CN111039329A - Hollow multi-shell metal oxide composite material and preparation method thereof - Google Patents

Hollow multi-shell metal oxide composite material and preparation method thereof Download PDF

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CN111039329A
CN111039329A CN201911410146.2A CN201911410146A CN111039329A CN 111039329 A CN111039329 A CN 111039329A CN 201911410146 A CN201911410146 A CN 201911410146A CN 111039329 A CN111039329 A CN 111039329A
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salt
solvent
combination
composite material
metal salt
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王丹
王欢
齐健
毛丹
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Institute of Process Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields

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  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention provides a preparation method of a hollow multi-shell metal oxide composite material, which comprises the following steps: (1) mixing a template agent, a first metal salt, a second metal salt, a first solvent, a second solvent and an acid to obtain a precursor solution; (2) preparing composite microspheres by using the precursor solution obtained in the step (1) as a raw material and adopting an electrostatic spraying method; (3) and (3) calcining the composite microspheres obtained in the step (2) to obtain the hollow multi-shell metal oxide composite material. The preparation method has the characteristics of simple steps, capability of accurately controlling the proportion of metal elements in the hollow spheres, high utilization rate of raw materials and the like.

Description

Hollow multi-shell metal oxide composite material and preparation method thereof
Technical Field
The invention belongs to the field of composite materials, relates to a metal oxide composite material and a preparation method thereof, and particularly relates to a hollow multi-shell metal oxide composite material and a preparation method thereof.
Background
The hollow multi-shell composite material has special optical, electric, magnetic, catalytic and other characteristics due to different compositions, sizes, shell numbers and the like, and is concerned. However, there are very few research reports on hollow multi-shell metal oxide composite materials designed for reactions such as CO catalytic oxidation, electrocatalysis, and photocatalysis. Wangdan et al (Angew. chem.2013,125,6545-6548) and Tang Chiyong et al (Nanoscale,2014,6,4072-3O4Multi-shell hollow sphere and CeO2The multi-shell hollow sphere is respectively measured for the lithium battery performance and the solar battery performance. However, the template method and the hydrothermal method have complex synthesis steps, complex experimental operation and difficult control of the proportion of metal ions, and only a small amount of metal ions can be adsorbed on the carbon spheres and most of the metal ions cannot be adsorbed in the process of adsorbing the metal ions by the carbon spheres, so that a large amount of metal salt is wasted. So far, the preparation of hollow multi-shell metal oxide composite materials by an electrostatic spraying method has not been reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hollow multi-shell metal oxide composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one purpose of the invention is to provide a preparation method of a hollow multi-shell metal oxide composite material, which is characterized by comprising the following steps:
(1) mixing a template agent, a first metal salt, a second metal salt, a first solvent, a second solvent and an acid to obtain a precursor solution;
(2) preparing composite microspheres by using the precursor solution obtained in the step (1) as a raw material and adopting an electrostatic spraying method;
(3) and (3) calcining the composite microspheres obtained in the step (2) to obtain the hollow multi-shell metal oxide composite material.
As a preferable technical scheme of the invention, the template agent in the step (1) is polyvinylpyrrolidone.
As a preferred technical solution of the present invention, the first metal salt in step (1) includes any one of cobalt salt, nickel salt, copper salt, aluminum salt or zinc salt or a combination of at least two of them, and the combination is exemplified by, typically but not limited to: combinations of cobalt salts and nickel salts, combinations of nickel salts and copper salts, combinations of copper salts and aluminum salts, combinations of aluminum salts and zinc salts, combinations of zinc salts and cobalt salts, or combinations of cobalt salts, nickel salts, and copper salts, and the like.
Preferably, the mass ratio of the first metal salt to the templating agent is 1 (1.8-26), such as 1:2, 1:3, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, 1:22, 1:25, or 1:26, but not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the second metal salt comprises any one of a cerium salt, an aluminium salt, a cobalt salt or an iron salt, or a combination of at least two of these, typical but non-limiting examples being: a combination of cerium and aluminum salts, a combination of aluminum and cobalt salts, a combination of cobalt and iron salts, a combination of iron and cerium salts, or a combination of cerium, aluminum and cobalt salts, and the like.
Preferably, the mass ratio of the second metal salt to the templating agent is 1 (1.8-26), such as 1:2, 1:3, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, 1:22, 1:25, or 1:26, but not limited to the recited values, and other values not recited within this range are equally applicable.
In the invention, if the total dosage of the first metal salt and the second metal salt is too large and the dosage of the template agent, the first solvent and the second solvent is not changed, the viscosity of the precursor solution is reduced, which is not beneficial to forming spheres; at the same time, the amount of the template is relatively small, which is not favorable for forming more shells (forming solid spheres) in the roasting process. If the dosage of the first metal salt and the second metal salt is too small and the dosage of the template agent, the first solvent and the second solvent is not changed, the dosage of the metal salt is not enough to form a shell layer in the roasting process, and a hollow multi-shell structure cannot be obtained.
Preferably, the cobalt salt comprises any one of cobalt acetate, cobalt nitrate or cobalt chloride or a combination of at least two of these, typical but non-limiting examples being: a combination of cobalt acetate and cobalt nitrate, a combination of cobalt nitrate and cobalt chloride, a combination of cobalt chloride and cobalt acetate, or a combination of cobalt acetate, cobalt nitrate, and cobalt chloride, or the like.
Preferably, the nickel salt comprises any one of nickel acetate, nickel nitrate or nickel chloride or a combination of at least two of these, typical but non-limiting examples being: a combination of nickel acetate and nickel nitrate, a combination of nickel nitrate and nickel chloride, a combination of nickel chloride and nickel acetate, a combination of nickel acetate, nickel nitrate and nickel chloride, or the like.
Preferably, the copper salt comprises any one of copper acetate, copper nitrate or copper chloride or a combination of at least two of these, typical but non-limiting examples being: a combination of copper acetate and copper nitrate, a combination of copper nitrate and copper chloride, a combination of copper chloride and copper acetate, a combination of copper acetate, copper nitrate and copper chloride, or the like.
Preferably, the aluminium salt comprises aluminium nitrate and/or aluminium chloride.
Preferably, the zinc salt comprises any one of zinc acetate, zinc nitrate or zinc chloride or a combination of at least two of these, typical but non-limiting examples being: combinations of zinc acetate and zinc nitrate, zinc nitrate and zinc chloride, zinc chloride and zinc acetate, or zinc acetate, zinc nitrate and zinc chloride, and the like.
Preferably, the cerium salt comprises cerium nitrate and/or cerium chloride.
As a preferred embodiment of the present invention, the first solvent includes any one or a combination of at least two of ethanol, acetone, isopropanol, dichloromethane or chloroform, and typical but non-limiting examples of the combination are: a combination of ethanol and acetone, a combination of acetone and isopropanol, a combination of isopropanol and dichloromethane, a combination of dichloromethane and trichloromethane or a combination of ethanol, acetone and dichloromethane, and the like.
Preferably, the second solvent comprises any one of water, N-dimethylformamide or dimethylsulfoxide, or a combination of at least two of these, typical but non-limiting examples being: a combination of water and N, N-dimethylformamide, a combination of N, N-dimethylformamide and dimethyl sulfoxide, a combination of dimethyl sulfoxide and water, or a combination of water, N-dimethylformamide and dimethyl sulfoxide, and the like.
Preferably, the volume ratio of the first solvent to the second solvent is 16 (1-10), such as 16:1, 16:2, 16:3, 16:4, 16:5, 16:6, 16:7, 16:8, 16:9, or 16:10, but not limited to the recited values, and other non-recited values within the range are also applicable.
Preferably, the mass-to-volume ratio of the templating agent to the first solvent is 4 (25-30), such as 4:25, 4:26, 4:27, 4:28, 4:29, or 4:30, but is not limited to the recited values, and other values not recited within this range are equally applicable.
As a preferred embodiment of the invention, the acid comprises any one of nitric acid, hydrochloric acid or perchloric acid, or a combination of at least two of these, typical but non-limiting examples being: a combination of nitric acid and hydrochloric acid, a combination of hydrochloric acid and perchloric acid, a combination of perchloric acid and nitric acid, or a combination of nitric acid, hydrochloric acid and perchloric acid, and the like.
Preferably, the volume ratio of the acid to the first solvent is 1 (40-80), such as 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, or 1:80, but not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferred embodiment of the present invention, the electrostatic spraying method in step (2) comprises:
placing the precursor solution obtained in the step 1) into an injector, then fixing the injector on a peristaltic pump, and simultaneously setting the propelling speed of the peristaltic pump, the voltage of an electrostatic spinning machine and the distance between a receiving polar plate and a needle head to carry out electrostatic spraying.
In a preferred embodiment of the present invention, the peristaltic pump has a propulsion rate of 0.5 to 0.8ml/h, such as 0.5ml/h, 0.55ml/h, 0.6ml/h, 0.65ml/h, 0.7ml/h, 0.75ml/h, or 0.8ml/h, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the electrostatic spinning machine has a voltage of 17-26 kV, such as 17kV, 18kV, 19kV, 20kV, 21kV, 22kV, 23kV, 24kV, 25kV or 26kV, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
In the invention, if the voltage is too large, filiform substances rather than spherical particles can be generated in the electrostatic spraying process, and a hollow multi-shell structure cannot be obtained after a sample is roasted; if the voltage is too small, the electrostatic force generated is not sufficient to overcome the surface tension of the liquid, and the primary droplets cannot be broken into smaller secondary droplets, so that the droplets cannot be completely dried during the falling process, and thus spherical precursor powder cannot be obtained.
Preferably, the distance between the receiving pad and the needle is 6-12 cm, such as 6cm, 7cm, 8cm, 9cm, 10cm, 11cm or 12cm, but not limited to the values listed, and other values not listed in this range are equally applicable.
As a preferred technical scheme of the present invention, the heating rate of the calcination in the step (3) is 1-10 ℃/min, such as 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the calcination is 500 to 700 ℃, such as 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃, 680 ℃, or 700 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the calcination time is 1 to 7 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours or 7 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the preparation method of the hollow multi-shell metal oxide composite material comprises the following steps:
(1) mixing a template agent, a first metal salt, a second metal salt, a first solvent, a second solvent and an acid to obtain a precursor solution, wherein the mass ratio of the first metal salt to the template agent is 1 (1.8-26), the mass ratio of the second metal salt to the template agent is 1 (1.8-26), the volume ratio of the first solvent to the second solvent is 16 (1-10), the mass ratio of the template agent to the first solvent is 4 (25-30), and the volume ratio of the acid to the first solvent is 1 (40-80);
(2) placing the precursor solution obtained in the step 1) into an injector, fixing the injector on a peristaltic pump, and performing electrostatic spraying after setting the propelling speed of the peristaltic pump to be 0.5-0.8 ml/h, the voltage of an electrostatic spinning machine to be 17-26 kV and the distance between a receiving polar plate and a needle head to be 6-12 cm;
(3) and (3) calcining the composite microspheres obtained in the step (2) at 500-700 ℃ for 1-7 h, wherein the heating rate is 1-10 ℃/min, so as to obtain the hollow multi-shell metal oxide composite material.
The invention also aims to provide a hollow multi-shell metal oxide composite material, which is prepared by any preparation method.
Preferably, the number of the shells of the hollow multi-shell metal oxide composite material is 3-6, such as 3, 4, 5 or 6.
Compared with the prior art, the invention at least has the following beneficial effects:
the invention provides a hollow multi-shell metal oxide composite material and a preparation method thereof.
Drawings
FIG. 1 shows a hollow multi-shell Co obtained in example 1 of the present invention3O4-CeO2An X-ray powder diffraction pattern of the composite material;
FIG. 2 shows a hollow multi-shell Co obtained in example 1 of the present invention3O4-CeO2Transmission electron microscope microscopic image of the composite material;
FIG. 3 shows a hollow multi-shell layer (Zn) obtained in example 6 of the present invention1/3Co2/3)Co2O4An X-ray powder diffraction pattern of the composite;
FIG. 4 shows a hollow multi-shell layer (Zn) obtained in example 6 of the present invention1/3Co2/3)Co2O4An X-ray photoelectron energy spectrum of the composite;
FIG. 5 shows a hollow multi-shell layer (Zn) obtained in example 6 of the present invention1/3Co2/3)Co2O4Transmission electron microscope microscopic image of the composite material;
FIG. 6 shows hollow multi-shell Co (Co) obtained in example 7 of the present invention7/2Al1/2)2O4An X-ray powder diffraction pattern of the composite;
FIG. 7 shows hollow multi-shell Co (Co) obtained in example 7 of the present invention7/2Al1/2)2O4An X-ray photoelectron energy spectrum of the composite;
FIG. 8 shows hollow multi-shell Co (Co) obtained in example 7 of the present invention7/2Al1/2)2O4Transmission electron microscopy microscopic image of the composite.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
electrostatic spraying was carried out using an electrostatic sprayer (TL-01) in the following examples; the quantitative propulsion of the injector adopts a peristaltic pump (SN-50); the roasting of the sample adopts a muffle furnace (SX 2-5-12); the X-ray powder diffraction spectrum is obtained by an X-ray powder diffractometer (X' Pert PRO); the X-ray photoelectron spectrum is obtained by an X-ray photoelectron spectrometer (220 i-XL); the transmission electron microscope photograph was obtained by using a lanthanum hexaboride transmission electron microscope (JEM-2100).
Example 1
(1) The first metal salt is Co (Ac) in cobalt salt2·4H2O and 1.0g is weighed, and the second metal salt is Ce (NO) in cerium salt3)3·6H2O and weighing 0.109 g; placing the mixture in a beaker filled with 4ml of deionized water (second solvent), and then carrying out ultrasonic treatment for 30 min; then weighing 2.4g of PVP as a template and placing the PVP in a beaker, weighing 16ml of absolute ethyl alcohol (first solvent) and adding the absolute ethyl alcohol into the beaker with the PVP, and magnetically stirring for 2 hours to form a uniform and clear light yellow solution; then adding the water solution of the first metal salt and the second metal salt into the ethanol solution of PVP, stirring for 10min to form a uniform and clear mauve solution, and finally adding 200 mul HNO into the solution3Then stirring for 10min by magnetic force to obtain the precursor solution of electrostatic spraying.
(2) Putting the precursor solution prepared in the step 1) into a 20ml syringe, then installing the syringe on a peristaltic pump, and setting the propelling speed of the peristaltic pump to be 0.8 ml/h; a needle head at the other end of the injection conduit is arranged on a needle head clamp in the electrostatic spinning machine, and the distance between the needle head and the collecting plate is set to be 8 cm; the voltage of the electrostatic spinning machine is set to be 22kV, then the main switch is turned on to start electrostatic spraying, and pink samples can be collected on the aluminum foil of the collecting plate, namely the composite microspheres.
(3) Placing the composite microspheres obtained in the step 2) in a muffle furnace for roasting, wherein the heating rate of the muffle furnace is set to be 1 ℃/min, the heat preservation temperature of the muffle furnace is set to be 500 ℃, and the heat preservation time is set to be 1h, obtaining hollow multi-shell Co after roasting3O4-CeO2(Co/Ce ═ 16/1) composite material. The X-ray powder diffraction spectrum (figure 1) shows that the multi-shell hollow sphere material contains Co3O4And CeO2Characteristic diffraction peaks of (a); the transmission electron micrograph (FIG. 2) shows that the hollow spheres have 3-5 shells with cavities between the shells.
Example 2
The procedure was followed as in example 1, except that the mass of template PVP in step 1) was 1.8 g. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 3
The procedure is as in example 1, except that the first metal salt in step (1) is selected from the group consisting of Co (Ac) in cobalt salts2·4H2The mass of O was 0.125 g. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 1/4) composite material.
Example 4
The procedure is as in example 1, except that the first metal salt in step (1) is Co (NO) in cobalt salt3)2·6H2O and the weighed mass was 1.164 g. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 5
The procedure is as in example 1, except that the first metal salt in step (1) is Ni (Ac) in a nickel salt2·4H2O and the weighed mass is 0.125 g. Finally obtaining the hollow multi-shell (Ni)1/3Co2/3)Co2O4A composite material.
Example 6
The procedure is as in example 1 except that the first metal salt in step (1) is Zn (NO) in a zinc salt3)3·6H2O, mass 0.149 g. Finally obtaining the hollow multi-shell layer (Zn)1/3Co2/3)Co2O4A composite material. The X-ray powder diffraction spectrum (figure 3) shows thatThe multi-shell hollow ball material is of a spinel structure; x-ray photoelectron spectroscopy (FIG. 4) shows Zn as the Zn element2+The form exists; the transmission electron micrograph (FIG. 5) shows that the hollow sphere has 3-4 shells with some gaps between the shells.
Example 7
The procedure was as in example 1, except that the second metal salt in step (1) was Al (NO) in the aluminum salt3)3·9H2O, mass 0.188 g. Finally obtaining hollow multi-shell Co (Co)7/2Al1/2)2O4A composite material. The X-ray powder diffraction spectrum (figure 6) shows that the multi-shell hollow sphere material has a spinel structure; x-ray photoelectron spectroscopy (FIG. 7) showed that Al is an element of Al3+The form exists; the tem image (fig. 8) shows that the hollow spheres have 3-4 shells with some gaps between the shells.
Example 8
The procedure was as in example 1, except that isopropanol was used as the first solvent in step (1) and the volume was 16 ml. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 9
The procedure was as in example 1, except that N, N-dimethylformamide was used as the second solvent in the step (1) and the volume thereof was 4 ml. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 10
The procedure is as in example 1, except that HClO is used as the acid in step (1)4And the volume thereof was 200. mu.l. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 11
The procedure is as in example 1, except that HClO is used as the acid in step (1)4And the volume thereof was 200. mu.l. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 12
The procedure was as in example 1 except that the advancing rate of the peristaltic pump in step (2) was set to 1.2 ml/h. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 13
The procedure was followed as in example 1 except that the distance from the needle to the collection plate in step (2) was set to 12 cm. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 14
The procedure was carried out as in example 1, except that the voltage of the electrospinning machine in the step (2) was set to 25 kV. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 15
The procedure was carried out as in example 1 except that the temperature-raising rate of the muffle furnace in step (2) was set to 10 ℃/min. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 16
The procedure was followed as in example 1, except that the holding temperature of the muffle furnace in step 3) was set to 700 ℃. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
Example 17
The procedure was as in example 1, except that the keeping warm time in step (3) was set to 7 hours. Finally obtaining hollow multi-shell Co3O4-CeO2(Co/Ce ═ 16/1) composite material.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. The preparation method of the hollow multi-shell metal oxide composite material is characterized by comprising the following steps of:
(1) mixing a template agent, a first metal salt, a second metal salt, a first solvent, a second solvent and an acid to obtain a precursor solution;
(2) preparing composite microspheres by using the precursor solution obtained in the step (1) as a raw material and adopting an electrostatic spraying method;
(3) and (3) calcining the composite microspheres obtained in the step (2) to obtain the hollow multi-shell metal oxide composite material.
2. The method according to claim 1, wherein the template agent in step (1) is polyvinylpyrrolidone.
3. The method according to claim 1 or 2, wherein the first metal salt in step (1) comprises any one of or a combination of at least two of a cobalt salt, a nickel salt, a copper salt, an aluminum salt, or a zinc salt;
preferably, the mass ratio of the first metal salt to the template is 1 (1.8-26);
preferably, the second metal salt comprises any one of cerium salt, aluminum salt, cobalt salt or iron salt or a combination of at least two of the same;
preferably, the mass ratio of the second metal salt to the template is 1 (1.8-26);
preferably, the cobalt salt comprises any one of cobalt acetate, cobalt nitrate or cobalt chloride or a combination of at least two thereof;
preferably, the nickel salt comprises any one of nickel acetate, nickel nitrate or nickel chloride or a combination of at least two of them;
preferably, the copper salt comprises any one of copper acetate, copper nitrate or copper chloride or a combination of at least two of the same;
preferably, the aluminium salt comprises aluminium nitrate and/or aluminium chloride;
preferably, the zinc salt comprises any one of zinc acetate, zinc nitrate or zinc chloride or a combination of at least two thereof;
preferably, the cerium salt comprises cerium nitrate and/or cerium chloride.
4. The production method according to any one of claims 1 to 3, wherein the first solvent comprises any one of ethanol, acetone, isopropanol, dichloromethane, or chloroform, or a combination of at least two thereof;
preferably, the second solvent comprises any one of water, N-dimethylformamide or dimethylsulfoxide, or a combination of at least two thereof;
preferably, the volume ratio of the first solvent to the second solvent is 16 (1-10);
preferably, the mass volume ratio of the template to the first solvent is 4 (25-30).
5. A production method according to any one of claims 1 to 3, wherein the acid comprises any one of nitric acid, hydrochloric acid, or perchloric acid, or a combination of at least two thereof;
preferably, the volume ratio of the acid to the first solvent is 1 (40-80).
6. The method according to any one of claims 1 to 5, wherein the electrostatic spraying in step (2) is carried out by:
placing the precursor solution obtained in the step 1) into an injector, then fixing the injector on a peristaltic pump, and simultaneously setting the propelling speed of the peristaltic pump, the voltage of an electrostatic spinning machine and the distance between a receiving polar plate and a needle head to carry out electrostatic spraying.
7. The preparation method according to claim 6, wherein the peristaltic pump has a propulsion rate of 0.5 to 0.8 ml/h;
preferably, the voltage of the electrostatic spinning machine is 17-26 kV;
preferably, the distance between the receiving polar plate and the needle head is 6-12 cm.
8. The method according to any one of claims 1 to 7, wherein the temperature increase rate of the calcination in the step (3) is 1 to 10 ℃/min;
preferably, the calcining temperature is 500-700 ℃;
preferably, the calcining time is 1-7 h.
9. The method of any one of claims 1 to 8, comprising the steps of:
(1) mixing a template agent, a first metal salt, a second metal salt, a first solvent, a second solvent and an acid to obtain a precursor solution, wherein the mass ratio of the first metal salt to the template agent is 1 (1.8-26), the mass ratio of the second metal salt to the template agent is 1 (1.8-26), the volume ratio of the first solvent to the second solvent is 16 (1-10), the mass ratio of the template agent to the first solvent is 4 (25-30), and the volume ratio of the acid to the first solvent is 1 (40-80);
(2) placing the precursor solution obtained in the step 1) into an injector, fixing the injector on a peristaltic pump, and performing electrostatic spraying after setting the propelling speed of the peristaltic pump to be 0.5-0.8 ml/h, the voltage of an electrostatic spinning machine to be 17-26 kV and the distance between a receiving polar plate and a needle head to be 6-12 cm;
(3) and (3) calcining the composite microspheres obtained in the step (2) at 500-700 ℃ for 1-7 h, wherein the heating rate is 1-10 ℃/min, so as to obtain the hollow multi-shell metal oxide composite material.
10. A hollow multi-shell metal oxide composite material, characterized in that the composite material is prepared by the preparation method of any one of claims 1 to 9;
preferably, the number of the shells of the hollow multi-shell metal oxide composite material is 3-6.
CN201911410146.2A 2019-01-16 2019-12-31 Hollow multi-shell metal oxide composite material and preparation method thereof Pending CN111039329A (en)

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CN113149077A (en) * 2021-03-04 2021-07-23 中国科学院过程工程研究所 Preparation method and application of amorphous metal oxide hollow multi-shell material
CN113909072A (en) * 2021-08-27 2022-01-11 青岛科技大学 Preparation method of metal-doped porous carbon microsphere/CNTs composite material
CN114479601A (en) * 2021-12-31 2022-05-13 扬州斯帕克实业有限公司 Infrared/radar compatible stealth air-supported film and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113149077A (en) * 2021-03-04 2021-07-23 中国科学院过程工程研究所 Preparation method and application of amorphous metal oxide hollow multi-shell material
CN113149077B (en) * 2021-03-04 2023-02-17 中国科学院过程工程研究所 Preparation method and application of amorphous metal oxide hollow multi-shell material
CN113909072A (en) * 2021-08-27 2022-01-11 青岛科技大学 Preparation method of metal-doped porous carbon microsphere/CNTs composite material
CN114479601A (en) * 2021-12-31 2022-05-13 扬州斯帕克实业有限公司 Infrared/radar compatible stealth air-supported film and preparation method thereof
CN114479601B (en) * 2021-12-31 2023-09-08 扬州斯帕克实业有限公司 Infrared/radar compatible stealth air-bearing film and preparation method thereof

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Application publication date: 20200421