CN111268741A - Method and device for batch and controllable preparation of graphite carbon-coated metal/metal oxide nanoparticles and application of graphite carbon-coated metal/metal oxide nanoparticles - Google Patents
Method and device for batch and controllable preparation of graphite carbon-coated metal/metal oxide nanoparticles and application of graphite carbon-coated metal/metal oxide nanoparticles Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002184 metal Substances 0.000 title claims abstract description 75
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 74
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 35
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 28
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 13
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 9
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Abstract
The invention relates to a method and a device for preparing metal/metal oxide nano particles coated with graphite carbon in batch and in a controllable manner and application thereof, wherein the method comprises the steps of polymerizing and coating the metal/metal oxide nano particles by using dopamine hydrochloride dispersed in a Tris buffer solution, then centrifugally separating and drying in vacuum to prepare a dopamine-coated metal/metal oxide nano material; and then, by utilizing the coupling wave-absorbing characteristic of the metal/metal oxide @ carbon and the mechanism of microwave selective action wave-absorbing medium, the prepared carbon-coated metal/metal oxide is subjected to targeted heating catalytic carbon layer graphitization conversion by adopting a microwave fluidized bed to obtain the graphite carbon-coated metal/metal oxide nano material. The graphite carbon-coated metal/metal oxide nano material obtained by the invention has uniform appearance, high purity and good monodispersity; the yield and the efficiency are high, the cost is relatively low, and the reaction device is relatively simple; and can realize large-scale preparation, and has industrial prospect.
Description
Technical Field
The invention belongs to a preparation method of graphite carbon-coated metal/metal oxide nanoparticles, and particularly relates to a preparation method of a series of carbon-coated metal/metal oxide nanoparticles with controllable appearance and size, which can be applied to the fields of catalytic materials, biomedicine, magnetic recording materials, electrode materials and the like.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The carbon-coated nano metal/metal oxide is a novel functional composite material with a core-shell structure. The coating shell layer is an amorphous carbon structure or a multilayer graphite layer structure, and the core is nano metal/metal oxide particles. This unique structure prevents hydrolysis of the core metal/metal oxide and also prevents growth and agglomeration of the core particles. The carbon-coated nano metal/metal oxide has the effects of surface effect, small-size effect, quantum tunneling effect and the like possessed by all nano materials, and the existence of the carbon coating layer also endows the core metal/metal oxide with some peculiar physicochemical characteristics. The material has wide application in the fields of catalytic materials, biomedicine, magnetic recording materials, electrode materials and the like. The traditional methods for preparing carbon-coated nano metal/metal oxide are many, and mainly comprise a pyrolysis method, a laser method, a mechanical ball milling method, a chemical vapor deposition method, a hydrothermal method, a sol-gel method and an arc discharge method.
The arc discharge method is the earliest and commonly used method, and is a preparation method of a mixed anode consisting of graphite and a target coated metal simple substance or metal oxide by arc discharge evaporation in a vacuum or inert atmosphere, and the method has the disadvantages of harsh reaction conditions, low yield, difficulty in controlling the structure of a product, more byproducts and difficulty in avoiding the byproducts. The methods of chemical vapor deposition, pyrolysis, high-temperature carbonization and the like are similar in nature, and are all characterized in that a carbon-containing substance is carbonized and deposited on the surface of metal particles at high temperature to complete a coating process, the difference is the types and states of a metal source and a carbon source, the preparation process is greatly restricted by raw materials and reaction conditions, and a large amount of byproducts (such as carbon atom cluster impurities such as carbon nanotubes, carbon nanocages, amorphous carbon and the like) are inevitably accompanied in a product, so that large-scale production cannot be realized. The sol-gel method and the hydrothermal method have outstanding advantages in the aspects of improving the yield and purity of products and regulating and controlling the size and the shape of particles, and the preparation process also has the characteristics of simpler equipment, mild reaction conditions and easy control, but the inventor finds that: because the reaction temperature is low, the carbon shell mainly consists of amorphous carbon, the graphitization degree is low, and the thermal stability and the chemical stability are poor.
Disclosure of Invention
In order to overcome the problems, the invention provides a method for preparing graphite carbon-coated metal/metal oxide nanoparticles in batch and controllably, and the carbon-coated metal/metal oxide nanoparticles prepared by the method have the advantages of high purity, uniform appearance, good monodispersity, simplicity and convenience and low cost.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
in the first aspect of the present invention, there is provided a method for batch and controlled preparation of graphite carbon-coated metal/metal oxide nanoparticles, comprising:
dispersing metal/metal oxide nanoparticles and dopamine hydrochloride in a buffer solution, uniformly mixing, centrifuging and drying to form dopamine-coated metal/metal oxide nanoparticles;
and carbonizing the dopamine-coated metal/metal oxide nano-particles in a microwave fluidized bed to obtain the graphite carbon-coated metal/metal oxide nano-particles.
The research of the invention finds that: the heating of the material by the microwave device alone causes problems of sintering and sticking of the material, while the heating efficiency of the conventional fluidized bed alone is low. Therefore, the invention combines the advantages of efficient selective heating of microwave, prevention of uneven heating of materials in static reaction by a fluidized bed and adhesion of materials in sintering, utilizes the coupling wave-absorbing property of metal/metal oxide @ carbon and the mechanism of microwave selective action wave-absorbing medium, and adopts the microwave fluidized bed to perform targeted heating catalytic carbon layer graphitization conversion on the prepared dopamine-coated metal/metal oxide to obtain the graphite carbon-coated metal/metal oxide nano material.
In some embodiments, the ratio of the metal/metal oxide nanoparticles to dopamine hydrochloride is 1: 1-1: 2, so as to effectively coat the metal/metal oxide nanomaterial to form a structure of graphite carbon-coated metal/metal oxide nanomaterial.
The research finds that: the coating amount of the metal/metal oxide nano material by the dopamine is increased along with the increase of the concentration of the metal/metal oxide nano particles, but when the concentration of the metal/metal oxide nano particles reaches a certain degree, the coating amount is not greatly increased by continuously increasing the metal/metal oxide nano material. Therefore, in some embodiments, the concentration of the metal/metal oxide nanoparticles in the buffer solution is 2-5 g/L to improve the coating efficiency.
In some embodiments, the drying is vacuum drying at 40-60 ℃ for 12-14 h to form dopamine coated metal/metal oxide nanoparticles.
In some embodiments, the carbonization is performed under an inert gas blanket. The method is based on the characteristic that metal/metal oxide is a strong wave-absorbing medium, utilizes the direct action of microwaves on the metal/metal oxide in the material to carbonize the externally coated dopamine, and is different from the common drying and dehydrating process.
In some embodiments, the carbonization temperature is 300-400 ℃ and the heating time is 5-15 min. Compared with the traditional heating mode, the microwave heating has the characteristics of uniform heating, high heating speed and selective heating. The microwave heating can effectively accelerate the chemical reaction rate, reduce the reaction time and improve the yield, and meanwhile, the microwave heating can start heating from the inside of the reactant, so that the uniformity and the quality of the reaction product can be improved. In some embodiments, the Tris buffer solution is prepared with 1.2114g/L deionized water, and the pH is adjusted to 8.5, so that the self-polymerization reaction of dopamine proceeds smoothly, and the coating effect is improved.
In a second aspect of the invention, there is provided the use of graphitic carbon-coated metal/metal oxide nanoparticles prepared by any of the above-described methods in the fields of catalytic materials, biomedicine, magnetic recording materials, and electrode materials.
In a third aspect of the present invention, there is provided an apparatus for batch and controlled preparation of graphite carbon-coated metal/metal oxide nanoparticles, comprising: the reactor is a hollow cavity, a sleeve is arranged inside the reactor, a sand core is arranged in the sleeve, and a vent pipe is further arranged at one end of the sleeve; the reactor is connected with a microwave source through a pipeline, and is also connected with a gas washing device, a temperature measuring device and a gas source. A fluidized bed reactor is a reactor in which powdered materials are suspended in a fluid by a gas, the materials are caused to flow in the reactor, the particles have certain apparent characteristics of the fluid, a fluidized state similar to that in a fluidized bed boiler is exhibited, and chemical reactions of the materials are performed. The reactor can uniformly heat the material in a fluidized state, so as to avoid the problems of nonuniform heating, material sintering adhesion and the like caused by static heating.
The invention has the beneficial effects that:
(1) the invention realizes the even heating of the fluidization of the material under microwave by simulating the fluidized bed, and prevents the property and structure of the material from changing due to the adhesion of the material caused by uneven heating in static microwave heating. The selective heating characteristics of microwaves allow heating from within the material. The lower part of the inner cavity has small sectional area, which can ensure that the gas flow velocity is large enough to meet the fluidization requirement, and the upper part has large sectional area, which can prevent the material from being carried out of the reactor along with the gas flow. The flow rate is controlled by an external flow meter for different materials to achieve the proper fluidization state.
(2) The method has the advantages of simple operation method, low cost, universality and easy large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows graphite carbon coated Fe prepared in an example of the present invention3O4The overall structure of the nanoparticle device is schematically shown.
Wherein: 1. an outer layer of the reactor; 2. a cavity; 3. a sand core; 4. a breather pipe; 5. a microwave source; 6. n is a radical of2A gas cylinder; 7. a flow meter; 8. a reactor; 9. exhausting by an external gas washing device; 10. and an infrared temperature measuring device is connected.
FIG. 2 shows Fe coated with graphite carbon prepared in example 1 of the present invention3O4Scanning Electron Microscope (SEM) images of nanoparticles.
FIG. 3 shows Fe coated with graphite carbon prepared in example 1 of the present invention3O4Nanoparticle Transmission Electron Microscopy (TEM) images.
FIG. 4 shows Fe coated with graphite carbon prepared in example 1 of the present invention3O4Nanoparticle Raman spectroscopy (Raman) images and comparisons thereof.
FIG. 5 shows Fe coated with graphite carbon prepared in example 1 of the present invention3O4Nanoparticle voltammograms.
FIG. 6 shows Fe coated with graphite carbon prepared in example 1 of the present invention3O4Nanoparticle cycle performance plot.
FIG. 7 shows Fe coated with graphite carbon prepared in example 1 of the present invention3O4Experimental flow diagram of nanoparticles.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the problems of low graphitization degree and poor thermal stability and chemical stability of the carbon-coated nano metal/metal oxide carbon prepared by the existing method are solved. Therefore, the invention provides a method for preparing graphite carbon-coated metal/metal oxide nanoparticles in batch and controllably, which comprises the following steps:
1. stirring and dissolving Tris in deionized water, preparing a Tris buffer solution, and adjusting the pH value by using concentrated hydrochloric acid;
2. proportionally dispersing metal/metal oxide nanoparticles and dopamine hydrochloride in a Tris buffer solution prepared in the first step, stirring at room temperature, centrifuging, and drying in vacuum;
3. and (3) heating the prepared dopamine-coated metal/metal oxide nano-particles in a microwave fluidized bed in a nitrogen atmosphere at a controlled temperature to prepare the graphite carbon-coated metal/metal oxide nano-particles.
In some embodiments, in the above method for preparing graphite carbon-coated metal/metal oxide nanoparticles in a controlled batch, the Tris buffer solution is prepared with 1.2114g/L deionized water, and the PH is adjusted to 8.5.
In some embodiments, in one of the above methods for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles, the metal/metal oxide nanoparticles are dispersed with dopamine hydrochloride in a ratio of 1:1 to 1:2 in a Tris buffer solution in a dispersion ratio of 2 to 5g per liter of metal/metal oxide nanoparticles under continuous stirring for 10 to 24 hours, and then centrifuged and vacuum-dried at 40 to 60 ℃ for 12 hours.
In some embodiments, in the above method for preparing graphite carbon-coated metal/metal oxide nanoparticles in a batch and controllable manner, the dopamine hydrochloride-coated metal/metal oxide nanoparticles are heated in a microwave fluidized bed at a temperature of 300 ℃ to 400 ℃ for 5-15 min.
In some embodiments, in one of the above methods for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles, the fluidization state of said dopamine hydrochloride-coated metal/metal oxide nanoparticles in the microwave fluidized bed is adjusted by changing the flow of nitrogen gas.
In some embodiments, in one of the above methods for batch, controlled production of graphitic carbon-coated metal/metal oxide nanoparticles, the thickness of the carbon shell is designed by adjusting the ratio of metal/metal oxide nanoparticles to dopamine hydrochloride.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1:
controllable preparation of graphite carbon coated Fe in batches3O4A method of nanoparticles comprising the steps of:
(1) 1.2114g of Tris is stirred and dissolved in 1L of deionized water to prepare a Tris buffer solution, and the PH value is adjusted to 8.5 by concentrated hydrochloric acid;
(2) 2.0g of Fe3O4And 2.0g dopamine hydrochloride in a ratio of 1:1 in the Tris buffer solution prepared in the first step, then continuously stirring for 10 hours at room temperature, centrifuging, and vacuum drying for 12 hours at 50 ℃;
(3) coating 1.0g of dopamine prepared above with Fe3O4And (3) in nitrogen atmosphere, constant heating is carried out for 15min at 1500W of a solid microwave source to prepare graphite carbon coated Fe3O4And (3) nanoparticles.
As can be seen from FIGS. 1 to 3, the fluidized bed is simulated to realize uniform heating of the material in fluidization under microwave, so that the change of the material property structure caused by the adhesion of the material due to nonuniform heating in static microwave heating is prevented.
As can be seen from FIG. 4, the graphitic carbon-coated Fe prepared according to the present invention3O4The nano-particles have a better graphitization degree.
As can be seen from FIGS. 5 to 6, the graphitic carbon-coated Fe prepared according to the present invention3O4The nano-particles have better electrochemical performance.
Example 2:
controllable preparation of graphite carbon coated Fe in batches3O4A method of nanoparticles comprising the steps of:
(1) 1.2114g of Tris is stirred and dissolved in 1L of deionized water to prepare a Tris buffer solution, and the PH value is adjusted to 8.5 by concentrated hydrochloric acid;
(2) 2.0g of Fe3O4And 4.0g dopamine hydrochloride in a ratio of 1:2 are dispersed in the Tris buffer solution prepared in the first step, and then the mixture is continuously stirred for 24 hours at room temperature, centrifuged and dried in vacuum for 12 hours at 60 ℃;
(3) coating 1.0g of dopamine prepared above with Fe3O4Constantly heating 1000W of a solid microwave source for 15min in a nitrogen atmosphere to prepare graphite carbon coated Fe3O4And (3) nanoparticles.
Example 3:
controllable preparation of graphite carbon coated Fe in batches3O4A method of nanoparticles comprising the steps of:
(1) 1.2114g of Tris is stirred and dissolved in 1L of deionized water to prepare a Tris buffer solution, and the PH value is adjusted to 8.5 by concentrated hydrochloric acid;
(2) 2.0g of Fe3O4And 3.0g dopamine hydrochloride in a ratio of 1:1.5 in the Tris buffer solution prepared in the first step, then continuously stirring for 16 hours at room temperature, centrifuging, and vacuum drying for 12 hours at 40 ℃;
(3) coating 1.0g of dopamine prepared above with Fe3O4Constant heating is carried out on a solid microwave source with 1500W for 5min in the nitrogen atmosphere to prepare graphite carbon coated Fe3O4And (3) nanoparticles.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. A method for preparing graphite carbon-coated metal/metal oxide nanoparticles in batch and in a controllable manner is characterized by comprising the following steps:
dispersing metal/metal oxide nanoparticles and dopamine hydrochloride in a buffer solution, uniformly mixing, centrifuging and drying to form dopamine-coated metal/metal oxide nanoparticles;
and carbonizing the dopamine-coated metal/metal oxide nano-particles in a microwave fluidized bed to obtain the graphite carbon-coated metal/metal oxide nano-particles.
2. The method for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles according to claim 1, wherein the ratio of metal/metal oxide nanoparticles to dopamine hydrochloride is 1:1 to 1: 2.
3. The method for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles according to claim 1, wherein the concentration of said metal/metal oxide nanoparticles in the buffer solution is 2-5 g/L.
4. The method for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles according to claim 1, wherein the drying is vacuum drying at 40-60 ℃ for 12-14 h.
5. The method for the batch, controlled production of graphitic carbon-coated metal/metal oxide nanoparticles according to claim 1, wherein said carbonizing is carried out under an inert gas blanket.
6. The method for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles as claimed in claim 1, wherein the carbonization temperature is 300-400 ℃ and the heating time is 5-15 min.
7. The method for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles according to claim 1, wherein the buffer solution is Tris buffer solution prepared in a ratio of 1.2114g/L deionized water, and the pH is adjusted to 8.5.
8. The method for the batch, controlled preparation of graphitic carbon-coated metal/metal oxide nanoparticles according to claim 1, wherein the specific step of mixing uniformly is stirring for 10-24 h.
9. Use of graphitic carbon-coated metal/metal oxide nanoparticles prepared according to the process of any one of claims 1 to 8 in the fields of catalytic materials, biomedicine, magnetic recording materials, electrode materials.
10. An apparatus for the batch, controlled production of graphitic carbon-coated metal/metal oxide nanoparticles, comprising: the reactor is a hollow cavity, a sleeve is arranged inside the reactor, a sand core is arranged in the sleeve, and a vent pipe is further arranged at one end of the sleeve; the reactor is connected with a microwave source through a pipeline, and is also connected with a gas washing device, a temperature measuring device and a gas source.
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