CN103265005B - Nano-carbon material/carbon aerogel (CA) microwave synthesis method - Google Patents
Nano-carbon material/carbon aerogel (CA) microwave synthesis method Download PDFInfo
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- CN103265005B CN103265005B CN201310143034.1A CN201310143034A CN103265005B CN 103265005 B CN103265005 B CN 103265005B CN 201310143034 A CN201310143034 A CN 201310143034A CN 103265005 B CN103265005 B CN 103265005B
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Abstract
The invention discloses a nano-carbon material/carbon aerogel (CA) microwave synthesis method. The nano-carbon material/CA microwave synthesis method comprises that resorcinol and formaldehyde as raw materials are synthesized into organic wet gel as an intermediate by a microwave synthesis method; acetone is added into the organic wet gel to extract water and impurities in the organic wet gel; and the treated organic wet gel is subjected to high temperature charing at a temperature of 900 DEG C in the nitrogen protective atmosphere for 2h to produce CA. The CA has the particle sizes less than 50nm and has a large specific surface area and high porosity. The nano-carbon material/CA microwave synthesis method has the advantages of fast synthesis speed, low energy consumption and small pollution.
Description
Technical field
The invention belongs to macromolecular material and electrochemical applications technical field, be specifically related to a kind of with Resorcinol (R) and formaldehyde (F) for raw material, applied microwave technology prepares the method for carbon nano-material/charcoal-aero gel (CA), this carbon nano-material/charcoal-aero gel is a kind of novel light porous material, there is multiple high-performance, as low density, homogeneity, high-specific surface area, high conductivity, relative to the conventional porous such as gac, activated carbon fiber Carbon Materials, its performance is better.Can be used for the aspects such as catalyzer, ultracapacitor, water treatment and Chu Qing.
Background technology
Carbon Materials, with its chemical stability, thermostability, biocompatibility, electroconductibility and the feature such as low price, wide material sources, gets more and more people's extensive concerning for a long time always.Scientist foretells: after entering 21 century, and Carbon Materials will replace iron and the silicon of a large amount of use at present, become the key material supporting advanced industry.
In recent years, the huge applications potentiality that novel charcoal material also exists in every field such as the energy, chemical industry, environmental protection as carbon molecular sieve, carbon nanotube, carbon nanofibers etc. are one of Disciplinary Frontiers of international scientific research always.Along with Carbon Materials science development, the appearance of Novel carbon nano-porous materials " charcoal-aero gel " arouses widespread concern.
Charcoal-aero gel (CA) is a kind of Mesoporous Carbon Materials with unique three-dimensional Specific surface area, this is a kind of nano level Carbon Materials of novelty, there is specific surface area large, porosity is high, low and the feature such as adjustable of density, because the electricity of its uniqueness, optics, calorifics, magnetics, catalytic performance make it have broad application prospects in military affairs, space flight, environmental protection, the energy, medicine and other fields.
People's routine prepares carbon nano-material charcoal-aero gel method, by Resorcinol and formaldehyde soluble in water with the mol ratio of 1:2, add catalyzer, close and be placed in 80 DEG C of water-bath 7d and generate organic wet gel.Then dry 5h in thermostatic drying chamber, obtains organic aerogel.Carbonize in high temperature carbonization furnace, be warming up to 900 DEG C ~ 1000 DEG C, and want blanketing with inert gas, finally obtain charcoal-aero gel (CA) powder of black.More than for the power consumption of traditional method technological process is excessive, and a large amount of production can not be used for.
Summary of the invention
Object of the present invention aims to provide a kind of microwave method synthetic method of carbon nano-material/charcoal-aero gel (CA), have studied emphatically the condition of intermediate product organic aerogel Microwave synthesize to the impact of charcoal-aero gel status color.The impact of catalyzer different in integrated survey microwave method process, microwave time, microwave power, catalyst proportion and productive rate.The method technological process is simple, and art breading is convenient, and microwave introduces experiment, and substantially reduce the reaction times, improve chemical reaction rate, productive rate is high, and product property is stablized.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of microwave method synthetic method of carbon nano-material/charcoal-aero gel (CA), is characterized in that, synthesize by following concrete steps:
With Resorcinol (R) and formaldehyde (F) for raw material, Resorcinol (R) is 1:2 with the mol ratio of formaldehyde (F), be under the condition of 400W ~ 800W at microwave power, appropriate deionized water and anhydrous sodium carbonate is added in raw material, stir, be 20min ~ 40min to the radiated time of raw material, temperature of reaction is 80 DEG C, synthetic intermediate;
Intermediate is aging 4d at insulation 80 DEG C further.Then add acetone soln at normal temperatures and pressures to remove the moisture in intermediate and impurity, obtain wine-colored organic aerogel.
The organic aerogel obtained carries out dry 0.5h in infrared drying oven, then dry 5h at 110 DEG C in thermostatic drying chamber, finally at rare gas element (N
2) carbonization in protection pipe type stove, be warming up to 900 DEG C, then carbonization 2h at 900 DEG C with 5 DEG C/min ~ 10 DEG C/min, naturally cooling is lowered the temperature, and obtains charcoal-aero gel (CA) powder of black.
The microwave method synthetic method of carbon nano-material/charcoal-aero gel (CA) of the present invention, adopts the mode of carry out microwave radiation heating, makes Resorcinol (R) and formaldehyde (F) generate the organic wet gel of intermediate rapidly.Result shows that microwave heating substantially increases synthesis rate and the productive rate of products therefrom, and product charcoal-aero gel (CA) stable in properties, aperture and particle diameter are relatively little and porosity is higher, and specific surface area is comparatively large, is mainly used in the aspects such as catalyzer, ultracapacitor, water treatment and Chu Qing.The present invention shortens the reaction times by microwave chemical technology, simplifies synthesis technique, and it is simple that this technique has process, and resultant velocity is fast, energy-conservation, pollutes few, the features such as product property is stable.
Embodiment
Technical thought of the present invention is, with Resorcinol and formaldehyde for raw material, applied microwave synthetic technology, under microwave condition, adds deionized water and catalyzer and carry out polyreaction and generate organic wet gel, need continuous stirring in Microwave synthesize process.Aging 4d at a certain temperature, recycling acetone is removed impurity, and finally high temperature carbonization obtains charcoal-aero gel (CA) again.
Concrete synthetic method is: with Resorcinol and formaldehyde for raw material, the mol ratio of Resorcinol and formaldehyde is 1:2, add deionized water and catalyzer in the feed, stir, be 400W ~ 800W with microwave power, be 20min ~ 40min to the radiated time of raw material, temperature of reaction is 80 DEG C, obtain the sticky shape of a kind of light red, transparent organic wet gel; Then aging 4d at organic wet gel being placed in 80 DEG C, then in infrared drying oven and thermostatic drying chamber, carry out drying and dehydrating, finally at rare gas element (N
2) protect carbonization in pipe type stove.Carbonization process is warming up to 900 DEG C with 5 DEG C ~ 10 DEG C temperature rise rates, then carbonization 2h at 900 DEG C, and naturally cooling is lowered the temperature, and obtains charcoal-aero gel (CA) powder of black.
Catalyzer adopts anhydrous sodium carbonate, and optimum amount is Resorcinol/anhydrous sodium carbonate=500.
Microwave best power needed for intermediate synthesis is 500W, and best radiated time is 25min, and optimal reaction temperature is 80 DEG C.
The organic wet gel acetone of intermediate removes impurity and moisture at least extracts 3 times.
In order to ensure that material is even, product property is stablized, and reacts completely.Usually will control microwave power, provide sufficient radiated time, optimum microwave power is 500W, and optimum radiated time is 25min, and optimum hydrolysis temperature is 80 DEG C, obtains scarlet to ruddy sticky shape, transparent organic wet gel.Charcoal-aero gel (CA) powder of black is obtained after removal of impurities, drying and high temperature carbonization.The body structure surface of the product obtained presents a large amount of comparatively ordered porous reticulated structure, and its particle diameter and aperture are all within 50nm.
Here is a series of embodiment that contriver provides, and these embodiments are preferably examples, and the present invention does not limit to these embodiments.
Embodiment 1: catalyst type and proportioning are on the impact of charcoal-aero gel synthesis rate
See table 1, be that 1:2 mixes by Resorcinol (R) and formaldehyde (F) with mol ratio, add different catalysts and different ratio, using water as solvent, put into three-necked bottle, add magnetic stir bar, under microwave field, microwave power is 500W, and adjustment microwave irradiation time is 25min, setting temperature of reaction is 80 DEG C, obtain the sticky shape of light red, transparent organic wet gel, then organic wet gel is placed in infrared drying oven and dries 0.5h, dewater in thermostatic drying chamber 5h, obtain the organic aerogel of rigid porous, temperature controls at 110 DEG C; Finally by organic aerogel in high temperature carbonization furnace at nitrogen (N
2) carbonize under protection, control temperature rise rate at 5 ~ 10 DEG C, at 900 DEG C, carbonize 2h.Naturally cooling is lowered the temperature, and obtains charcoal-aero gel (CA) powder of black.Anhydrous Na can be obtained from table 1
2cO
3it is more satisfactory catalyzer.
Table 1: catalyst type and proportioning are on the impact of charcoal-aero gel synthesis rate
Embodiment 2: the time is on the impact of charcoal-aero gel color state
Be that 1:2 mixes by Resorcinol (R) and formaldehyde (F) with mol ratio, add anhydrous sodium carbonate and make catalyzer, R/C=500, using water as solvent, put into three-necked bottle, add magnetic stir bar, under microwave field, microwave power is 500W, regulate microwave irradiation time, table 2 is time impacts on charcoal-aero gel color state, and setting temperature of reaction is 80 DEG C, obtains organic wet gel, then organic wet gel is placed in infrared drying oven and dries 0.5h, dewater in thermostatic drying chamber 5h, obtains the organic aerogel of rigid porous, and temperature controls at 110 DEG C; Finally by organic aerogel in high temperature carbonization furnace at nitrogen (N
2) carbonize under protection, control temperature rise rate at 5 ~ 10 DEG C, at 900 DEG C, carbonize 2h.Naturally cooling is lowered the temperature, and obtains charcoal-aero gel (CA) powder of black.As can be seen from Table 2, the organic wet gel of thick redness is better, so choosing the microwave time is 25min.
Table 2: the microwave time is on the impact of organic wet gel color state
Embodiment 3: microwave power affects organic wet gel color state
Be that 1:2 mixes by Resorcinol (R) and formaldehyde (F) with mol ratio, add anhydrous sodium carbonate and make catalyzer, R/C=500, using water as solvent, put into three-necked bottle, add magnetic stir bar, under microwave field, regulate microwave power, microwave power affects see table 3 organic wet gel color state, setting microwave irradiation time is 25min, temperature of reaction is 80 DEG C, obtain organic wet gel, then organic wet gel is placed in infrared drying oven and dries 0.5h, dewater in thermostatic drying chamber 5h, obtain the organic aerogel of rigid porous, temperature controls at 110 DEG C, finally by organic aerogel in high temperature carbonization furnace at nitrogen (N
2) carbonize under protection, control temperature rise rate at 5 ~ 10 DEG C/min, at 900 DEG C, carbonize 2h.Naturally cooling is lowered the temperature, and obtains charcoal-aero gel (CA) powder of black.Better and the convenient transfer of color state when 500W can be obtained, so choosing microwave power is 500W from table 3.
Table 3: microwave power affects organic wet gel color state
Embodiment 4: catalyst proportion (R/C) affects organic wet gel color state
By Resorcinol (R) and formaldehyde (F) mole to mix for the ratio of 1:2, add anhydrous sodium carbonate and make catalyzer, table four is that different catalysts proportioning (R/C) affects organic wet gel color state, using water as solvent, put into three-necked bottle, add magnetic stir bar, under microwave field, regulate microwave power, table 4 is that microwave power affects organic wet gel color state, adjustment microwave irradiation time is 25min, setting temperature of reaction is 80 DEG C, obtain organic wet gel, then organic wet gel is placed in infrared drying oven and dries 0.5h, dewater in thermostatic drying chamber 5h, obtain the organic aerogel of rigid porous, temperature controls at 110 DEG C, finally by organic aerogel in high temperature carbonization furnace at nitrogen (N
2) carbonize under protection, control temperature rise rate at 5 ~ 10 DEG C/min, at 900 DEG C, carbonize 2h.Naturally cooling is lowered the temperature, and obtains charcoal-aero gel (CA) powder of black.Can obtain catalyst proportion from table four is a very important factor, along with the increase gradually of catalyst proportion, causes sol-gel process incomplete, occurs the phenomenon of partial white.Simultaneously along with the increase of catalyst proportion, the aperture of charcoal-aero gel and particle diameter are also increase,
In order to keep it within 50nm, select R/C=500.
Table 4: catalyst proportion is on organic wet gel color state impact impact
Claims (4)
1. a microwave method synthetic method for carbon nano-material/charcoal-aero gel (CA), is characterized in that, synthesizes by following concrete steps:
Step one, with Resorcinol (R) and formaldehyde (F) for raw material, Resorcinol (R) is 1:2 with the mol ratio of formaldehyde (F), be under the condition of 400 ~ 800W at microwave power, appropriate deionized water and anhydrous sodium carbonate is added in raw material, stir, the consumption mol ratio of described anhydrous sodium carbonate is: Resorcinol (R)/anhydrous sodium carbonate=500, be 20 ~ 40min to the radiated time of raw material, temperature of reaction is 80 DEG C, synthetic intermediate;
Step 2, by the intermediate aging 4d at insulation 80 DEG C further of synthesis, then adds acetone soln at normal temperatures and pressures and removes the moisture in intermediate and impurity, obtain wine-colored organic aerogel;
Step 3, carries out dry 0.5h by the organic aerogel obtained in infrared drying oven, then dry 5h at 110 DEG C in thermostatic drying chamber, finally at rare gas element N
2carbonization in protection pipe type stove, be slowly warming up to 900 DEG C, then carbonization 2h at 900 DEG C, naturally cooling is lowered the temperature, and obtains charcoal-aero gel (CA) powder of black.
2. method as claimed in claim 1, it is characterized in that, the microwave power in the Microwave synthesize process of described step one is 500W, and radiated time is 25min, and temperature of reaction is 80 DEG C.
3. method as claimed in claim 1, it is characterized in that, the intermediate of described step 2 need remove impurity with acetone and moisture at least extracts 3 times.
4. method as claimed in claim 1, is characterized in that, organic aerogel temperature rise rate when high temperature carbonization of described step 3 controls at 5 DEG C/min ~ 10 DEG C/min.
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