CN109485102A - A kind of preparation method of special construction metallic compound/carbon composite - Google Patents
A kind of preparation method of special construction metallic compound/carbon composite Download PDFInfo
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- CN109485102A CN109485102A CN201811552270.8A CN201811552270A CN109485102A CN 109485102 A CN109485102 A CN 109485102A CN 201811552270 A CN201811552270 A CN 201811552270A CN 109485102 A CN109485102 A CN 109485102A
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- metallic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
Abstract
The invention belongs to technical field of material, provide a kind of preparation method of special construction metallic compound/carbon composite.Step are as follows: react to obtain metallic compound/carbon matrix precursor with 2- amino terephthalic acid (TPA) using solid-state ZnO, introduce other metal salts in situ by synthesis process, final high temperature is calcined to obtain a kind of special construction metallic compound/carbon composite.Gained composite material of the invention is three dimensional micron ball made of being stacked as hollow two-dimensional nano piece, carbon material is as material of main part, load has uniform metal compound nanoparticles on it, and special construction can effectively promote the specific surface area and electric conductivity of such material.
Description
Technical field
The invention belongs to technical field of material, are related to a kind of system of special construction metallic compound/carbon composite
It is standby.
Background technique
Porous carbon materials are due to its big specific surface area, high conductivity and excellent physical and chemical stability, in daily life
It has a wide range of applications in living and industrial production, such as: pernicious gas absorption, the absorption of pollutant, the storage of gas and separation.
Electrode material of the porous carbon materials for supercapacitor also early has been commercialized.In addition, nearest studies have shown that is into porous carbon
Introducing hetero-atoms, porous carbon materials also show excellent catalytic property.After carbon material and metallic compound are compound, pass through
The chemical property of carbon and intermetallic interaction and metal itself, the chemical property and catalytic performance of composite material can be into one
Step is promoted.Currently, common metallic compound/carbon composite method for preparing has metal organic precursor pyrolysismethod, Xiang Duo
Modification introduces metallic compound method etc. after in the carbon of hole, and every kind of method has the unique advantage of oneself, but there is also certain to lack
Point.Such as metallic compound/carbon composite that pyrogenic metal organic precursors obtain, distribution of the metallic compound in carbon is more
Uniformly, but metal organic precursor price lattice costly.Using cheap carbon material, metallic compound is introduced by rear modification,
The problems such as reuniting and be unevenly distributed there is metallic compound again.
On the other hand, the structure for rationally controlling material, can significantly promote the property of material.It is nearest that researches show that carbon
The electrochemical properties of material depend significantly on its structure.The specific surface area and electric conductivity for improving carbon material are to improve the weight of its property
Means are wanted, two-dimensional layer material has very high electric conductivity and specific surface area, but two-dimensional nano piece is easy to stack, and then cannot
Make full use of its specific surface area.If two-dimensional nano piece is assembled into three-dimensional manometer ball, its stacking will be effectively inhibited, from
And improve the utilization rate of material.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of special construction metallic compound/carbon composite
Preparation method, the material are the three-dimensional microballoons assembled by two-dimensional nano piece, and synthesis process is simple, low in cost.The material
Material reacts to obtain metallic compound/carbon matrix precursor using solid-state ZnO with 2- amino terephthalic acid (TPA) first, passes through synthesis process original
Position introduces other metal salts, and final high temperature is calcined to obtain a kind of special construction metallic compound/carbon composite.
In order to achieve the above object, the present invention specifically includes the following steps:
The first step prepares metallic compound/carbon matrix precursor
Solid-state ZnO nano material is put into organic solvent and deionized mixed solution, 2- amino is then added to benzene
Dioctyl phthalate and other metal salt stand 3-10 days at room temperature.It is then centrifuged for separating, after deionized water washing is dry, obtain
Special construction metallic compound/carbon composite presoma.
The amount of the 2- amino terephthalic acid (TPA) is adjusted according to the amount of ZnO, in order to obtain preferable pattern, ZnO
And the molar ratio of 2- amino terephthalic acid (TPA) controls between 3:1-1:3.The amount of the metal salt can be with foundation 2- amino pair
The amount of phthalic acid is adjusted, in order to obtain preferable pattern, the molar ratio control of metal salt and 2- amino terephthalic acid (TPA)
Between 0-1:1.
The metal salt, wherein metal can be iron, cobalt, nickel, copper, manganese etc., and the form of salt can be acetate, hydrochloric acid
Salt, nitrate, sulfate, acetylacetonate etc..The purpose for adding metal salt is catalysis also proper energy in order to improve material to oxygen
Power.
The solid-state ZnO nano material can be ZnO nanorod, ZnO nano-wire, ZnO nanotube/, ZnO nano ball etc.
It is common to obtain appearance of nano material.
In the organic solvent and deionized mixed solution, the volume ratio of organic solvent and water is 3:1-1:3.It is described
Organic solvent be N,N-dimethylformamide (DMF), methanol, ethyl alcohol etc. be easy to the molten of 2- amino terephthaldehyde's acid dissolution
Agent.
The room temperature is not strict with temperature, and reaction standing time is related with temperature.In general, summer
3-6 days are needed, winter needs 6-10 days.
Second step prepares metallic compound/carbon composite
Metallic compound/carbon composite presoma that the first step obtains is placed in tube furnace, calcined gas atmosphere
It encloses and obtains metallic compound/carbon composite of special construction after calcining 1-4 hours at 800-1200 DEG C for inert gas.
The existence form of the metallic compound prepared in the present invention depend on the first step used in metal salt type and
Calcination time and temperature in second step, the metal Fe salt such as used, what is typically resulted in is ferroso-ferric oxide；Use metal Co
Salt, what is obtained is metal Co simple substance.
The particle size of the metallic compound prepared in the present invention is related with the addition amount of metal salt, with addition metal salt
Amount increases, and metallic compound size is increased, and generally between 2-50nm, is uniformly embedded in carbon structure.
Metallic compound/carbon composite of special construction prepared by the present invention, structural particularity depend on carbon material
Structure, resulting carbon material is three dimensional micron ball made of being stacked as hollow two-dimensional nano piece.According to using ZnO nano shape
Looks, three dimensional micron ball can be hollow or non-hollow structure.
The inert gas is Ar gas or N2Gas.
Compared with prior art, the invention has the benefit that for the first time using cheap ZnO nano material and 2- amino pair
Phthalic acid reacts to control the pattern of material.In pyrolytic process, 2- amino terephthalic acid (TPA) is converted into porous carbon, material
Pattern is retained.During high temperature pyrolysis, ZnO is reduced to Zn simple substance by carbon and then volatilizees, and improves the specific surface area of material.
The higher boiling metal salt additionally added is embedded in porous carbon in the form of metallic compound.The present invention prepares predecessor process
Temperature is low, can effectively reduce energy consumption；Metallic compound/carbon composite of synthesis has special two-dimensional structure, should
Structure is the three dimensional micron ball being self-assembly of for hollow two-dimensional nano piece, is conducive to the specific surface area and conduction that improve material
Property.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of " metallic compound/carbon matrix precursor " in embodiment 1.
Fig. 2 is the scanning electron microscope diagram of " metallic compound/carbon composite " in embodiment 1.
Fig. 3 is the X-ray diffractogram of " metallic compound/carbon composite " in embodiment 1.
Fig. 4 is the scanning electron microscope diagram of " metallic compound/carbon composite " in embodiment 2.
Fig. 5 is the scanning electron microscope diagram of " metallic compound/carbon composite " in embodiment 3.
Specific embodiment
Present invention will be further explained below with reference to specific examples.These embodiments are merely to illustrate the present invention and do not have to
In limiting the scope of the invention.Technical staff in the art belongs to this hair to the simple replacement of the invention done or improvement
Within bright protected technical solution.
Case study on implementation 1
10g natrium carbonicum calcinatum is distributed in 22.5ml deionized water, clear solution is stirred to get, anhydrous 100mg is added
Zinc chloride, stirs to get homogeneous phase solution, moves into reaction kettle, 140 degree at a temperature of, hydro-thermal reaction 12 hours.Temperature fall
To room temperature, it is washed out, it is dry, obtain dry ZnO nanorod.
36ml n,N-Dimethylformamide (DMF) is mixed with 12ml deionized water, stirs to get mixed solvent, then
Above-mentioned solution is added in 82mg ZnO nanorod, stirs to get homogeneous solution.The stirring of 182mg 2- amino terephthalic acid (TPA) is added
Homogeneous phase solution is obtained, the anhydrous FeCl of 162mg is then added3, 6 days are stood in 31 degree of room temperature.It is then centrifuged for, centrifugal rotational speed
8000r/min, centrifugation 5 minutes, are centrifuged 5 times, are washed every time with dehydrated alcohol every time.Then again dry 10 under 60 degree of vacuum
Hour, obtain dry iron-containing Zn-MOF.
Dry metallic compound/the carbon matrix precursor of 200mg is calcined 3 hours in 900 degree of tubular type, calcined gas atmosphere
For nitrogen, 5 DEG C/min of heating rate obtains metallic compound/carbon composite.
Case study on implementation 2
10g natrium carbonicum calcinatum is distributed in 25ml deionized water, clear solution is stirred to get, anhydrous 100mg chlorine is added
Change zinc, stir to get homogeneous phase solution, move into reaction kettle, 145 degree at a temperature of, hydro-thermal reaction 11 hours.Temperature fall arrives
Room temperature is washed out, dry, obtains dry ZnO nanorod.
36ml n,N-Dimethylformamide (DMF) is mixed with 12ml deionized water, stirring obtains mixed solvent in 2 minutes,
Then above-mentioned solution is added in 82mg ZnO nanorod, stirring obtains homogeneous solution in 10 minutes.182mg 2- amino is added to benzene
Dioctyl phthalate stirs 5 minutes, and the anhydrous FeCl of 162mg is then added3, 6 days are stood in 32 degree of room temperature.It is then centrifuged for, centrifugation turns
Fast 8000r/min, centrifugation 5 minutes, are centrifuged 5 times, are washed every time with dehydrated alcohol every time.Then dry under 70 degree of vacuum again
8 hours, obtain dry metallic compound/carbon matrix precursor.
300mg metallic compound/carbon matrix precursor is calcined 2 hours in 900 degree of tubular type, calcined gas atmosphere is nitrogen
Gas, 6 DEG C/min of heating rate, obtains metal-containing compound/carbon composite.
Case study on implementation 3
10g natrium carbonicum calcinatum is distributed in 25ml deionized water, clear solution is stirred to get, anhydrous 100mg chlorine is added
Change zinc, stir to get homogeneous phase solution, move into reaction kettle, 145 degree at a temperature of, hydro-thermal reaction 11 hours.Temperature fall arrives
Room temperature is washed out, dry, obtains dry ZnO nanorod.
36ml n,N-Dimethylformamide (DMF) is mixed with 12ml deionized water, stirring obtains mixed solvent in 2 minutes,
Then above-mentioned solution is added in 82mg ZnO nanorod, stirring obtains homogeneous solution in 10 minutes.182mg 2- amino is added to benzene
Dioctyl phthalate stirs 5 minutes, and the anhydrous FeCl of 0mg is then added3, 6 days are stood in 32 degree of room temperature.It is then centrifuged for, centrifugal rotational speed
8000r/min, centrifugation 5 minutes, are centrifuged 5 times, are washed every time with dehydrated alcohol every time.Then again dry 8 under 70 degree of vacuum
Hour, obtain dry metallic compound/carbon matrix precursor.
300mg metallic compound/carbon matrix precursor is calcined 2 hours in 1000 degree of tubular type, calcined gas atmosphere is nitrogen
Gas, 5 DEG C/min of heating rate, obtains metal-containing compound/carbon composite.
Case study on implementation 4
10g natrium carbonicum calcinatum is distributed in 25ml deionized water, clear solution is stirred to get, anhydrous 100mg chlorine is added
Change zinc, stir to get homogeneous phase solution, move into reaction kettle, 135 degree at a temperature of, hydro-thermal reaction 11 hours.Temperature fall arrives
Room temperature is washed out, dry, obtains dry ZnO nanorod.
12ml n,N-Dimethylformamide (DMF) is mixed with 36ml deionized water, stirring obtains mixed solvent in 2 minutes,
Then above-mentioned solution is added in 82mg ZnO nanorod, stirring obtains homogeneous solution in 10 minutes.60.6mg 2- amino is added to benzene
Dioctyl phthalate stirs 6 minutes, and 59.1mg acetic anhydride cobalt is then added, stands 6 days in 33 degree of room temperature.It is then centrifuged for, is centrifuged
Revolving speed 8000r/min, centrifugation 5 minutes, are centrifuged 5 times, are washed every time with dehydrated alcohol every time.Then it is done under 80 degree of vacuum again
Dry 6 hours, obtain dry metallic compound/carbon matrix precursor.
400mg metallic compound/carbon matrix precursor is calcined 1 hour in 1200 degree of tubular type, calcined gas atmosphere is nitrogen
Gas, 7 DEG C/min of heating rate, obtains metal-containing compound/carbon composite.
Case study on implementation 5
10g natrium carbonicum calcinatum is distributed in 20ml deionized water, clear solution is stirred to get, anhydrous 100mg chlorine is added
Change zinc, stir to get homogeneous phase solution, move into reaction kettle, 135 degree at a temperature of, hydro-thermal reaction 13 hours.Temperature fall arrives
Room temperature is washed out, dry, obtains dry ZnO nanorod.
24ml n,N-Dimethylformamide (DMF) is mixed with 24ml deionized water, stirs to get mixed solvent, then
Above-mentioned solution is added in 82mg ZnO nanorod, stirs to get homogeneous solution.The stirring of 546mg 2- amino terephthalic acid (TPA) is added
Homogeneous phase solution is obtained, the anhydrous nickel acetylacetonate of 768mg is then added, stands 6 days in 30 degree of room temperature.It is then centrifuged for, is centrifuged
Revolving speed 8000r/min, centrifugation 5 minutes, are centrifuged 5 times, are washed with dehydrated alcohol every time.Then drying 12 is small under 50 degree of vacuum again
When, obtain dry Zn-MOF.
Dry metallic compound/the carbon matrix precursor of 100mg is calcined 4 hours in 800 degree of tubular type, calcined gas atmosphere
For nitrogen, 4 DEG C/min of heating rate obtains metallic compound/carbon composite.
Embodiment described above only expresses embodiments of the present invention, and but it cannot be understood as to the invention patent
Range limitation, it is noted that for those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (5)
1. a kind of preparation method of special construction metallic compound/carbon composite, it is characterised in that following steps:
The first step prepares metallic compound/carbon matrix precursor
Solid-state ZnO nano material is put into organic solvent and deionized mixed solution, 2- amino terephthaldehyde is then added
Sour and other metal salt, after standing 3-10 days at room temperature, centrifuge separation, deionized water wash drying, obtain special construction
Metallic compound/carbon composite presoma；
The amount of the 2- amino terephthalic acid (TPA) is adjusted according to the amount of ZnO nano material, ZnO nano material and 2- amino
The molar ratio of terephthalic acid (TPA) is 3:1-1:3；The amount of the amount foundation 2- amino terephthalic acid (TPA) of the metal salt is adjusted,
The molar ratio of metal salt and 2- amino terephthalic acid (TPA) is 0-1:1；
Second step prepares metallic compound/carbon composite
Metallic compound/carbon composite presoma that the first step obtains is placed in tube furnace, calcined gas atmosphere is
Inert gas obtains metallic compound/carbon composite of special construction after calcining 1-4 hours at 800-1200 DEG C；Product
Particle size it is related with the addition amount of metal salt, increase with metal salt amount is added, metallic compound size increases, in 2-
It between 50nm, is uniformly embedded in carbon structure, wherein carbon material is three dimensional micron ball made of being stacked as two-dimensional nano piece.
2. a kind of preparation method of special construction metallic compound/carbon composite according to claim 1, feature exist
In in metal salt described in the first step, metal can be iron, cobalt, nickel, copper, manganese, and the form of salt can be acetate, salt
Hydrochlorate, nitrate, sulfate, acetylacetonate.
3. a kind of preparation method of special construction metallic compound/carbon composite according to claim 1 or 2, special
Sign is, in organic solvent described in the first step and deionized mixed solution, the volume ratio of organic solvent and water is 3:1-
1:3。
4. a kind of preparation method of special construction metallic compound/carbon composite according to claim 1 or 2, special
Sign is that the organic solvent is n,N-Dimethylformamide DMF, methanol, ethyl alcohol.
5. a kind of preparation method of special construction metallic compound/carbon composite according to claim 3, feature exist
In the organic solvent is n,N-Dimethylformamide DMF, methanol, ethyl alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110357068A (en) * | 2019-08-15 | 2019-10-22 | 中国科学技术大学 | A kind of synthetic method of classifying porous carbon nanomaterial |
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| CN110357068A (en) * | 2019-08-15 | 2019-10-22 | 中国科学技术大学 | A kind of synthetic method of classifying porous carbon nanomaterial |
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