CN109867265B - Method for preparing macroporous ordered metal oxide by utilizing supermolecule self-assembly - Google Patents
Method for preparing macroporous ordered metal oxide by utilizing supermolecule self-assembly Download PDFInfo
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Abstract
The invention belongs to the technical field of material synthesis, and particularly relates to a universal method for preparing a macroporous ordered metal oxide by utilizing supermolecule self-assembly. The method comprises the steps of firstly obtaining a supermolecule-metal cation intermediate with regular appearance by a low-temperature hydrothermal method, and then calcining the intermediate by a tube furnace to obtain the macroporous ordered metal oxide. The macroporous ordered metal oxide prepared by the invention has macropores of more than 200 nm. Compared with the prior art, the method has the characteristics of strong universality, simple synthesis process, no use of hard templates and surfactants, high controllability and mass production; the metal oxide prepared by the method has uniform size, large specific surface area and rich pore structure, and provides a new idea for preparing the macroporous ordered metal oxide.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a universal method for preparing a macroporous ordered metal oxide by using supermolecule self-assembly.
Background
The metal oxide has become a research hotspot in various fields at home and abroad because of the advantages of rich reserves, environmental protection, stability, easy preparation and the like. However, the metal oxide material has small specific surface area, easy agglomeration and poor dispersibility, and the application of the metal oxide material is limited. The main approach to solve the above problems is to prepare metal oxides with a specific morphology and structure. Among them, the macroporous ordered metal oxide has a large specific surface area, a high porosity, rich active sites, and excellent dispersibility, and has become one of the hot spots of the scientific research of materials.
At present, the main preparation methods of macroporous ordered metal oxides are a hard template method, a soft template method and a self-template method. The hard template method is the most common method for preparing macroporous ordered metal oxide, and usually takes ordered mesoporous silica, mesoporous carbon, polymethyl methacrylate, polystyrene colloidal crystal microspheres and the like as template agents. The hard template method can effectively enlarge the specific surface area of the metal oxide, but the preparation period of the method is long, and the steps are complex. Meanwhile, during the synthesis, HF or NH with strong corrosiveness is generally used 4 HF 2 The template is removed, which is environmentally unfriendly and dangerous. In addition, the soft template method using the surfactant and the ionic liquid has the advantages of simple operation, low price and the like. However, the soft template method also has the problems of poor structural stability, low efficiency and the like, and the most significant challenge is to remove the template agent. Therefore, there is a need to find a simple and efficient method for preparing macroporous ordered metal oxides. The supermolecule self-assembly method can obtain the macroporous ordered metal oxide with high yield without any template and surfactant, and the method has the advantages of cheap and easily-obtained raw materials, simple and convenient operation and universality, and is a novel route for preparing the macroporous ordered metal oxide.
Disclosure of Invention
The invention aims to provide a method for preparing macroporous ordered metal oxide by utilizing supermolecule self-assembly, which overcomes the defects of the prior art. The method comprises the steps of firstly obtaining a supermolecule-metal cation intermediate with regular appearance by a low-temperature hydrothermal method, and then calcining the supermolecule-metal cation intermediate by a tube furnace to obtain the macroporous ordered metal oxide. The macroporous ordered metal oxide prepared by the invention has macropores of more than 200 nm.
The technical scheme for realizing the aim of the invention is as follows:
a method for preparing macroporous ordered metal oxide by utilizing supermolecule self-assembly comprises the following preparation steps:
(1) Placing metal nitrate in deionized water, and magnetically stirring and uniformly dispersing at normal temperature to obtain a metal salt solution;
(2) Adding melamine into the obtained metal salt solution, and uniformly dispersing the melamine by magnetic stirring at normal temperature to obtain uniform dispersion liquid;
(3) Transferring the obtained dispersion liquid into a hydrothermal reaction kettle for reaction, cooling to room temperature, performing centrifugal separation, washing and drying to obtain a supermolecule-metal cation intermediate;
(4) Adding the supermolecule-metal cation intermediate into the crucible, then placing the crucible into a tubular furnace, introducing gas, heating to a certain temperature at a certain heating speed, and then keeping for a certain time to obtain the macroporous ordered metal oxide.
In the preparation method, in the step 1, the mass ratio of the metal nitrate to the deionized water is 1-3; the magnetic stirring time at normal temperature is 20-60min; the metal nitrate is Zn (NO) 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 O，Fe(NO 3 ) 3 ·9H 2 O or Mn (NO) 3 ) 2 。
In the preparation method, in the step 2, the mass ratio of the melamine to the metal nitrate is 0.3-1:1-3, wherein the magnetic stirring time at normal temperature is 30-60min.
In the preparation method, in the step 3, the reaction temperature is 150-220 ℃, and the reaction time is 8-16 h.
In the preparation method, in the step 4, the mass of the supramolecular-metal cation intermediate is 0.5-2g, the calcining temperature is 650-1000 ℃, the heating rate is 1-5 ℃/min, the calcining temperature is kept for 2-5 hours, the gas is argon, and the gas flow rate is 100mL/min.
Compared with the prior art, the invention has the following remarkable advantages:
1. does not need any template and surfactant, and has very good universality on metal oxides.
2. The preparation method of the material has no special requirements on equipment, has extremely high yield, is simple to operate, easy to control, good in repeatability, green and environment-friendly, and is beneficial to industrial large-scale production.
Drawings
FIG. 1 is an SEM image of the macroporous ordered ZnO prepared by the present invention.
FIG. 2 is a diagram of macroporous ordered Co prepared by the present invention 3 O 4 SEM image of (d).
FIG. 3 is a diagram of macroporous ordered Fe prepared by the present invention 2 O 3 SEM image of (d).
FIG. 4 shows a macroporous ordered MnO prepared according to the present invention 2 SEM image of (d).
Detailed Description
The invention is explained in further detail below with reference to the drawing.
The methods described in the following examples are conventional methods unless otherwise specified; the material reagents, unless otherwise specified, are commercially available.
Example 1: the method for preparing the macroporous ordered ZnO by using the supermolecule self-assembly specifically comprises the following steps:
the first step is as follows: 2g of Zn (NO) 3 ) 2 ·6H 2 Placing O in 50mL of deionized water, magnetically stirring at normal temperature for 20min, and uniformly dispersing to obtain Zn 2+ An aqueous solution;
the second step: adding 0.5g of melamine into the obtained metal salt solution, and magnetically stirring at normal temperature for 30min to uniformly disperse to obtain uniform dispersion liquid;
the third step: transferring the obtained dispersion liquid to a 50mL hydrothermal reaction kettle for reaction, putting the reaction kettle into a constant-temperature oven for reaction at 180 ℃ for 12 hours, cooling the reaction kettle to room temperature, and then carrying out centrifugal separation, washing and drying to obtain supermolecule-Zn 2+ An intermediate;
the fourth step: respectively weighing two parts of 1.5g of supramolecular-metal cation intermediate, placing the supramolecular-metal cation intermediate into two crucibles, covering the crucibles, placing the two crucibles on a square boat, placing the crucible in a central temperature control area of a tubular furnace, and calcining the crucible under the argon atmosphere (the gas flow rate is 100 mL/min); the heating parameters were as follows: uniformly heating from room temperature to 800 ℃ within 400 minutes, and keeping at 800 ℃ for 4 hours; and then naturally cooling, and obtaining a sample which is the macroporous ordered ZnO and can be used without grinding.
Fig. 1 is an SEM image of the macroporous ordered ZnO prepared in this example. As can be seen from FIG. 1, the prepared sample has rich macroporous structure, uniform size and ordered arrangement.
Example 2: in contrast to example 1, the starting material Zn (NO) was reacted 3 ) 2 ·6H 2 Changing O to Co (NO) 3 ) 2 ·6H 2 O, the resulting SEM image is shown in fig. 2. As can be seen from FIG. 2, the prepared sample has a rich and well-ordered macroporous structure.
Example 3: in contrast to example 1, the starting material Zn (NO) was reacted 3 ) 2 ·6H 2 Changing O to Fe (NO) 3 ) 3 ·9H 2 O, the resulting SEM image is shown in fig. 3. As can be seen from FIG. 3, the prepared sample has a rich and well-ordered macroporous structure.
Example 4: in contrast to example 1, the starting material Zn (NO) was reacted 3 ) 2 ·6H 2 Changing O to Mn (NO) 3 ) 2 The resulting SEM image is shown in FIG. 4. As can be seen from FIG. 4, the prepared sample has a rich and well-ordered macroporous structure.
Claims (4)
1. A method for preparing macroporous ordered metal oxide by utilizing supermolecule self-assembly is characterized by comprising the following specific preparation steps:
(1) Placing metal nitrate in deionized water, and magnetically stirring and uniformly dispersing at normal temperature to obtain a metal salt solution;
(2) Adding melamine into the obtained metal salt solution, and magnetically stirring and uniformly dispersing at normal temperature to obtain uniform dispersion liquid;
(3) Transferring the obtained dispersion liquid into a hydrothermal reaction kettle for reaction, cooling to room temperature, performing centrifugal separation, washing and drying to obtain a supermolecule-metal cation intermediate;
(4) Adding into a crucibleAdding the super-molecule-metal cation intermediate into a tubular furnace, introducing gas, heating to a certain temperature at a certain heating rate, and calcining for a certain time to obtain macroporous ordered metal oxide; the mass of the intermediate of supramolecular-metal cation is 0.5-2g, and the calcining temperature is 650 ◦ C-1000 ◦ C, the temperature rise speed is 1 to 5 ◦ C/min, the calcination temperature is kept for 2-5 hours, the gas is argon, and the gas flow rate is 100mL/min.
2. The method for preparing a macroporous ordered metal oxide by supramolecular self-assembly as claimed in claim 1, wherein in step (1), the mass ratio of the metal nitrate to the deionized water is 1-3; the magnetic stirring time at normal temperature is 20-60min; the metal nitrate is Zn (NO) 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 O，Fe(NO 3 ) 3 ·9H 2 O or Mn (NO) 3 ) 2 。
3. The method for preparing a macroporous ordered metal oxide by supramolecular self-assembly as claimed in claim 1, wherein in the step (2), the mass ratio of melamine to metal nitrate is 0.3-1:1-3, wherein the magnetic stirring time at normal temperature is 30-60min.
4. The method for preparing a macroporous ordered metal oxide by supramolecular self-assembly as claimed in claim 1, wherein in step (3), the reaction temperature is 150-220 ℃, and the reaction time is 8-16 h.
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| CN1962441A (en) * | 2006-12-01 | 2007-05-16 | 北京化工大学 | One step method for preparing high specific surface area micro/meso porous aluminate |
| CN109019556A (en) * | 2018-08-07 | 2018-12-18 | 中国石油大学(北京) | It is a kind of to load the preparation method and gained carbon material for having the carbon material of metal oxide |
| CN109046428A (en) * | 2018-08-22 | 2018-12-21 | 广州大学 | A kind of mesoporous class graphite phase carbon nitride and its preparation method and application |
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Patent Citations (3)
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| CN1962441A (en) * | 2006-12-01 | 2007-05-16 | 北京化工大学 | One step method for preparing high specific surface area micro/meso porous aluminate |
| CN109019556A (en) * | 2018-08-07 | 2018-12-18 | 中国石油大学(北京) | It is a kind of to load the preparation method and gained carbon material for having the carbon material of metal oxide |
| CN109046428A (en) * | 2018-08-22 | 2018-12-21 | 广州大学 | A kind of mesoporous class graphite phase carbon nitride and its preparation method and application |
Non-Patent Citations (3)
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| Direct Synthesis of Porous Nanorod-Type Graphitic Carbon Nitride/CuO Composite from Cu–Melamine Supramolecular Framework towards Enhanced Photocatalytic Performance;Jiangpeng Wang等;《Chem. Asian J.》;20150413;第10卷;第1276-1280页 * |
| Facile synthesis of nanorod-type graphitic carbon nitride/Fe2O3 composite with enhanced photocatalytic performance;Jiangpeng Wang等;《Journal of Solid State Chemistry》;20160329;第238卷;第247页scheme 1和第2.2节synthesis部分 * |
| Switching charge transfer of C3N4/W18O49 from type-II to Z-scheme by interfacial band bending for highly efficient photocatalytic hydrogen evolution;Zhen-Feng Huang等;《Nano Energy》;20170819;第40卷;第308-316页 * |
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