe 2 O 3 Hollow nano-meterA tube, the shell being Co 9 S 8 Hollow nanocage polyhedral material.
One kind of Fe of the invention 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe 2 O 3 A hollow nanotube process:
mixing ferric chloride solution and ammonium dihydrogen phosphate solution in proportion, diluting the mixed solution, and synthesizing to obtain Fe through hydrothermal reaction 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
subjecting the Fe obtained in step a to 2 O 3 Dispersing 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
subjecting the Fe obtained in step b to 2 O 3 The @ 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 Fe 2 O 3 @Co 9 S 8 A double hollow core-shell structure nano composite material.
In a preferred embodiment of the present invention, in the step a, the Fe 2 O 3 The 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 0.5-1mol/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 0.01-0.05mol/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 a solid product and performing post-treatment:
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 rotating speed of 8000-10000rpm for 5-10min, discarding the supernatant, adding deionized water or ethanol into the product for re-suspension, and centrifuging again to finish the step of separating a solid product for one time;
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 Fe 2 O 3 Hollow nanotubes.
In a preferred embodiment of the present invention, in the step b, the Fe is 2 O 3 The 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 a 2 O 3 Dispersing the hollow nano-tube in an anhydrous methanol solvent to form a mixed solution A 1 Setting Fe 2 O 3 The concentration of the hollow nano-tube is 0.5-3g/L;
b-2, dispersing polyvinylpyrrolidone in the mixed solution A 1 Stirring at room temperature for 5-15min, and standing for 10-20min to obtain mixed solution A 2 Said poly (A) isVinylpyrrolidone in A 2 The concentration of the mixed solution is 20-24g/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 a soluble cobalt salt, wherein the molar concentration of the cobalt nitrate hexahydrate is 0.5-1mmol/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 30-50mmol/L;
b-5, simultaneously mixing the mixed solution B and the mixed solution C with the mixed solution A 2 Mixing, and performing coordination reaction, wherein the mixed solution B, the mixed solution C and the mixed solution A 2 The volume ratio of the used amount of the organic solvent to the used amount of the organic solvent is 1;
b-6, separating a solid product, comprising the following steps: centrifuging the solid product at 8000-10000rpm for 5-10min, discarding supernatant, adding methanol for resuspension, and centrifuging again; 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 Fe 2 O 3 @ 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 b 2 O 3 The @ ZIF-67 core-shell structure nano composite material is dispersed in organic solvent isopropanol and subjected to ultrasonic oscillation to form uniform Fe 2 O 3 @ ZIF-67 solution of said Fe 2 O 3 The 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 Fe 2 O 3 3.5-12g 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 is then added at a rate of 8000-1Centrifuging at 0000rpm 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 Fe 2 O 3 @Co 9 S 8 A nano composite material with double hollow core-shell structure.
As a preferred technical scheme of the invention, in the step a, the prepared Fe 2 O 3 The whole 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 reaction 2 O 3 Outside the hollow nanotube, fe is obtained 2 O 3 The average size of the @ ZIF-67 core-shell structure nano composite material particles is 400-600 nm.
One kind of Fe of the invention 2 O 3 @Co 9 S 8 The application of the nano composite material with the double hollow core-shell structure is characterized in that: said Fe 2 O 3 @Co 9 S 8 The 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 invention 2 O 3 @Co 9 S 8 Preparation method of nano composite material with double hollow core-shell structure, using Fe 2 O 3 The 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 coated 2 O 3 @ ZIF-67 is chemically etched and annealed to convert it into Fe assembled by hollow nanotubes and hollow nanocages 2 O 3 @Co 9 S 8 The nano composite material with double hollow core-shell structure realizes structural design, shape regulation and control and multiple elementsSynergistic effects of the compounds;
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 invention 2 O 3 @Co 9 S 8 Preparation method of nano composite material with double hollow core-shell structure, not only in Fe 2 O 3 The 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 1 2 O 3 Scanning Electron Microscope (SEM) images of (a).
FIG. 2 is Fe prepared in example 1 2 O 3 @ ZIF-67 Transmission Electron Microscope (TEM) image.
FIG. 3 is Fe prepared in example 1 2 O 3 @Co 9 S 8 Transmission Electron Microscope (TEM) images of (a).
FIG. 4 is Fe prepared in example 1 2 O 3 @Co 9 S 8 X-ray diffraction (XRD) pattern of (a).
FIG. 5 is Fe prepared in example 5 2 O 3 @Co 9 S 8 Transmission Electron Microscope (TEM) images of (a).
FIG. 6 is Fe prepared in example 6 2 O 3 @Co 9 S 8 Transmission Electron Microscope (TEM) images of (a).
FIG. 7 is Fe prepared in example 7 versus example 1 2 O 3 @Co 9 S 8 The 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 Fe 2 O 3 @Co 9 S 8 The 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 Fe 2 O 3 Hollow nanotubes, the shell being Co 9 S 8 Hollow nanometer cage polyhedral material.
In this example, fe 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe 2 O 3 The 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, a hydrothermal synthesis reaction process and a 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 Fe 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe 2 O 3 Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10min; 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 simultaneously for mixing, and magnetic stirring is carried out at room temperature for 2 hoursPerforming 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite 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 12h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe 2 O 3 @Co 9 S 8 A 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 example 2 O 3 The Scanning Electron Microscope (SEM) picture of the hollow nanotube shows that the nanotube has complete structure, smooth surface, even dispersion and uniform size, the integral length is 200-400 nm, the outer diameter of the nanotube is 90-110 nm, and the inner diameter is 40-80 nm. FIG. 2 shows Fe prepared in this example 2 O 3 A Transmission Electron Microscope (TEM) picture of the @ ZIF-67 core-shell structure nanocomposite material can see that the ZIF-67 grows uniformly on Fe 2 O 3 The average particle size of the hollow nanotube is 400-600 nm. FIG. 3 shows Fe prepared in this example 2 O 3 @Co 9 S 8 In a Transmission Electron Microscope (TEM) image of the double-hollow core-shell structure nanocomposite, fe can be seen 2 O 3 @ ZIF-67 after thioacetamide vulcanization at normal temperature, the substance maintains the integral morphology. Fe 2 O 3 The hollow nano tube is not obviously changed, and ZIF-67 is vulcanized into Co with a hollow structure 9 S 8 Nanocage, and Co 9 S 8 The surface of the hollow nano cage is not smooth any more, so that a large amount of the nano cage is exposedThe active site of (1). FIG. 4 shows Fe prepared in this example 2 O 3 @Co 9 S 8 The 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.19-0364 2 O 3 Diffraction peaks and Co 9 S 8 The diffraction peaks are completely matched, and the obtained product is well proved to be Fe 2 O 3 @Co 9 S 8 A composite material.
Example 2:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
in this example, fe 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe 2 O 3 The 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 lining 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 Fe 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite process:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe 2 O 3 Mixing the hollow nanotube methanol solution in a chamberMagnetically stirring at room temperature for 5min, and standing for 10min; 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 the mixture is magnetically stirred at room temperature for carrying out coordination reaction for 2 hours; 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite 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 12h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe 2 O 3 @Co 9 S 8 A 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, fe 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe 2 O 3 A hollow nanotube process:
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:
mixing the solutionTransferring the solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, placing the 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 Fe 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 The 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 Fe 2 O 3 Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10min; 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 the mixture is magnetically stirred at room temperature for carrying out coordination reaction for 2 hours; centrifuging and separating the product after the reaction is finished, adding methanol for re-suspension, centrifuging and washing for 3 times, and drying in an oven at 60 ℃ for 12h to obtain Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe 2 O 3 The @ 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 12h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe 2 O 3 @Co 9 S 8 A 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, fe 2 O 3 @Co 9 S 8 The preparation method of the nano composite material with the double hollow core-shell structure comprises the following steps：
a. Synthesis of Fe 2 O 3 The 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, a hydrothermal synthesis reaction process and a primary separation treatment:
transferring the mixed solution into a polytetrafluoroethylene lining 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 Fe 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 2g/L Fe 2 O 3 Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10min; 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 simultaneously for mixing, and are magnetically stirred at room temperature for carrying out coordination reaction for 2 hours; 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite is dispersed in 200mL of isopropanol and ultrasonically vibrated to form a uniform solution; 7.48g thioacetamide was added and stirred magnetically at room temperatureAfter chemical etching is carried out for 12 hours, centrifugal separation is carried out, ethanol is added for resuspension, then centrifugal washing is carried out for 3 times, and the obtained product is dried for 12 hours in a vacuum oven at the temperature of 60 ℃; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe 2 O 3 @Co 9 S 8 A nano composite material with double hollow core-shell structure.
Example 5:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, fe 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe 2 O 3 A hollow nanotube process:
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 Fe 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe 2 O 3 Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10min; then 50mL of cobalt nitrate hexahydrate methanol solution with the molar concentration of 0.69mmol/L and 100mL of 2-methylimidazol methanol with the molar concentration of 36mmol/L are addedPouring the solution into the solution simultaneously, mixing, magnetically stirring at room temperature, and performing coordination reaction for 2h; 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe 2 O 3 The @ 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 12h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe 2 O 3 @Co 9 S 8 A double hollow core-shell structure nano composite material.
Experimental test analysis:
FIG. 5 shows Fe prepared in this example 2 O 3 @Co 9 S 8 A double hollow core-shell structure nano composite material. As can be seen, the product Fe 2 O 3 Co outside of hollow nanotubes 9 S 8 The 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, fe 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material comprises the following steps:
a. synthesis of Fe 2 O 3 The 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, a hydrothermal synthesis reaction process and a 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 Fe 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite process:
1.2g polyvinylpyrrolidone was added to 50mL of 1g/L Fe 2 O 3 Mixing the hollow nanotube methanol mixed solution, magnetically stirring at room temperature for 5min, and standing for 10min; 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 simultaneously for mixing, and are magnetically stirred at room temperature for carrying out coordination reaction for 2 hours; 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
120mg of Fe 2 O 3 The @ 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 12h; annealing the obtained product at the temperature of 300 ℃ for 2h to obtain the Fe 2 O 3 @Co 9 S 8 A double hollow core-shell structure nano composite material.
Experimental test analysis:
FIG. 6 shows Fe prepared in this example 2 O 3 @Co 9 S 8 A nano composite material with double hollow core-shell structure. As can be seen, the product is Fe 2 O 3 Co outside of hollow nanotubes 9 S 8 The 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 with the following steps:
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 an 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 ) Determined from Cyclic Voltammograms (CV) at different scan rates (10 mV/s, 20mV/s, 40mV/s, 60mV/s, 80mV/s, 100 mV/s). The tafel slope is calculated and converted from a linear sweep voltammogram.
FIG. 7 shows Fe prepared in this example for example 1 2 O 3 @Co 9 S 8 And (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, fe 2 O 3 @Co 9 S 8 The catalyst has excellent catalytic efficiency. a linear sweep voltammogram at 10mAcm -2 The overpotential is only 205mV at 100mAcm -2 Under the current density, the overpotential reaches 281mV, the b diagram shows that the Tafel slope of the material is only 69mVdec -1 Calculating electrochemical double-layer capacitance by cyclic voltammogram of graph c, such as graph dThe electrochemical double layer capacitance of the material reaches 15.47mF cm -2 . This indicates that Fe 2 O 3 @Co 9 S 8 The 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. Example Fe above 2 O 3 @Co 9 S 8 The 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 method 2 O 3 A hollow nanotube; 2) Mixing Fe 2 O 3 Dispersing 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite; 3) Mixing Fe 2 O 3 Dissolving the @ ZIF-67 composite material in an organic solvent, adding thioacetamide for etching, stirring, separating, washing, drying, and annealing to obtain Fe 2 O 3 @Co 9 S 8 A nano composite material with double hollow core-shell structure. 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 Fe 2 O 3 @Co 9 S 8 The nano composite material has excellent electrochemical performance, so that the nano composite material is applied to electrolytic water oxygen evolution catalytic reaction.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes can be made according to the purpose of the invention, and the changes can be made according to the spirit and principle of the technical solution of the present inventionVariations, modifications, substitutions, combinations, or simplifications are intended to be equivalent substitutions without departing from the scope of the invention 2 O 3 @Co 9 S 8 The technical principles and inventive concepts of the double-hollow core-shell structure nano composite material, the preparation method and the application thereof all belong to the protection scope of the invention.
Claims (8)
1. Fe 2 O 3 @Co 9 S 8 The nano composite material with the double hollow core-shell structure 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 Fe 2 O 3 Hollow nanotubes, the shell being Co 9 S 8 Hollow nanocage polyhedral materials; said Fe 2 O 3 @Co 9 S 8 The double-hollow core-shell structure nano composite material is prepared by the following steps:
a. synthesis of Fe 2 O 3 The 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 reaction 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
subjecting the Fe obtained in step a to 2 O 3 Dispersing 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
subjecting the Fe obtained in step b to 2 O 3 The @ 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 anddrying to obtain Fe 2 O 3 @Co 9 S 8 A double hollow core-shell structure nano composite material.
2. Fe as defined in claim 1 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material is characterized by comprising the following steps:
a. synthesis of Fe 2 O 3 The 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 reaction 2 O 3 A hollow nanotube;
b. preparation of Fe 2 O 3 The process of the @ ZIF-67 core-shell structure nano composite material is as follows:
subjecting the Fe obtained in step a to 2 O 3 Dispersing 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite;
c.Fe 2 O 3 @Co 9 S 8 the preparation process of the double-hollow core-shell structure nano composite material comprises the following steps:
subjecting the Fe obtained in step b to 2 O 3 @ ZIF-67 core-shell structure nanocomposite is dissolved in organic solvent, thioacetamide is added for etching, and after stirring, solid product separation, washing and drying are carried out to obtain Fe 2 O 3 @Co 9 S 8 A double hollow core-shell structure nano composite material.
3. Fe according to claim 2 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step a, fe is used 2 O 3 The 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 0.5-1mol/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 0.01-0.05mol/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, filling 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 purified product solution;
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 rotating speed of 8000-10000rpm for 5-10min, discarding the supernatant, adding deionized water or ethanol into the product for re-suspension, and centrifuging again to finish the step of separating the solid product for one time;
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 Fe 2 O 3 A hollow nanotube.
4. Fe according to claim 2 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step b, fe is used 2 O 3 The preparation method of the @ ZIF-67 core-shell structure nano composite material comprises the following steps:
b-1. Will be in said step aFe prepared in (1) 2 O 3 Dispersing the hollow nano-tube in an anhydrous methanol solvent to form a mixed solution A 1 Setting Fe 2 O 3 The concentration of the hollow nano-tube is 0.5-3g/L;
b-2, dispersing polyvinylpyrrolidone in the mixed solution A 1 Stirring at room temperature for 5-15min, and standing for 10-20min to obtain mixed solution A 2 The polyvinylpyrrolidone is in A 2 The concentration of the mixed solution is 20-24g/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 a soluble cobalt salt, wherein the molar concentration of the cobalt nitrate hexahydrate is 0.5-1mmol/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 30-50mmol/L;
b-5, simultaneously mixing the mixed solution B and the mixed solution C with the mixed solution A 2 Mixing, and performing coordination reaction, wherein the mixed solution B, the mixed solution C and the mixed solution A 2 The volume ratio of the used amount of the compound is 1;
b-6, separating a solid product, comprising the following steps: centrifuging the solid product at 8000-10000rpm for 5-10min, discarding the supernatant, adding methanol, resuspending, and centrifuging again; 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 Fe 2 O 3 @ ZIF-67 core-shell structure nanocomposite.
5. Fe according to claim 2 2 O 3 @Co 9 S 8 The 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 b 2 O 3 @ ZIF-67 core-shell structure nano composite material is dispersed in organic solvent isopropanol and ultrasonically vibrated to form uniform Fe 2 O 3 @ ZIF-67 solution of said Fe 2 O 3 The dosage ratio of the @ ZIF-67 core-shell structure nano composite material to the isopropanol is (10-15) mg, (16-20) mL;
c-2. In said Fe 2 O 3 3.5-12g 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 8000-10000rpm for 5-10min, discarding supernatant, adding ethanol, resuspending, centrifuging again, repeating the above centrifuging operation for 3-5 times, and washing the 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 Fe 2 O 3 @Co 9 S 8 A double hollow core-shell structure nano composite material.
6. Fe according to any one of claims 2 to 5 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step a, the prepared Fe 2 O 3 The whole 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 2 to 5 2 O 3 @Co 9 S 8 The preparation method of the double-hollow core-shell structure nano composite material is characterized in that in the step b, ZIF-67 is uniformly grown on Fe through coordination reaction 2 O 3 Outside the hollow nanotube, fe is obtained 2 O 3 The average size of the @ ZIF-67 core-shell structure nano composite material particles is 400-600 nm.
8. Fe as defined in claim 1 2 O 3 @Co 9 S 8 The application of the nano composite material with the double hollow core-shell structure is characterized in that: said Fe 2 O 3 @Co 9 S 8 The 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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| 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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| 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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| Fe3O4-Decorated Co9S8 Nanoparticles In Situ Grown on Reduced Graphene Oxide: A New and Efficient Electrocatalyst for Oxygen Evolution Reaction;Jing Yang等;《Adv. Funct. Mater.》;20160712;第26卷(第26期);第4712-4721页 * |
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