CN109205681B - Three-dimensional hierarchical structure metal oxide and preparation method thereof - Google Patents
Three-dimensional hierarchical structure metal oxide and preparation method thereof Download PDFInfo
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- CN109205681B CN109205681B CN201811059549.2A CN201811059549A CN109205681B CN 109205681 B CN109205681 B CN 109205681B CN 201811059549 A CN201811059549 A CN 201811059549A CN 109205681 B CN109205681 B CN 109205681B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/46—Metal oxides
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Abstract
The invention provides a three-dimensional hierarchical structure metal oxide and a preparation method thereof, wherein a metal hydroxide precursor is ultrasonically dispersed in concentrated sulfuric acid and is subjected to soaking treatment for 6-12 hours at 100 ℃; and then placing the treated sample in a tube furnace, and calcining the sample in the air at 500 ℃ for 2h to obtain the metal oxide nano material. The invention utilizes concentrated H2SO4The strong oxidizing property and the dehydration property are adopted, and in the dipping process, redundant impurities are removed by oxidation and simultaneously dehydration is carried out, so that a rich and staggered pore structure is formed in the material, and the metal oxide with large specific surface area is prepared. Compared with untreated metal hydroxide, the metal hydroxide treated by concentrated sulfuric acid has larger specific surface area and richer pore structure after being calcined, and provides a new idea for preparing the three-dimensional hierarchical metal oxide nano material.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a three-dimensional hierarchical metal oxide and a preparation method thereof.
Background
Metal oxides have many unique properties and have a wide application prospect and are at the leading edge of research in material science in recent decades. The physical and chemical properties of metal oxides at the nanometer scale can be changed greatly. As is well known, the physical and chemical properties of nanomaterials are closely related to their size, surface structure, exposed crystal plane, dimension, etc., so that the ability to control any one of these parameters can effectively control their properties. In order to widely apply the metal oxide nano materials with excellent characteristics, the reasonable design of the simple, economic, effective and environment-friendly preparation method has very important significance for realizing the control of the size, the shape and the structure of the nano materials. To date, there are many technical methods for preparing metal oxide nanomaterials, such as calcination, thermal decomposition, ion exchange, dehydration, and the like.
The metal oxide nano material is used as a catalyst to improve the reaction efficiency of a system due to small size, large specific surface area, more active centers, unique crystal structure and special surface characteristics (high surface activity and surface energy). Therefore, the construction of nanomaterial catalysts and their application in the field of catalysis are receiving wide attention. In addition, many efforts are put into research on novel and efficient energy conversion and storage elements, and currently, most researches mainly include sodium ion batteries, lithium ion batteries, zinc-air batteries, super capacitors and the like. The electrode material is the core composition of a battery or a capacitor, and the storage mode, the capacitance performance and the cycle life of the charge are determined by the properties of the electrode material. Among them, metal oxides are an important electrode material. Metal oxides have many oxidation states, programmable specific structures, high theoretical specific capacitance, low toxicity and low cost, and are considered to be one of the most potential electrode materials.
Disclosure of Invention
The invention aims to provide a preparation method of a novel metal oxide nano material with a three-dimensional hierarchical structure.
It is still another object of the present invention to provide a fuel cell electrode catalyst, a capacitor electrode material and a heavy metal adsorption material prepared from the three-dimensional hierarchical structure metal oxide nanomaterial.
A preparation method of a three-dimensional hierarchical structure metal oxide comprises the following steps:
(1) adding metal salt and sodium hydroxide into water according to a certain molar ratio, stirring to uniformly mix the metal salt and the sodium hydroxide, and reacting for 4-16 h at room temperature; after the reaction is finished, filtering and drying to obtain a metal hydroxide precursor;
(2) and (3) placing the metal hydroxide into concentrated sulfuric acid, soaking for 6-12 h at 100 ℃, then placing the treated sample into a tubular furnace, and calcining in the air to obtain the metal oxide nano material.
Further, the method for producing a three-dimensional hierarchical structure metal oxide as described above, the metal salt includes: ferric chloride, nickel acetate, cobalt acetate or cobalt nitrate.
Further, in the method for producing a three-dimensional hierarchical structure metal oxide as described above, the drying conditions of the metal hydroxide precursor in the step (1) are: vacuum drying at 60 deg.C for 24 h.
Further, in the method for preparing a three-dimensional hierarchical metal oxide as described above, the molar ratio of the metal salt to the sodium hydroxide is 1: 3.
further, the method for producing a three-dimensional hierarchical structure metal oxide as described above, the calcination in the step (2) is carried out under the condition of 500 ℃ for 2 hours.
The three-dimensional hierarchical structure metal oxide prepared by the method as described in any one of the above.
Has the advantages that:
1. the oxide formed by treating the hydroxide with concentrated sulfuric acid and then calcining has more pores and a larger specific surface area than the oxide obtained by directly calcining the hydroxide.
2. The concentrated sulfuric acid treatment of the hydroxide facilitates the construction of three-dimensional hierarchical oxides.
3. Concentrated sulfuric acid can be recycled in the experiment, and the experiment process is simple and the loss is small.
Drawings
FIG. 1 shows Fe obtained after concentrated sulfuric acid treatment2O3SEM picture of (1);
FIG. 2 shows direct calcination of Fe (OH)3Formed Fe2O3And concentrated sulfuric acid treatment of Fe (OH)3Fe obtained thereafter2O3XRD pattern of (a);
FIG. 3 shows 20% wtPT/C and Fe2O3-linear cyclic voltammetric profiles of Pt/C in 0.1M KOH solution;
FIG. 4 shows 20% wtPT/C and Fe2O3Cyclic voltammetry test plots of Pt/C in 0.1M KOH solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. 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.
The invention develops a novel synthesis method, and concentrated sulfuric acid is introduced to treat a hydroxide precursor. The influence on the appearance and the structure of the metal hydroxide is large when the metal hydroxide is treated by concentrated sulfuric acid, so that the preparation of the metal oxide nano material with the three-dimensional hierarchical structure is realized. The invention utilizes concentrated sulfuric acid to treat metal hydroxide precursor and then calcines the metal hydroxide precursor to obtain the metal oxide with a three-dimensional hierarchical structure. The oxide has more pore structures, and the specific surface area is increased while the catalytic activity is enhanced. Has better application prospect in the aspects of electrocatalytic oxygen reduction, capacitors, heavy metal adsorption and the like.
The preparation method of the three-dimensional hierarchical structure metal oxide nano material comprises the following process steps:
(1) adding metal salt and sodium hydroxide into water according to a certain molar ratio, stirring to uniformly mix the metal salt and the sodium hydroxide, and reacting for 4-16 h at room temperature; after the reaction is finished, carrying out suction filtration and drying to obtain a metal hydroxide precursor;
(2) and (3) placing the metal hydroxide precursor into concentrated sulfuric acid, soaking for 6-12 h at 100 ℃, then placing the treated sample into a tubular furnace, and calcining for 2h at 500 ℃ in the air to obtain the metal oxide nano material.
The material of the invention is prepared by treating Fe (OH) with concentrated sulfuric acid3The precursor is calcined at high temperature to obtain Fe with three-dimensional hierarchical structure2O3. FIG. 1 shows a three-dimensional hierarchical structure of Fe2O3Scanning Electron Microscope (SEM) images of nanomaterials. As can be seen in fig. 1, the material is distributed in a three-dimensional network.
FIG. 2 shows three-dimensional hierarchical structure Fe prepared by the present invention2O3XRD pattern of the nanomaterial. As can be seen from FIG. 2, the direct calcination of Fe (OH)3Formed Fe2O3The XRD has sharper peak and narrower peak width, which indicates that the directly calcined material is agglomerated to form a large block, and concentrated sulfuric acid is positionedIn the treated sample, XRD peaks are relatively weak, and peak width is wider, which is also corresponding to the formation of three-dimensional hierarchical structure shown in FIG. 1.
The invention relates to three-dimensional hierarchical structure Fe2O3The preparation method of the nano material catalyst is to use FeCl3With NaOH in a ratio of 1: 3, adding the mixture into water, stirring the mixture to be uniformly mixed, and reacting the mixture for 4 hours at room temperature; after the reaction is finished, filtering, drying to obtain Fe (OH)3A precursor; putting ferric hydroxide into concentrated sulfuric acid, soaking for 12h at 100 ℃, putting the treated sample into a tubular furnace, calcining for 2h at 500 ℃ in the air to obtain Fe2O3。
Three-dimensional hierarchical structure Fe prepared as described above2O3And (3) performance test of the nano material catalyst: mixing Fe2O3The catalyst obtained when mixed with 20% wtPt/C was subjected to a linear cyclic voltammetry test in 0.1M KOH solution and compared to 20% wtPt/C alone. FIG. 3 shows 20% wtPT/C and Fe2O3Cyclic voltammetry test plots of Pt/C in 0.1M KOH solution. From FIG. 3, Fe can be seen2O3The oxygen reduction initiation potential of the Pt/C catalyst was relatively advanced compared to 20% wtPt/C in the linear cyclic voltammetry test. It is demonstrated that the iron oxide material of the three-dimensional hierarchical structure formed by the present invention contributes to catalyzing oxygen reduction.
Three-dimensional hierarchical structure Fe2O3And (3) testing the catalytic durability of the nano material catalyst to oxygen reduction: mixing Fe2O3The catalyst obtained when mixed with 20% wtPt/C was subjected to cyclic voltammetry in 0.1M KOH solution and compared to 20% wtPt/C alone. FIG. 4 shows 20% wtPT/C and Fe2O3Cyclic voltammetry test plots of Pt/C in 0.1M KOH solution. From FIG. 4, Fe can be seen2O3The Pt/C catalyst has the advantages that the area of a dehydrogenation zone is reduced little in 1000 circles in a cyclic voltammetry test, and the area of the dehydrogenation zone is greatly reduced in 1000 circles in a 20% wtPt/C catalyst, so that the iron oxide material with a three-dimensional hierarchical structure formed by the invention is beneficial to the improvement of the stability of 20% wtPt/C.
In conclusion, the metal oxide catalyst disclosed by the invention is good in stability, high in activity and long in service life. The catalyst shows good catalytic activity in the oxygen reduction process and can be used as a fuel cell catalyst.
Example 1
(1) Three-dimensional hierarchical structure Fe2O3Preparation of nanomaterials
In a 100ml round-bottom flask, 1mmol FeCl was added3And 30ml of H2O, stirring uniformly; 0.12g of sodium hydroxide was added, stirring was continued, and the reaction was carried out at room temperature for 4 h: after the reaction is finished, filtering, washing and drying at 70 ℃ for 10h to obtain Fe (OH)3A precursor.
Mixing Fe (OH)3Soaking in concentrated sulfuric acid at 100 deg.C for 12h, placing the sample treated with concentrated sulfuric acid in a tubular furnace, calcining in air at 500 deg.C for 2h to obtain Fe with three-dimensional hierarchical structure2O3。
(2) Preparation of Mixed 20% wtPt/C catalyst
60mg of 20% wtPt/C and 15mg Fe2O3Ball milling to mix them uniformly, so that in the catalyst Fe2O3The mass ratio to 20% wtPt/C was 1: 4.
Fe2O3The initial potential of the Pt/C catalyst in the oxygen reduction performance test was earlier than 20% wtPt/C. In addition, the iron oxide having a three-dimensional hierarchical structure has a certain effect on heavy metal adsorption.
Example 2
(1) Preparation of three-dimensional hierarchical NiO nano material
2mmol of Ni (CH)3COO)2 is added into 60mL of water, stirred until completely dissolved, the formed green transparent solution is transferred into a 100mL reaction kettle, reacted for 6h at 200 ℃, centrifugally separated, washed, dried for 10h at 70 ℃ to obtain Ni (OH)2A precursor.
Reacting Ni (OH)2And placing the precursor in concentrated sulfuric acid, soaking for 12h at 100 ℃, then placing a sample treated by the concentrated sulfuric acid in a tubular furnace, and calcining for 2h at 500 ℃ in air to finally obtain the three-dimensional reticular NiO.
(2) Preparation of capacitor electrode material
8mg of NiO, 1mg of acetylene black and 1 microliter of PTFE are mixed to prepare a sample, and the sample is pressed on the foamed nickel to prepare the electrode.
The specific capacitance of the NiO electrode reaches 315F/g under the current density of 2A/g when the test is carried out in 6M KOH.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (2)
1. A preparation method of a three-dimensional hierarchical structure metal oxide is characterized by comprising the following steps:
(1) adding metal salt and sodium hydroxide into water according to a certain molar ratio, stirring to uniformly mix the metal salt and the sodium hydroxide, and reacting for 4-16 h at room temperature; after the reaction is finished, filtering and drying to obtain a metal hydroxide precursor;
(2) placing the metal hydroxide in concentrated sulfuric acid, soaking for 6-12 hours at 100 ℃, then placing the treated sample in a tubular furnace, and calcining in air to obtain a metal oxide nano material;
the drying conditions of the metal hydroxide precursor in the step (1) are as follows: vacuum drying at 60 deg.C for 24 hr;
calcining at 500 ℃ for 2h in the calcining condition in the step (2);
the metal salt includes: ferric chloride, nickel acetate, cobalt acetate or cobalt nitrate.
2. The method for producing a three-dimensional hierarchical structure metal oxide according to claim 1, characterized in that: the molar ratio of the metal salt to the sodium hydroxide is 1: 3.
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