CN109867265A - A method of the orderly metal oxide of macropore is prepared using Supramolecular self assembly - Google Patents
A method of the orderly metal oxide of macropore is prepared using Supramolecular self assembly Download PDFInfo
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- CN109867265A CN109867265A CN201910179587.XA CN201910179587A CN109867265A CN 109867265 A CN109867265 A CN 109867265A CN 201910179587 A CN201910179587 A CN 201910179587A CN 109867265 A CN109867265 A CN 109867265A
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Abstract
The invention belongs to field of material synthesis technology more particularly to a kind of universality methods that the orderly metal oxide of macropore is prepared using Supramolecular self assembly.The method that this method passes through low-temperature hydrothermal first obtains supermolecule-metal cation intermediate of regular appearance, then calcines to obtain the orderly metal oxide of macropore by tube furnace.The orderly metal oxide of macropore prepared by the present invention, with the macropore for being more than 200nm.Compared with prior art, the present invention has the characteristics that universality is strong, synthesis technology is simple, high without using hard template and surfactant, controllability and can be mass-produced；Abundant using the metal oxide size uniformity of this method preparation, large specific surface area, pore structure, the preparation for the orderly metal oxide of macropore provides new approaches.
Description
Technical field
The invention belongs to field of material synthesis technology more particularly to a kind of using Supramolecular self assembly, to prepare macropore orderly golden
Belong to the universality method of oxide.
Background technique
Metal oxide, because it has many advantages, such as rich reserves, environmental-friendly, stable and easily prepared, it has also become domestic
The research hotspot of outer every field.But metal oxide materials specific surface area is small, easy to reunite, bad dispersibility, constrains it and answers
With.The main method to solve the above problems at present is to prepare the metal oxide with special appearance and structure.Wherein, macropore has
Sequence metal oxide has big specific surface area, high porosity, active site abundant, splendid dispersibility, becomes material
Expect one of the hot spot of scientific research.
Currently, the main preparation methods of the orderly metal oxide of macropore have hard template method, soft template method and self-template methods.Firmly
Template is to prepare the most common method of the orderly metal oxide of macropore, usually with ordered mesoporous silica dioxide, mesoporous carbon, poly- first
Base methyl acrylate and polystyrene colloidal crystal microballoon etc. are template.Hard template method can effectively expand the ratio table of metal oxide
Area, but this method long preparation period, step are complicated.Meanwhile in the synthesis process, usually using strong corrosive HF or
NH4HF2Removing template is removed, this is disagreeableness to environment and is dangerous.In addition, using surfactant, the soft mode of ionic liquid
Plate method has many advantages, such as easy to operate, cheap.But the problems such as that there is also structural stabilities is poor for soft template method, low efficiency, and
Its maximum challenge is the removal to template.Therefore, it is necessary to explore it is a kind of it is easy, efficiently prepare the orderly metal oxygen of macropore
The method of compound.Supramolecular self assembly method can obtain high yield in the case where no any template and surfactant
The orderly metal oxide of macropore, and raw material is cheap and easily-available, easy to operate, universality, prepares the orderly metal oxide of macropore
Novel route.
Summary of the invention
The orderly metal oxide of macropore is prepared using Supramolecular self assembly it is an object of the present invention to provide a kind of
Method, overcome the deficiencies in the prior art.The method that this method passes through low-temperature hydrothermal first obtains supermolecule-metal of regular appearance
Cationic intermediates, then calcine to obtain the orderly metal oxide of macropore by tube furnace.The orderly metal of macropore prepared by the present invention
Oxide, with the macropore for being more than 200nm.
Realize the technical solution of the object of the invention specifically:
A method of the orderly metal oxide of macropore being prepared using Supramolecular self assembly, preparation step is as follows:
(1) metal nitrate is placed in deionized water, room temperature magnetic force is dispersed with stirring uniformly, obtains metal salt solution；
(2) melamine is added in resulting metal salt solution, room temperature magnetic force is dispersed with stirring uniformly, is obtained uniform
Dispersion liquid；
(3) resulting dispersion liquid is transferred in hydrothermal reaction kettle and is reacted, after being cooled to room temperature, be centrifugated, wash
It washs, be dried to obtain supermolecule-metal cation intermediate；
(4) it to addition supermolecule-metal cation intermediate inside crucible, places into tube furnace, is passed through gas, then
It is warming up to certain temperature with certain heating rate, then keeps certain time, can be obtained the orderly metal oxide of macropore.
In above-mentioned preparation method, in the step 1, the mass ratio of metal nitrate and deionized water is 1-3:30-80；
The time of room temperature magnetic agitation is 20-60min；The metal nitrate is Zn (NO3)2·6H2O, Co (NO3)2·6H2O, Fe
(NO3)3·9H2O or Mn (NO3)2。
In above-mentioned preparation method, in the step 2, the mass ratio of melamine and metal nitrate is 0.3-1:1-3,
The room temperature magnetic force mixing time is 30-60min.
In above-mentioned preparation method, in the step 3, reaction temperature is 150 DEG C -220 DEG C, and the reaction time is
8h-16h。
In above-mentioned preparation method, in the step 4, weight is 0.5-2g, calcining among supermolecule-metal cation
Temperature is 650 DEG C -1000 DEG C, and the heating rate is 1-5 DEG C/min, and the calcination temperature retention time is 2-5 hours,
The gas is argon gas, and the gas flow rate is 100mL/min.
Compared with prior art, the present invention its remarkable advantage:
1, any template and surfactant are not needed, there is extraordinary universality to metal oxide.
2, the preparation method of the invention material has high yield to equipment without particular/special requirement, easy to operate, is easy to control
System, it is reproducible, it is environmentally protective, be conducive to industrialized large-scale production.
Detailed description of the invention
The SEM that Fig. 1 is the orderly ZnO of macropore prepared by the present invention schemes.
Fig. 2 is the orderly Co of macropore prepared by the present invention3O4SEM figure.
Fig. 3 is the orderly Fe of macropore prepared by the present invention2O3SEM figure.
Fig. 4 is the orderly MnO of macropore prepared by the present invention2SEM figure.
Specific embodiment
The present invention is illustrated in further detail with reference to the accompanying drawing.
Method described in following example is unless otherwise specified conventional method；The material agents, such as without special
Illustrate, it is commercially middle to obtain.
Embodiment 1: the method for preparing the orderly ZnO of macropore using Supramolecular self assembly, specifically includes the following steps:
Step 1: by the Zn (NO of 2g3)2·6H2O is placed in 50mL deionized water, and room temperature magnetic agitation 20min dispersion is equal
It is even, obtain Zn2+Aqueous solution；
Step 2: the melamine of 0.5g is added in resulting metal salt solution, room temperature magnetic agitation 30min dispersion
Uniformly, uniform dispersion liquid is obtained；
It is reacted step 3: resulting dispersion liquid is transferred in 50mL hydrothermal reaction kettle, is put into 180 DEG C of constant temperature oven
Lower reaction 12h after being cooled to room temperature, is centrifugated, washs, being dried to obtain supermolecule-Zn2+Intermediate；
It is placed in two crucibles step 4: weighing two parts of 1.5g supermolecule-metal cation intermediates respectively, crucible need to add
Lid, two crucibles are placed on a Noah's ark and are placed on tube furnace center temperature controlled region, under an argon atmosphere (gas flow rate 100mL/
Min it) is calcined；Heating parameters are as follows: being arranged from room temperature, are at the uniform velocity warming up to 800 DEG C in 400 minutes, and protect at 800 DEG C
It holds 4 hours；Then natural cooling, the sample of acquisition are the orderly ZnO of macropore, be can be used without grinding.
The SEM figure that Fig. 1 is the orderly ZnO of macropore prepared by the present embodiment.From figure 1 it appears that prepared
Sample has macroporous structure abundant, and size uniformity, orderly aligned.
Embodiment 2: different from embodiment 1, by reaction raw materials Zn (NO3)2·6H2O is changed to Co (NO3)2·6H2O, institute
The SEM figure obtained is as shown in Figure 2.From figure 2 it can be seen that prepared sample has abundant and orderly aligned macropore knot
Structure.
Embodiment 3: different from embodiment 1, by reaction raw materials Zn (NO3)2·6H2O is changed to Fe (NO3)3·9H2O, institute
The SEM figure obtained is as shown in Figure 3.From figure 3, it can be seen that prepared sample has abundant and orderly aligned macropore knot
Structure.
Embodiment 4: different from embodiment 1, by reaction raw materials Zn (NO3)2·6H2O is changed to Mn (NO3)2, resulting
SEM figure is as shown in Figure 4.Figure 4, it is seen that prepared sample has abundant and orderly aligned macroporous structure.
Claims (5)
1. a kind of method for preparing the orderly metal oxide of macropore using Supramolecular self assembly, which is characterized in that specific preparation step
It is rapid as follows:
(1) metal nitrate is placed in deionized water, room temperature magnetic force is dispersed with stirring uniformly, obtains metal salt solution；
(2) melamine is added in resulting metal salt solution, room temperature magnetic force is dispersed with stirring uniformly, is uniformly dispersed
Liquid；
(3) resulting dispersion liquid is transferred in hydrothermal reaction kettle and is reacted, after being cooled to room temperature, centrifuge separation, is done washing
It is dry to obtain supermolecule-metal cation intermediate；
(4) it to addition supermolecule-metal cation intermediate inside crucible, places into tube furnace, gas is passed through, then with one
Fixed heating rate is warming up to certain temperature, then keeps certain time, can be obtained the orderly metal oxide of macropore.
2. a kind of method for preparing the orderly metal oxide of macropore using Supramolecular self assembly as described in claim 1, special
Sign is, in the step (1), the mass ratio of metal nitrate and deionized water is 1-3:30-80；Room temperature magnetic agitation when
Between be 20-60min；The metal nitrate is Zn (NO3)2·6H2O, Co (NO3)2·6H2O, Fe (NO3)3·9H2O or Mn
(NO3)2。
3. a kind of method for preparing the orderly metal oxide of macropore using Supramolecular self assembly as described in claim 1, special
Sign is, in the step (2), the mass ratio of melamine and metal nitrate is 0.3-1:1-3, and the room temperature magnetic force stirs
Mixing the time is 30-60min.
4. a kind of method for preparing the orderly metal oxide of macropore using Supramolecular self assembly as described in claim 1, special
Sign is, in the step (3), reaction temperature is 150 DEG C -220 DEG C, and the reaction time is 8h-16h.
5. a kind of method for preparing the orderly metal oxide of macropore using Supramolecular self assembly as described in claim 1, special
Sign is, in the step (4), weight is 0.5-2g among supermolecule-metal cation, and calcination temperature is 650 DEG C -1000
DEG C, the heating rate is 1-5 DEG C/min, and the calcination temperature retention time is 2-5 hours, and the gas is argon
Gas, the gas flow rate are 100mL/min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2019
- 2019-03-11 CN CN201910179587.XA patent/CN109867265B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| JIANGPENG WANG等: "Direct Synthesis of Porous Nanorod-Type Graphitic Carbon Nitride/CuO Composite from Cu–Melamine Supramolecular Framework towards Enhanced Photocatalytic Performance", 《CHEM. ASIAN J.》 * |
| JIANGPENG WANG等: "Facile synthesis of nanorod-type graphitic carbon nitride/Fe2O3 composite with enhanced photocatalytic performance", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
| ZHEN-FENG HUANG等: "Switching charge transfer of C3N4/W18O49 from type-II to Z-scheme by interfacial band bending for highly efficient photocatalytic hydrogen evolution", 《NANO ENERGY》 * |
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