CN103395768A - Preparation method of microporous nanocarbon balls with high specific surface area and uniform and regular aperture - Google Patents
Preparation method of microporous nanocarbon balls with high specific surface area and uniform and regular aperture Download PDFInfo
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Abstract
The invention discloses a preparation method of microporous nanocarbon balls with high specific surface area and uniform and regular aperture. The microporous nanocarbon balls with uniform aperture are obtained by synthesizing ionic liquid, preparing powder, treating the powder, carbonizing, performing aftertreatment and activating. By the mode and according to the preparation method of the microporous nanocarbon balls with high specific surface area and uniform and regular aperture, various metal salts and organic ligands can be selected to synthesize raw materials in the ionic liquid and carbonize in inert gases, and metal oxide is removed by an inorganic acid, so that the production cost is greatly reduced, the production flow is safe and reliable, the practical value is prominent, and industrialized production is promoted.
Description
Technical field
The present invention relates to the preparation field of porous carbon materials, particularly relate to a kind of method for preparing the even and regular porous nano carbon ball of high-specific surface area, different size, aperture with metal-salt and organic ligand.
Background technology
Carbon is one of important element that forms all life body, is distributed in a variety of forms nature.It is long-standing that carbon is regarded as important inorganic materials, and extensively be present in organic polymer material as in cotton, silk, rubber, plastics, and the development of carbon material is maked rapid progress especially, and porous nano carbon ball is one of typical case.Porous nano carbon ball itself has low density, and the advantages such as high-specific surface area and high stability are being contained important potential application in the fields such as gas adsorption, catalytic carrier, solar cell.
At present, prepare porous nano carbon ball three kinds of methods are arranged: 1, chemical Vapor deposition process: gas or steam (ethene, acetylene, vinylbenzene, benzene, toluene, methane etc.) the Pintsch process Formed that will contain carbon source; 2, hard template method: at first select suitable porous material, for example classical as SBA-15, MCM-41 equimolecular sieve, then inject furfuryl alcohol or with the gas (ethene of costliness, propylene etc.) be carbon source, high temperature cabonization under protection of inert gas, then remove hard template with hydrofluoric acid; 3, polymkeric substance carbonization: first synthetic polymer, then high temperature cabonization under protection of inert gas, finally obtain nano carbon microsphere.Although above method can access nano carbon microsphere to a certain extent, but use or carbon source expensive or that toxicity is larger in synthetic system, aftertreatment need to be used the hydrofluoric acid to the human body severe corrosive, preparation procedure is loaded down with trivial details, this has just limited aforesaid method and has prepared the porous carbon ball, causes it in industry, to be difficult to promotion and application.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of different size (preparation method of porous nano carbon ball of 5nm ~ 1000nm) of pollution-free, cheap and suitable suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: the evenly preparation method of the porous nano carbon ball of rule of a kind of high-specific surface area aperture is provided, comprises that step is:
(1) synthetic ionic liquid: choline chloride 60 and urea are at room temperature mixed to rear stirring 12 ~ 20 hours according to the ratio of mol ratio 1:2 ~ 10, obtain ionic liquid;
(2) prepare powder: organic ligand is joined in the synthetic ionic liquid of step (1), after dissolving, organic ligand adds metal-salt, and constantly stir, under 60 ~ 80 ℃ of conditions, reacted 5 ~ 10 hours, be down to suction filtration after room temperature, with distilled water, repeatedly rinse, and then oven dry obtains powder under 60 ~ 80 ℃ of conditions, wherein the mol ratio of metal-salt, organic ligand, ionic liquid is 10:1 ~ 2:4 ~ 5;
(3) powder treatment: the powder that step (2) is obtained, with methyl alcohol or alcohol immersion, changed one time solvent every 12 ~ 20 hours, and this process repeats 2 ~ 4 times, then naturally dries, and obtains powder;
(4) carbonization: the powder that step (3) is obtained is warming up to 600 ~ 1100 ℃ by room temperature and carries out carbonization under protection of inert gas, drop to afterwards room temperature;
(5) aftertreatment: be that at room temperature stir process is centrifugal after 12 ~ 24 hours for 1% ~ 10% mineral acid with massfraction by step (4) products therefrom, repeat aforesaid operations, until supernatant liquor is without metallic element, then by centrifugal after product washing with water repeatedly, until the pH value is 7 ~ 8, then naturally dry, obtain carbon dust;
(6) activation: the carbon dust in step (5) is joined in Qing Yangization Jia ﹑ Qing Yangization Na ﹑ clorox or calcium hydroxide; the mass ratio of carbon dust and Qing Yangization Jia ﹑ Qing Yangization Na ﹑ clorox or calcium hydroxide is 1:4 ~ 1:8; then under protection of inert gas, by room temperature, being warming up to 700 ~ 900 ℃ activates; naturally cool to afterwards room temperature; finally with distilled water, repeatedly rinse; until the pH value is 7 ~ 8; under 80 ~ 100 ℃ of conditions, dry again, obtain the porous nano carbon ball of aperture homogeneous.
In a preferred embodiment of the present invention, described in step (2), metal-salt is cupric nitrate, nickel acetate, aluminum nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate, zinc acetate, cadmium acetate, cadmium nitrate, europium nitrate or Terbium trinitrate, when the boiling point of the metal oxide that generates, during lower than carbonization temperature, omit step (5).
In a preferred embodiment of the present invention, organic ligand described in step (2) is methylimidazole, terephthalic acid, trimesic acid, N-Methylimidazole, pyridine dicarboxylic acid, thiophene dicarboxylic acid, 4,4-dipyridyl, 1,4-naphthalene diacid, 1,2,4-triazole, benzoglyoxaline, fumaric acid, nicotinic acid or γ-picolinic acid.
In a preferred embodiment of the present invention, temperature-rise period described in step (4) is the temperature-rise period gradually of 1,2 or 3 section, temperature-fall period is also the temperature-fall period gradually of 1,2 or 3 section, every section heats up or after temperature-fall period completes, kept 1 ~ 10 hour, and then carry out intensification or the temperature-fall period of next section, heat up or the speed of cooling is 0.5 ~ 5 ℃/min.
In a preferred embodiment of the present invention, described in step (5), mineral acid is hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hypochlorous acid or silicic acid.
The invention has the beneficial effects as follows: the present invention uses ionic liquid as reaction system, with traditional hydrothermal method, compares, and ionic liquid has many advantages.For example ionic liquid is non-combustible, and is non-volatile, tasteless, and the advantage of extremely low vapour pressure is used it, the problems such as environmental pollution of also having avoided volatile organic compound to cause under high vacuum condition.Simultaneously organic compound and inorganic salt are had to stronger dissolving power, under homogeneous phase condition, can react.The more important thing is that ionic liquid has satisfactory stability, be easy to product separation, recyclable and recycle.
With the soft template carbonization, compare, the present invention avoids using expensive polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer to be tensio-active agent, directly utilizes cheap metal-salt and organic ligand carbonization in tube furnace, and operation is simple, low price, be suitable for suitability for industrialized production.
The present invention uses metal-salt and organic ligand synthetic materials to carry out carbonization, with traditional carbonization, compare, organic ligand in the present invention directly provides carbon source, without the extra furfuryl alcohol that injects, toxic liquid and the ethene such as tetracol phenixin, the gaseous carbon sources that propylene etc. are expensive, no matter from security standpoint or price angle, the present invention has more superiority, is more suitable for suitability for industrialized production.
The present invention is in the carbonization last handling process, directly use the mineral acid (hydrochloric acid of easily preparation and safety, sulfuric acid, nitric acid etc.), when even carbonization temperature is higher than the oxide compound temperature, can save this step, this has replaced the harmful hydrofluoric acid that in the past used, not only greatly reduced production cost, and Production Flow Chart is more safe and reliable, and practical value is more outstanding, more is conducive to suitability for industrialized production.
The accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, in below describing embodiment, the accompanying drawing of required use is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also according to these accompanying drawings, obtain other accompanying drawing, wherein:
Fig. 1 is the x-ray diffraction pattern of porous nano carbon ball of the present invention, and this figure is the XRD diffractogram after embodiment mono-to 14 gained porous nano carbon ball carbonization, and as can be seen from the figure last carbon ball is so long as graphite-phase and amorphous phase;
Fig. 2 is the electron scanning micrograph of embodiment mono-porous nano carbon ball, and carbon ball size is 20nm;
Fig. 3 is the electron scanning micrograph of embodiment five porous nano carbon balls, and carbon ball size is 90nm;
Fig. 4 is the electron scanning micrograph of embodiment nine porous nano carbon balls, and carbon ball size is 500nm;
Fig. 5 is the transmission electron microscope photo of embodiment six nano carbon microspheres, and pore size is 0.3nm;
Fig. 6 is the nitrogen adsorption figure of embodiment eight nano carbon microspheres, and specific surface area is about 1300m
2/ g, aperture is divided into 0.25nm.
Embodiment
Below will the technical scheme in the embodiment of the present invention be clearly and completely described, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making all other embodiment that obtain under the creative work prerequisite, belong to the scope of protection of the invention.
Embodiment mono-:
(1) ratio that is 2:1 by urea and choline chloride 60 according to mol ratio mixes, and with glass stick, firmly stirs, and then is placed on magnetic stirring apparatus and stirs 12 hours, obtains ionic liquid;
(2) reaction mixture nitrate trihydrate copper: N-Methylimidazole: the mol ratio of ionic liquid is 5:0.5:2.5.Its concrete operations are: get the 0.073g ionic liquid, add 0.014g N-Methylimidazole, be placed on heating while stirring in 60 ℃ of heating jackets, after the N-Methylimidazole dissolves, add again 0.4097g nitrate trihydrate copper, continue to stir 30 minutes, then put into 60 ℃ of baking ovens, after 5 hours, take out, naturally drop to room temperature, suction filtration, rinse 3 times repeatedly with distilled water, then puts into 80 ℃ of baking ovens and dry.
(3) finally the sample of oven dry is soaked with methyl alcohol, and constantly stir, every 12 hours, change one time methyl alcohol, this process repeats 2 times, naturally dries.
(4) step (3) is obtained to sample and put into tube furnace, pass into rare gas element, after 1 hour, start carbonization.Concrete carbodiimide procedure is: the speed with 0.5 ℃/min is heated to 200 ℃ from room temperature, and kept 2 hours, then the speed with 0.5 ℃/min is heated to 600 ℃ from 200 ℃, and kept 1 hour, speed with 1 ℃/min is heated to 800 ℃ from 600 ℃ subsequently, and kept 5 hours, finally naturally drop to room temperature.
(5) it is, in 10% hydrochloric acid, at room temperature to stir 12 hours that the sample of step (4) being obtained is dissolved in massfraction, centrifugal, then to be dissolved in massfraction be, in 10% hydrochloric acid, to repeat this step, until supernatant liquor detects without cupric ion through ICP.Again centrifugal after product is rinsed repeatedly with distilled water, until the pH value is 7, then sample is dried naturally.
(6) by mass ratio, be that sample and potassium hydroxide solution in the step (5) of 1:4 mixes, put into tube furnace, pass into argon gas, the rare gas elementes such as nitrogen, speed with 1 ℃/min is heated to 400 ℃ from room temperature, keeps 3 hours, and then the speed with 5 ℃/min is heated to 700 ℃ from 400 ℃, kept 1.5 hours, and naturally cooled to afterwards room temperature.Then with distilled water, repeatedly rinse, until the pH value is 7, then puts into 100 ℃ of baking ovens and dry, the carbon ball that obtains is of a size of 20nm, and big or small homogeneous, micropore size are 1.2nm, and specific surface area is 1500m
2/ g.
Embodiment bis-:
Preparation process is similar to embodiment mono-, and difference is that metal-salt, organic ligand and the carbodiimide procedure selected are different.Concrete difference is as follows:
The metal-salt that this example is selected is four water acetic acid nickel, and organic ligand is terephthalic acid, and the mol ratio of reaction mixture nickel acetate, terephthalic acid, ionic liquid is 5:1:2.5.
Concrete carbodiimide procedure is: the speed with 0.5 ℃/min is heated to 300 ℃ from room temperature, then with the speed of 0.5 ℃/min, is heated to 600 ℃ from 300 ℃ equally, and keeps 5 hours, finally naturally drops to room temperature.
This routine resulting porous nano carbon ball size is 70nm, and big or small homogeneous, micropore size are 0.8nm, and specific surface area is 1300m
2/ g.
Embodiment tri-:
Preparation process is similar to embodiment 1, and difference is the metal-salt of selecting, and organic ligand is different with carbodiimide procedure.Concrete difference is as follows:
The metal-salt that this example is selected is nine water aluminum nitrates, and organic ligand is glyoxal ethyline, and the mol ratio of reaction mixture nine water aluminum nitrates, glyoxal ethyline, ionic liquid is 5:0.5:2.
Concrete carbodiimide procedure is: the speed with 1 ℃/min is heated to 700 ℃ from room temperature, and keeps 8 hours, then naturally drops to room temperature.
This routine resulting porous nano carbon ball size is 200nm, and big or small homogeneous, micropore size are 1.3nm, and specific surface area is 1700m
2/ g.
Embodiment tetra-:
Preparation process is similar to embodiment mono-, and its difference is metal-salt, organic ligand, carbodiimide procedure and the last carbon ball treatment process difference of selecting.Concrete difference is as follows:
The metal-salt that this example is selected is six water acetic acid zinc, and organic ligand is terephthalic acid.The mol ratio of reaction mixture six water acetic acid zinc, terephthalic acid, ionic liquid is 5:0.8:2.Concrete carbodiimide procedure is: the speed with 1 ℃/min is heated to 400 ℃ from room temperature, and keeps 5 hours, then with the speed of 0.5 ℃/min, is heated to 1000 ℃ from 400 ℃, and keeps 8 hours, and finally the speed with 2 ℃/min drops to room temperature from 1000 ℃.Because this program carbonization temperature is 1000 ℃, higher than the boiling point of zinc oxide (800 ℃ of boiling points), zinc oxide along with rare gas element overflows, saves the last handling process described in summary of the invention with the form of steam, directly obtains porous nano carbon ball.
This routine resulting porous nano carbon ball size is 300nm, and big or small homogeneous, micropore size are 2nm, and specific surface area is 1570m
2/ g.
Embodiment five:
Preparation process is similar to embodiment mono-, and its difference is that the metal-salt, organic ligand and the carbodiimide procedure that adopt are different.Concrete difference is as follows:
The metal-salt that this example is selected is cobalt nitrate hexahydrate, and organic ligand is terephthalic acid.The mol ratio of reaction mixture cobalt nitrate hexahydrate, terephthalic acid, ionic liquid is 5:0.6:2.Concrete carbodiimide procedure is: the speed with 0.5 ℃/min is heated to 200 ℃ from room temperature, and kept 2 hours, then with the speed of 0.5 ℃/min from 500 ℃ of 200 ℃ of heating, and kept 4 hours, finally with the speed of 1 ℃/min, be heated to 1000 ℃ from 500 ℃, and kept 6 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 1 ℃/min, drop to 500 ℃ from 1000 ℃, then with the speed of 0.5 ℃/min, drop to 200 ℃ from 500 ℃, finally with 0.5 ℃/min of same speed, from 200 ℃, drop to room temperature.
This routine resulting porous nano carbon ball size is 90nm, and big or small homogeneous, micropore size are 1.5nm, and specific surface area is 1800m
2/ g.
Embodiment six:
Preparation process is similar to embodiment five, and its difference is that the organic ligand, the carbodiimide procedure that adopt are different with the mode of cooling gradually.Concrete difference is as follows:
The metal-salt that this example is selected remains cobalt nitrate hexahydrate, and organic ligand is the N-Methylimidazole.The mol ratio of reaction mixture cobalt nitrate hexahydrate, N-Methylimidazole, ionic liquid is 5:0.6:2.2.Concrete carbodiimide procedure is: the speed with 3 ℃/min is heated to 280 ℃ from room temperature, and kept 2 hours, then with the speed of 2 ℃/min from 600 ℃ of 280 ℃ of heating, and kept 4 hours, finally with the speed of 1 ℃/min, be heated to 900 ℃ from 600 ℃, and kept 6 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 0.5 ℃/min, drop to 600 ℃ from 900 ℃, then with the speed of 0.5 ℃/min, drop to 400 ℃ from 600 ℃, finally the speed with 1 ℃/min drops to room temperature from 200 ℃.
This routine resulting porous nano carbon ball size is 800nm, and big or small homogeneous, micropore size are 0.3nm, and specific surface area is 1200m
2/ g.
Embodiment seven:
Preparation process is similar to embodiment seven, and its difference is metal-salt, the organic ligand that adopts, and carbodiimide procedure is different with the mode of cooling gradually.Concrete difference is as follows:
The metal-salt that this example is selected is zinc nitrate hexahydrate, and organic ligand is terephthalic acid.The mol ratio of reaction mixture zinc nitrate hexahydrate, terephthalic acid, ionic liquid is 5:1:2.2.Concrete carbodiimide procedure is: the speed with 0.5 ℃/min is heated to 600 ℃ from room temperature, and kept 2 hours, then with the speed of 1 ℃/min from 800 ℃ of 600 ℃ of heating, and kept 4 hours, finally with the speed of 0.5 ℃/min, be heated to 1100 ℃ from 800 ℃, and kept 4 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 0.5 ℃/min, drop to 800 ℃ from 1100 ℃, then with the speed of 1 ℃/min, drop to 600 ℃ from 800 ℃, finally the speed with 0.5 ℃/min drops to room temperature from 600 ℃.Because the metal-salt in this embodiment is zinc, similar with embodiment tetra-, without with the final carbonized product of mineral acid treatment, zinc oxide at high temperature with the form of steam along with rare gas element overflows, directly obtain porous nano carbon ball.
This routine resulting porous nano carbon ball size is 780nm, and big or small homogeneous, micropore size are 1.8nm, and specific surface area is 1900m
2/ g.
Embodiment eight:
Preparation process is similar to embodiment seven, and its difference is metal-salt, the organic ligand of selecting, and carbodiimide procedure is different with the mode of cooling gradually.Concrete difference is as follows:
The metal-salt that this example is selected is the acetate dihydrate cadmium, and organic ligand is the N-Methylimidazole.The mol ratio of reaction mixture acetate dihydrate cadmium, N-Methylimidazole, ionic liquid is 5:0.8:2.5.Concrete carbodiimide procedure is: the speed with 2 ℃/min is heated to 400 ℃ from room temperature, and kept 3 hours, then with the speed of 1 ℃/min from 800 ℃ of 400 ℃ of heating, and kept 4 hours, finally with the speed of 0.5 ℃/min, be heated to 1200 ℃ from 800 ℃, and kept 4 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 1 ℃/min, drop to 800 ℃ from 1200 ℃, then the speed with 1 ℃/min drops to room temperature from 800 ℃.Because the metal-salt in this embodiment is cadmium, similar with embodiment seven, without with the final carbonized product of mineral acid treatment, Cadmium oxide at high temperature with the form of steam along with rare gas element overflows, directly obtain porous nano carbon ball.
This routine resulting porous nano carbon ball size is 900nm, and big or small homogeneous, micropore size are 0.25nm, and specific surface area is 1350m
2/ g.
Embodiment nine:
Preparation process is similar to embodiment mono-, and its difference is metal-salt, and organic ligand is different with carbodiimide procedure.Concrete difference is as follows:
The metal-salt that this example is selected is europium nitrate, and organic ligand is Isosorbide-5-Nitrae-naphthalene diacid.The mol ratio of reaction mixture europium nitrate, Isosorbide-5-Nitrae-naphthalene diacid, ionic liquid is 5:0.8:2.2.Concrete carbodiimide procedure is: the speed with 3 ℃/min is heated to 250 ℃ from room temperature, and kept 3 hours, then with the speed of 1 ℃/min from 600 ℃ of 250 ℃ of heating, and kept 4 hours, finally with the speed of 0.5 ℃/min, be heated to 1100 ℃ from 600 ℃, and kept 5 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 1 ℃/min, drop to 700 ℃ from 1100 ℃, then with the speed of 1 ℃/min, drop to 200 ℃ from 700 ℃, finally with 1 ℃/min of same speed, from 200 ℃, drop to room temperature.
This routine resulting porous nano carbon ball size is 500nm, and big or small homogeneous, micropore size are 1.3nm, and specific surface area is 1680m
2/ g.
Embodiment ten:
Preparation process is similar to embodiment tetra-, and its difference is metal-salt, the organic ligand that adopts, and carbodiimide procedure is different with the mode of cooling gradually.Concrete difference is as follows:
The metal-salt that this example is selected is Terbium trinitrate, and organic ligand is benzoglyoxaline.The mol ratio of reaction mixture nitric acid spy, benzoglyoxaline, ionic liquid is 5:0.55:2.Concrete carbodiimide procedure is: the speed with 0.5 ℃/min is heated to 500 ℃ from room temperature, and kept 2 hours, then with the speed of 1 ℃/min from 800 ℃ of 500 ℃ of heating, and kept 3 hours, finally with the speed of 0.5 ℃/min, be heated to 1100 ℃ from 800 ℃, and kept 4 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 0.5 ℃/min, drop to 700 ℃ from 1100 ℃, then with the speed of 1 ℃/min, drop to 400 ℃ from 700 ℃, finally the speed with 0.5 ℃/min drops to room temperature from 400 ℃.
This routine resulting porous nano carbon ball size is 14nm, and big or small homogeneous, micropore size are 0.8nm, and specific surface area is 1485m
2/ g.
Embodiment 11:
Preparation process is similar to embodiment five, and its difference is the organic ligand that adopts, and carbodiimide procedure is different with the mode of cooling gradually.Concrete difference is as follows:
The metal-salt that this example is selected remains cobalt nitrate hexahydrate, and organic ligand is 1,2,4-triazole.Reaction mixture cobalt nitrate hexahydrate, 1,2, the mol ratio of 4-triazole, ionic liquid are 5:0.52:2.4.Concrete carbodiimide procedure is: the speed with 7 ℃/min is heated to 280 ℃ from room temperature, and kept 2 hours, then with the speed of 5 ℃/min from 600 ℃ of 280 ℃ of heating, and kept 7 hours, finally with the speed of 1 ℃/min, be heated to 900 ℃ from 600 ℃, and kept 3 ~ 5 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 0.5 ℃/min, drop to 600 ℃ from 900 ℃, then with the speed of 1 ℃/min, drop to 400 ℃ from 600 ℃, finally the speed with 1 ℃/min drops to room temperature from 400 ℃.
This routine resulting porous nano carbon ball size is 600nm, and big or small homogeneous, micropore size are 1.7nm, and specific surface area is 1350m
2/ g.
Embodiment 12:
Preparation process is similar to embodiment tetra-, and its difference is metal-salt, the organic ligand that adopts, and carbodiimide procedure is different with the mode of cooling gradually.Concrete difference is as follows:
The metal-salt that this example is selected is nitrate trihydrate copper, and organic ligand is Isosorbide-5-Nitrae-naphthalene diacid.The mol ratio of reaction mixture nitrate trihydrate copper, Isosorbide-5-Nitrae-naphthalene diacid, ionic liquid is 5:1:2.4.Concrete carbodiimide procedure is: the speed with 5 ℃/min is heated to 600 ℃ from room temperature, and kept 3 hours, then with the speed of 0.5 ℃/min from 800 ℃ of 600 ℃ of heating, and kept 4 hours, finally with the speed of 0.5 ℃/min, be heated to 1000 ℃ from 800 ℃, and kept 4 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 0.5 ℃/min, drop to 800 ℃ from 1000 ℃, then with the speed of 2 ℃/min, drop to 600 ℃ from 800 ℃, finally the speed with 0.5 ℃/min drops to room temperature from 600 ℃.
This routine resulting porous nano carbon ball size is 600nm, and big or small homogeneous, micropore size are 1.5nm, and specific surface area is 1100m
2/ g.
Embodiment 13:
Preparation process is similar to embodiment five, and its difference is that carbodiimide procedure is different with the mode of cooling gradually.Concrete difference is as follows:
The metal-salt that this example is selected remains cobalt nitrate hexahydrate, and organic ligand is terephthalic acid.The mol ratio of reaction mixture cobalt nitrate hexahydrate, terephthalic acid, ionic liquid is 5:0.55:2.2.Concrete carbodiimide procedure is: the speed with 3 ℃/min is heated to 260 ℃ from room temperature, and kept 3 hours, then with the speed of 2 ℃/min from 500 ℃ of 260 ℃ of heating, and kept 7 hours, finally with the speed of 0.5 ℃/min, be heated to 900 ℃ from 500 ℃, and kept 3 ~ 6 hours.In temperature-fall period, taked gradually the method for temperature, at first with the speed of 0.5 ℃/min, drop to 500 ℃ from 900 ℃, then with the speed of 2 ℃/min, drop to 260 ℃ from 500 ℃, finally the speed with 3 ℃/min drops to room temperature from 260 ℃.
This routine resulting porous nano carbon ball size is 5nm, and big or small homogeneous, micropore size are 1 nm, and specific surface area is 1050m
2/ g.
Embodiment 14:
Preparation process is similar to embodiment mono-, and its difference is the carbodiimide procedure difference.Concrete difference is as follows:
The metal-salt that this example is selected is still nitrate trihydrate copper, and organic ligand is the N-Methylimidazole.The mol ratio of reaction mixture nitrate trihydrate copper, N-Methylimidazole, ionic liquid is 5:1:2.3.Concrete carbodiimide procedure is: the speed with 1 ℃/min is heated to 350 ℃ from room temperature, then with the speed of 1 ℃/min, is heated to 800 ℃ from 350 ℃ equally, and keeps 6 hours, finally naturally drops to room temperature.
This routine resulting porous nano carbon ball size is 1000nm, and big or small homogeneous, micropore size are 0.5nm, and specific surface area is 1580m
2/ g.
The present invention can select various metal-salts and organic ligand synthetic raw material in ionic liquid, then carbonization in rare gas element, finally with mineral acid, remove metal oxide, this has not only greatly reduced production cost, and Production Flow Chart is more safe and reliable, practical value is more outstanding, more is conducive to suitability for industrialized production.
This invention utilizes metal-salt and organic ligand to be starting material, organic ligand directly provides carbon source, having overcome the expensive gases such as the liquid such as the poisonous furfuryl alcohol of rear injection, tetracol phenixin and ethene, propylene is the defect of carbon source, according to instead should time ﹑ temperature degree ﹑ proportioning etc. difference synthesize and have different size (the micropore of 5nm ~ the 1000nm) (nano carbon microsphere of 0.25nm ~ 2nm).The porous nano carbon ball of different size has wide DEVELOPMENT PROSPECT in the fields such as absorption, energy storage, catalysis, light, battery.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical field, all in like manner be included in scope of patent protection of the present invention.
Claims (5)
1. the preparation method of the porous nano carbon ball of the even rule in high-specific surface area aperture, is characterized in that, comprises that step is:
(1) synthetic ionic liquid: choline chloride 60 and urea are at room temperature mixed to rear stirring 12 ~ 20 hours according to the ratio of mol ratio 1:2 ~ 10, obtain ionic liquid;
(2) prepare powder: organic ligand is joined in the synthetic ionic liquid of step (1), after dissolving, organic ligand adds metal-salt, and constantly stir, under 60 ~ 80 ℃ of conditions, reacted 5 ~ 10 hours, be down to suction filtration after room temperature, with distilled water, repeatedly rinse, and then oven dry obtains powder under 60 ~ 80 ℃ of conditions, wherein the mol ratio of metal-salt, organic ligand, ionic liquid is 10:1 ~ 2:4 ~ 5;
(3) powder treatment: the powder that step (2) is obtained, with methyl alcohol or alcohol immersion, changed one time solvent every 12 ~ 20 hours, and this process repeats 2 ~ 4 times, then naturally dries, and obtains powder;
(4) carbonization: the powder that step (3) is obtained is warming up to 600 ~ 1100 ℃ by room temperature and carries out carbonization under protection of inert gas, drop to afterwards room temperature;
(5) aftertreatment: be that at room temperature stir process is centrifugal after 12 ~ 24 hours for 1% ~ 10% mineral acid with massfraction by step (4) products therefrom, repeat aforesaid operations, until supernatant liquor is without metallic element, then by centrifugal after product washing with water repeatedly, until the pH value is 7 ~ 8, then naturally dry, obtain carbon dust;
(6) activation: the carbon dust in step (5) is joined in Qing Yangization Jia ﹑ Qing Yangization Na ﹑ clorox or calcium hydroxide; the mass ratio of carbon dust and Qing Yangization Jia ﹑ Qing Yangization Na ﹑ clorox or calcium hydroxide is 1:4 ~ 1:8; then under protection of inert gas, by room temperature, being warming up to 700 ~ 900 ℃ activates; naturally cool to afterwards room temperature; finally with distilled water, repeatedly rinse; until the pH value is 7 ~ 8; under 80 ~ 100 ℃ of conditions, dry again, obtain the porous nano carbon ball of aperture homogeneous.
2. preparation method according to claim 1, it is characterized in that, described in step (2), metal-salt is cupric nitrate, nickel acetate, aluminum nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate, zinc acetate, cadmium acetate, cadmium nitrate, europium nitrate or Terbium trinitrate, when the boiling point of the metal oxide that generates, during lower than carbonization temperature, omit step (5).
3. preparation method according to claim 1, it is characterized in that, organic ligand described in step (2) is methylimidazole, terephthalic acid, trimesic acid, N-Methylimidazole, pyridine dicarboxylic acid, thiophene dicarboxylic acid, 4,4-dipyridyl, 1,4-naphthalene diacid, 1,2,4-triazole, benzoglyoxaline, fumaric acid, nicotinic acid or γ-picolinic acid.
4. preparation method according to claim 1, it is characterized in that, temperature-rise period described in step (4) is the temperature-rise period gradually of 1,2 or 3 section, temperature-fall period is also the temperature-fall period gradually of 1,2 or 3 section, every section heats up or after temperature-fall period completes, kept 1 ~ 10 hour, and then carry out intensification or the temperature-fall period of next section, the speed of intensification or cooling is 0.5 ~ 5 ℃/min.
5. preparation method according to claim 1, is characterized in that, described in step (5), mineral acid is hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hypochlorous acid or silicic acid.
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