CN111233048A - Double-shell MnCo2O4Hollow nanosphere material and synthesis method thereof - Google Patents
Double-shell MnCo2O4Hollow nanosphere material and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a double-shell MnCo2O4A synthesis method of hollow nanosphere material comprises the steps of taking glucose oligomer molecule cyclodextrin with a hollow structure as a quasi-template to be dispersed in ethanol, taking cobalt salt and manganese salt as raw materials to be dispersed in a mixed solvent of ethanol and deionized water, dropwise adding salt solution into cyclodextrin dispersion liquid, and preparing MnCo through hydrothermal and simple calcination methods2O4Hollow nanospheres. The method does not need to synthesize a template independently or add any surfactant, and is suitable for preparing the multi-element transition metal oxide hollow nanospheres of different systems; prepared MnCo2O4The hollow nanospheres have important application value in the fields of catalysis, energy storage, conversion and the like, and the synthesis method has the advantages of simple process, high efficiency, strong controllability, environmental friendliness, wide source of raw materials, low price and easiness in obtaining, and is easy to realize scale productionAnd (4) producing.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a double-shell MnCo2O4Hollow nanosphere materials and methods of synthesis thereof.
Background
Transition metal oxides have received great attention in the fields of nanomaterials, energy sources, and catalysis due to their excellent functional characteristics. Among many metal oxides, a binary metal oxide can be considered as a composite compound formed by adding another metal atom to a single-phase metal oxide. Because two transition metal atoms exist, the binary metal oxide has richer chemical valence states than a single metal oxide, thereby showing higher electrochemical activity and catalytic activity; meanwhile, due to the mixed occupation and electronic interaction of two different metal atoms in crystal lattices, the binary metal oxide has better conductivity.
In order to further improve the performance and utilization rate of materials, attempts are continuously made to design and prepare various nanostructures (nanoneedles, nanosheets, nanorods) and multilevel structures (hollow structures, core-shell structures). The hollow nanospheres are nano materials with special structures, have the advantages of high specific surface area, large internal cavity, surface permeability and the like due to the nanoscale and unique hollow structures of the hollow nanospheres, and have great application potential in the fields of lithium ion batteries, supercapacitors, catalysts and the like.
Research and analysis have reported literature that methods for preparing transition metal oxides with hollow structures include a template method, a solvothermal method, a microemulsion method and a sol-gel method. The method is characterized in that the hollow structure nanospheres are prepared by a template method, and a multi-step process of synthesizing a hard template or a soft template, adsorbing or depositing a metal oxide shell on the surface of the template, removing the template and the like is needed. The method has the advantages of complex synthetic steps, complex process, difficult control of the synthetic process and low synthetic efficiency, and greatly limits the large-scale production and application of the method; in addition, in the process of template dispersion, a surfactant and the like are required to be added to ensure that the template is uniformly dispersed in a solvent, and factors such as the molecular structure, polarity and the like of the solvent, the surfactant and the oxide raw material must be considered in the synthesis process, so that the applicability of the template to different system materials is limited.
Therefore, the transition metal oxide hollow nanosphere material with excellent structural performance is developed, a preparation method which is simple, convenient and efficient, controllable in process, high in universality and low in cost is provided, and important research significance and application value are achieved.
Disclosure of Invention
In view of the above, the present invention is directed to provide a double-shell MnCo2O4A hollow nanosphere material; simultaneously providing the double-shell MnCo2O4A method for synthesizing hollow nanosphere material. The invention adopts glucose oligomer molecular cyclodextrin with a hollow structure as a quasi-template, and MnCo can be prepared by solvothermal and simple calcination methods2O4Hollow nanosphere material, and preparation of the resulting MnCo2O4Has unique double-shell hollow structure and uniform grain size. The synthesis method does not need to synthesize a soft template or a hard template independently, does not need to add any surfactant, can directly adjust the structures such as the size, the shell layer number and the like of the nanosphere by changing the synthesis conditions such as the molecular shape of the glucose oligomer, the solvent and the like, is simple and efficient, and has strong universality on different material systems.
In order to achieve the purpose, the invention adopts the following technical scheme:
double-shell MnCo2O4The synthesis method of the hollow nanosphere material comprises the following steps:
(1) dissolving cyclodextrin in ethanol, and performing ultrasonic dispersion until the cyclodextrin is uniformly mixed to obtain a solution A;
(2) uniformly mixing ethanol and deionized water through magnetic stirring to serve as a solvent, adding soluble cobalt salt and manganese salt, and performing ultrasonic treatment until the soluble cobalt salt and the manganese salt are completely dissolved to form a uniform solution B;
(3) dropwise adding the solution B into the solution A under magnetic stirring, and continuously stirring to obtain uniform reaction liquid;
(4) transferring the reaction solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven for heating and carrying out heat preservation reaction, then naturally cooling to room temperature, carrying out centrifugal separation on the product, washing with deionized water and alcohol, and drying to obtain a powdery product;
(5) calcining the powdery product in a heating furnace to obtain double-shell MnCo2O4A hollow nanosphere material.
The cyclodextrin molecule has a hollow cylindrical three-dimensional ring structure, the interior of the cavity of which is hydrophobic, and the exterior of which is hydrophilic. In the reaction process, as the temperature and the pressure of the system are increased, the molecular motion of the cyclodextrin is accelerated and the cyclodextrin is aggregated under the action of hydrogen bonds between hydroxyl groups to form a quasi-template. The metal ions in the cobalt chloride and the manganese chloride are continuously hydrolyzed and deposited on the surface of the cyclodextrin template through the action of hydroxyl to form MnCo2O4The hollow nanosphere has an original skeleton structure. Because the cyclodextrin aggregation process and the metal ion hydrolysis deposition process occur simultaneously, a double-shell structure can be formed.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the concentration of the cyclodextrin in the step (1) is 0.05-0.4mol/L, and the cyclodextrin is any one of α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin.
The beneficial effects of the above technical scheme are: if the concentration of cyclodextrin is too low, too few templates in the solution are not conducive to synthesis of hollow structures and the product yield is low; if the concentration is too high, the cyclodextrin is not easy to disperse, obvious large particles are easy to form during dispersion, and the structure and the uniformity of the hollow sphere are influenced.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the addition amount of the ethanol in the step (2) is40-80% of the volume of the solvent, and the addition amount of the deionized water is 20-60% of the volume of the solvent.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the ratio of the amount of the cobalt salt to the amount of the manganese salt in the step (2) is 2:1, the concentration of the cobalt salt in the solution is 0.02-0.2mol/L, and the concentration of the manganese salt is 0.01-0.1 mol/L.
The beneficial effects of the above technical scheme are: the concentration ranges of the two solutions are determined by comprehensively considering the product amount, the solubility and the difficulty degree of dissolution in the experiment.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the cobalt salt in the step (2) is any one of cobalt chloride, cobalt acetate, cobalt oxalate, cobalt phosphate, cobalt carbonate, cobalt sulfate and cobalt nitrate or any one of hydrates thereof.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the manganese salt in the step (2) is any one of manganese chloride, manganese acetate, manganese oxalate, manganese phosphate, manganese carbonate, manganese sulfate and manganese nitrate or any one of hydrates thereof.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the ultrasonic time in the step (2) is 1-2 h.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the volume ratio of the solution A to the solution B in the step (3) is 1: 1.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the stirring time is 1-4 hours after the dropwise addition in the step (3) is finished, so that the reaction can be ensured to be more sufficient.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the heating temperature in the step (4) is 120-200 ℃; the reaction time is 6-24 h; the above-mentionedThe drying temperature is 60-80 ℃, and the drying time is 24-48 h; the washing is 3-5 times of deionized water and alcohol respectively.
The beneficial effects of the above technical scheme are: the proper hydrothermal reaction temperature is favorable for MnCo2O4The crystal grains are assembled into a regular hollow ball structure, and if the temperature is lower than 120 ℃ or higher than 200 ℃, the full assembly of the crystal grains is not facilitated; the higher the temperature, the larger the hollow sphere size.
Preferably, MnCo is contained in the double-shell layer2O4In the synthesis method of the hollow nanosphere material, the calcination in the step (5) is carried out in a muffle furnace or a tubular furnace, the calcination temperature is 500-600 ℃, the time is 2-4h, and the atmosphere is a natural environment.
The beneficial effects of the above technical scheme are: the calcination time and temperature are determined according to the decomposition temperature of the cyclodextrin carbonaceous material on one hand, and ensure that the cyclodextrin is completely decomposed and changed into gas to escape on the other hand, and simultaneously avoid MnCo caused by too high temperature2O4And (5) decomposing.
The invention also provides double-shell MnCo synthesized by the method2O4Hollow nanosphere material, said nanosphere material being formed from MnCo2O4The nano crystal particles are assembled to form a hollow nano spherical structure, and the nano sphere material is of a single-shell, double-shell or multi-shell structure.
It should be noted that the particle size and shell thickness of the hollow sphere can be achieved by simply adjusting the reactant concentration, reaction time and temperature, and solvent ratio. Specifically, under a certain cyclodextrin concentration, the higher the concentrations of cobalt salt and manganese salt, the thicker the hollow sphere shell layer is, and the higher the ethanol content in the mixed solvent is, the more favorable the formation of a multi-shell layer structure is.
According to the technical scheme, compared with the prior art, the invention discloses and provides the double-shell MnCo2O4The hollow nanosphere material has the following advantages:
(1) the method of the invention prepares MnCo2O4The hollow nanosphere does not need to be independently synthesized into a template or added with any surfactant, and is suitable for usePreparing multi-element transition metal oxide hollow nanosphere materials with different systems;
(2) the technical method provided by the invention has the advantages of simple and efficient synthetic process, strong controllability, environmental friendliness, wide raw material source, low price and easiness in obtaining, and is easy to realize large-scale production;
(3) MnCo prepared by adopting the method of the invention2O4The hollow sphere has a unique double-shell hollow structure, the shell structure is clear in hierarchy and uniform in structure, the hollow sphere is endowed with a richer effective specific surface area, and the hollow sphere has important application values in the fields of catalysis, energy storage, conversion and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a diagram of a double-shell MnCo prepared in example 1 of the present invention2O4XRD diffractogram of hollow nanospheres;
FIG. 2 is a drawing showing a double-shell MnCo prepared in example 1 of the present invention2O4Scanning electron micrographs of hollow nanospheres;
FIG. 3 is a drawing showing a double-shell MnCo prepared in example 1 of the present invention2O4Transmission electron microscopy images of hollow nanospheres;
FIG. 4 is a drawing showing a double-shell MnCo prepared in example 1 of the present invention2O4High power transmission electron microscope image of the hollow nano spherical shell layer;
FIG. 5 is a single-shell MnCo alloy prepared according to example 2 of the present invention2O4Transmission electron microscopy images of hollow nanospheres;
FIG. 6 is a drawing showing a double-shell MnCo prepared in example 3 of the present invention2O4Scanning electron micrographs of hollow nanospheres;
FIG. 7 is a drawing showing a double-shell MnCo prepared in example 3 of the present invention2O4Transmission electron microscopy images of hollow nanospheres;
FIG. 8 is a single-shell MnCo alloy prepared in example 4 of the present invention2O4Transmission electron microscopy images of hollow nanospheres;
FIG. 9 is a single-shell MnCo alloy prepared in example 5 of the present invention2O4Transmission electron microscopy images of hollow nanospheres;
FIG. 10 is a drawing showing a multi-shell MnCo prepared in example 6 of the present invention2O4Transmission electron microscopy images of hollow nanospheres.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 5mmol β -cyclodextrin and 50ml ethanol into a beaker, uniformly mixing by ultrasonic stirring for 30min, wherein the concentration of β -cyclodextrin is 0.1mol/L, uniformly mixing 30ml ethanol and 20ml deionized water by magnetic stirring to serve as a solvent, adding 5mmol cobalt chloride hexahydrate and 2.5mmol manganese chloride tetrahydrate, and completely dissolving a reagent by ultrasonic stirring for 1h to form a uniform solution, wherein the concentrations of cobalt chloride and manganese chloride are respectively 0.1mol/L and 0.05mol/L, dropwise adding the cobalt chloride and manganese chloride solutions into a cyclodextrin dispersion liquid under magnetic stirring, continuously stirring for 1h to obtain a uniform reaction liquid, transferring the reaction liquid into a hydrothermal kettle, heating to 180 ℃ in an oven, carrying out heat preservation reaction for 12h, naturally cooling to room temperature, centrifugally separating a product, washing with deionized water and ethanol for 5 times, drying for 12h at 80 ℃ to obtain a powdery product, calcining the obtained product in a muffle furnace at 500 ℃ for 2h to obtain double-shelled MnCo2O4Hollow nanospheres.
As shown in the XRD spectrogram of FIG. 1, the double-shell MnCo prepared in example 1 of the invention2O4The hollow nanospheres have good crystallinity; as shown in the characterization result of scanning electron microscope of FIG. 2, the double-shell MnCo2O4The hollow nanospheres have a hollow structure with uniform particle size; the transmission electron microscope result of FIG. 3 shows that the MnCo with double shells is double-shell2O4The hollow nanosphere has an obvious double-shell structure, and the shell of the hollow nanosphere is made of MnCo2O4The thickness of the primary crystal grain is about 15-25nm, the particle size of the hollow sphere is about 300-700nm, and the particle size of the inner shell is about 80-120 nm; as can be seen from the high resolution tem image of fig. 4, the grains have a distinct stripe structure, indicating good crystallinity.
Example 2
Adding 5mmol β -cyclodextrin and 50ml ethanol into a beaker, uniformly mixing by ultrasonic stirring for 30min, wherein the concentration of β -cyclodextrin is 0.1mol/L, uniformly mixing 30ml ethanol and 20ml deionized water by magnetic stirring to serve as a solvent, adding 5mmol cobalt chloride hexahydrate and 2.5mmol manganese chloride tetrahydrate, and completely dissolving a reagent by ultrasonic stirring for 1h to form a uniform solution, wherein the concentrations of cobalt chloride and manganese chloride are respectively 0.1mol/L and 0.05mol/L, dropwise adding the cobalt chloride and manganese chloride solutions into a cyclodextrin dispersion liquid under magnetic stirring, continuously stirring for 1h to obtain a uniform reaction liquid, transferring the reaction liquid into a hydrothermal kettle, heating to 180 ℃ in an oven, carrying out heat preservation reaction for 6h, naturally cooling to room temperature, centrifugally separating a product, washing with deionized water and ethanol for 5 times, drying for 24h at 80 ℃ to obtain a powdery product, calcining the obtained product in a muffle furnace at 500 ℃ for 2h to obtain MnCo2O4Hollow nanospheres.
As shown in FIG. 5, the single-shell-structured MnCo prepared in example 2 of the present invention was used2O4Hollow nanospheres with the particle size of about 300-400nm, and the hydrothermal reaction time in the embodiment is shorter, and part of MnCo2O4The nanocrystals are not completely assembled.
Example 3
Adding 5mmol β -cyclodextrin and 50ml ethanol into a beaker, ultrasonically stirring for 30min to mix uniformly for later use, wherein the concentration of β -cyclodextrin is 0.1mol/L, and magnetically stirring 20ml ethanol and 30ml deionized waterUniformly mixing the mixture to be used as a solvent, adding 10mmol of cobalt chloride hexahydrate and 5mmol of manganese chloride tetrahydrate, and carrying out ultrasonic treatment for 1 hour to completely dissolve a reagent to form a uniform solution. Wherein, the concentrations of the cobalt chloride and the manganese chloride are respectively 0.2mol/L and 0.1 mol/L. Under magnetic stirring, dropwise adding cobalt chloride and manganese chloride solution into the cyclodextrin dispersion liquid, and continuously stirring for 1h to obtain a uniform reaction liquid. And transferring the reaction solution into a hydrothermal kettle, placing the hydrothermal kettle into an oven, heating the hydrothermal kettle to 180 ℃, preserving heat, reacting for 24 hours, naturally cooling the hydrothermal kettle to room temperature, centrifugally separating the product, washing the product with deionized water and alcohol for 5 times respectively, and drying the product for 24 hours at the temperature of 80 ℃ to obtain a powdery product. Calcining the obtained product in a muffle furnace at 500 ℃ for 2h to obtain double-shell MnCo2O4Hollow nanospheres.
MnCo prepared by using example 3 of the present invention as shown in FIG. 62O4The scanning electron microscope photo of the hollow nanospheres shows that the particle size distribution of the hollow spheres is within the range of 500-800nm, the cavity structure is obvious, and the shell layer is thicker; the transmission electron micrograph shown in FIG. 7 shows MnCo2O4The hollow sphere has an obvious double-shell structure, the shell layer of the hollow sphere is formed by assembling multiple layers of primary crystal grains, the thickness of the shell layer is about 100-130nm, and the shell layer of the hollow sphere is thicker due to the fact that the concentrations of the cobalt salt and the manganese salt are larger in the embodiment.
Example 4
Adding 20mmol β -cyclodextrin and 50ml ethanol into a beaker, uniformly mixing by ultrasonic stirring for 30min, wherein the concentration of β -cyclodextrin is 0.4mol/L, uniformly mixing 30ml ethanol and 20ml deionized water by magnetic stirring to serve as a solvent, adding 10mmol cobalt chloride hexahydrate and 5mmol manganese chloride tetrahydrate, and completely dissolving a reagent by ultrasonic stirring for 2h to form a uniform solution, wherein the concentrations of cobalt chloride and manganese chloride are respectively 0.2mol/L and 0.1mol/L, dropwise adding the cobalt chloride and manganese chloride solutions into a cyclodextrin dispersion liquid under magnetic stirring, continuously stirring for 4h to obtain a uniform reaction liquid, transferring the reaction liquid into a hydrothermal kettle, heating to 180 ℃ in an oven, carrying out heat preservation reaction for 12h, naturally cooling to room temperature, carrying out centrifugal separation on a product, washing for 5 times by deionized water and ethanol, and drying for 24h at 80 ℃ to obtain a powdery product, calcining the obtained product in a tubular furnace under natural atmosphere at 600 ℃ for 2hObtaining single-shell MnCo2O4Hollow nanospheres.
As shown in FIG. 8, MnCo prepared in example 4 of the present invention2O4The transmission electron microscope photo of the hollow nanosphere shows that the nanosphere has a single-shell structure, the particle size of the hollow sphere is distributed in the range of 300-700nm, and the shell thickness is about 30-60 nm. In the embodiment, because the concentration of the cyclodextrin is high, cobalt ions and manganese ions in the reaction solution are simultaneously deposited on the surface of the cyclodextrin, so that a single-shell structure is formed.
Example 5
Adding 2.5mmol α -cyclodextrin and 50ml ethanol into a beaker, stirring with ultrasound for 30min to mix uniformly for later use, wherein the concentration of α -cyclodextrin is 0.05mol/L, stirring 30ml ethanol and 20ml deionized water with magnetic force to mix uniformly as a solvent, adding 1mmol cobalt chloride hexahydrate and 0.5mmol manganese chloride tetrahydrate, and stirring with ultrasound for 1h to completely dissolve a reagent to form a uniform solution, wherein the concentrations of cobalt chloride and manganese chloride are 0.02mol/L and 0.01mol/L respectively, stirring with magnetic force, dropwise adding the cobalt chloride and manganese chloride solutions into the cyclodextrin dispersion, stirring for 1h to obtain a uniform reaction solution, transferring the reaction solution into a hydrothermal kettle, heating to 120 ℃ in an oven, reacting for 24h with thermal insulation, naturally cooling to room temperature, centrifugally separating the product, washing with deionized water and ethanol for 3 times, drying for 48h at 60 ℃ to obtain a powdery product, calcining the obtained product in a 600 ℃ tubular calcining furnace for 4h in natural atmosphere to obtain a single-shell MnCo layer2O4Hollow nanospheres.
As shown in FIG. 9, MnCo prepared in example 5 of the present invention2O4The transmission electron microscope photo of the hollow nanosphere shows a single-shell structure, the particle size distribution of the hollow sphere is within the range of 200-500nm, and the shell thickness is about 40-100 nm. And part of MnCo is caused by lower hydrothermal reaction temperature in the embodiment2O4The nanoparticles are not completely assembled.
Example 6
Adding 5mmol of gamma-cyclodextrin and 50ml of ethanol into a beaker, and ultrasonically stirring for 30min to uniformly mix for later use, wherein the concentration of the gamma-cyclodextrin is 1.0 mol/L. 40ml of ethanol and 10ml of deionized water are mixed evenly by magnetic stirringAs a solvent, 5mmol of cobalt acetate and 2.5mmol of manganese acetate are added, and the reagent is completely dissolved by ultrasonic treatment for 1h to form a uniform solution. Wherein, the concentrations of the cobalt chloride and the manganese chloride are respectively 0.1mol/L and 0.05 mol/L. Under magnetic stirring, dropwise adding cobalt chloride and manganese chloride solution into the cyclodextrin dispersion liquid, and continuously stirring for 1h to obtain a uniform reaction liquid. And transferring the reaction solution into a hydrothermal kettle, placing the hydrothermal kettle into an oven, heating the hydrothermal kettle to 200 ℃, preserving heat, reacting for 12 hours, naturally cooling the hydrothermal kettle to room temperature, centrifugally separating the product, washing the product for 3 times by using deionized water and alcohol respectively, and drying the product for 48 hours at the temperature of 60 ℃ to obtain a powdery product. Calcining at 600 ℃ for 4h in a tube furnace in natural atmosphere to obtain multi-shell MnCo2O4Hollow nanospheres.
FIG. 10 shows MnCo prepared in example 6 of the present invention2O4The transmission electron microscope photo of the hollow nanosphere shows a multi-shell structure, the particle size distribution of the hollow nanosphere is within about 500-1000nm, and the shell thickness is about 60-120 nm. MnCo in the present example2O4The particle size of the hollow sphere is larger, which is related to the high concentration of cyclodextrin and the higher reaction temperature, and the high content of ethanol in the mixed solvent is beneficial to forming a multi-shell structure.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. Double-shell MnCo2O4The synthesis method of the hollow nanosphere material is characterized by comprising the following steps of:
(1) dissolving cyclodextrin in ethanol, and performing ultrasonic dispersion until the cyclodextrin is uniformly mixed to obtain a solution A;
(2) uniformly mixing ethanol and deionized water through magnetic stirring to serve as a solvent, adding soluble cobalt salt and manganese salt, and performing ultrasonic treatment until the soluble cobalt salt and the manganese salt are completely dissolved to form a uniform solution B;
(3) dropwise adding the solution B into the solution A under magnetic stirring, and continuously stirring to obtain uniform reaction liquid;
(4) transferring the reaction solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven for heating and carrying out heat preservation reaction, then naturally cooling to room temperature, carrying out centrifugal separation on the product, washing with deionized water and alcohol, and drying to obtain a powdery product;
(5) calcining the powdery product in a heating furnace to obtain double-shell MnCo2O4A hollow nanosphere material.
2. A double-shelled MnCo as claimed in claim 12O4The synthesis method of the hollow nanosphere material is characterized in that the concentration of the cyclodextrin in the step (1) is 0.05-0.4mol/L, and the cyclodextrin is any one of α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin.
3. A double-shelled MnCo as claimed in claim 12O4The synthesis method of the hollow nanosphere material is characterized in that the adding amount of the ethanol in the step (2) is 40-80% of the volume of the solvent, and the adding amount of the deionized water is 20-60% of the volume of the solvent.
4. A double-shelled MnCo as claimed in claim 12O4The synthesis method of the hollow nanosphere material is characterized in that the ratio of the amount of the cobalt salt to the manganese salt in the step (2) is 2:1, the concentration of the cobalt salt in the solution is 0.02-0.2mol/L, and the manganese salt isThe concentration of (A) is 0.01-0.1 mol/L.
5. A double-shelled MnCo according to claim 1 or 42O4The synthesis method of the hollow nanosphere material is characterized in that the cobalt salt in the step (2) is any one of cobalt chloride, cobalt acetate, cobalt oxalate, cobalt phosphate, cobalt carbonate, cobalt sulfate and cobalt nitrate or any one of hydrates thereof.
6. A double-shelled MnCo according to claim 1 or 42O4The synthesis method of the hollow nanosphere material is characterized in that the manganese salt in the step (2) is any one of manganese chloride, manganese acetate, manganese oxalate, manganese phosphate, manganese carbonate, manganese sulfate and manganese nitrate or any one of hydrates thereof.
7. A double-shelled MnCo as claimed in claim 12O4The synthesis method of the hollow nanosphere material is characterized in that the volume ratio of the solution A to the solution B in the step (3) is 1: 1.
8. A double-shelled MnCo as claimed in claim 12O4The synthesis method of the hollow nanosphere material is characterized in that the heating temperature in the step (4) is 120-200 ℃; the reaction time is 6-24 h; the drying temperature is 60-80 ℃, and the drying time is 24-48 h; the washing is 3-5 times of deionized water and alcohol respectively.
9. A double-shelled MnCo as claimed in claim 12O4The synthesis method of the hollow nanosphere material is characterized in that the calcination in the step (5) is carried out in a muffle furnace or a tubular furnace, the calcination temperature is 500-600 ℃, the calcination time is 2-4h, and the atmosphere is natural environment.
10. Double-shell MnCo synthesized by the method of any one of claims 1 to 92O4Hollow nanosphere materials characterized byCharacterized in that the nanosphere material is made of MnCo2O4The nano crystal particles are assembled to form a hollow nano spherical structure, and the nano sphere material is of a single-shell, double-shell or multi-shell structure.
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