CN101774581B - Method for preparing tungsten carbide/carbon aerogel composite material by alternate microwave heating - Google Patents
Method for preparing tungsten carbide/carbon aerogel composite material by alternate microwave heating Download PDFInfo
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- CN101774581B CN101774581B CN2010101012953A CN201010101295A CN101774581B CN 101774581 B CN101774581 B CN 101774581B CN 2010101012953 A CN2010101012953 A CN 2010101012953A CN 201010101295 A CN201010101295 A CN 201010101295A CN 101774581 B CN101774581 B CN 101774581B
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Abstract
The invention discloses a method for preparing a tungsten carbide/carbon aerogel composite material by alternate microwave heating. The method comprises the following steps: (1) respectively dissolving tungsten source precursors and carbon source precursors and then mixing; (2) adding an alkaline catalyst into solution of carbon source precursor, reacting completely, and performing heating reaction on the product to obtain an intermediate product; and (3) drying the intermediate and then performing heating treatment by using microwave carbon bath to obtain the tungsten carbide/carbon aerogel composite material. The spatial aperture range of aerogel can be controlled by changing the ratio of the carbon aerogel to the tungsten carbide. The method has simple operation and cheap raw materials and uses cheap water as a polymerization medium to composite carbon materials and the tungsten carbide in situ.
Description
Technical field
The invention belongs to field of materials, relate generally to a kind of method of utilizing intermittent microwave to add hot preparation wolfram varbide/carbon aerogel composite material.
Background technology
Scheele found wolfram varbide first in 1781, but Henri Moissan has just synthesized wolfram varbide with the artificial method after more than 100 years.Wolfram varbide is that carbon atom is filled into the interstitial compound that forms in the tungsten lattice, and this carbide material has unique physics and chemical property.Their characteristic combines the character of covalent compound, ionic crystal and three kinds of materials of transition metal.They have the high strong hardness and the fragility of covalent compound, the characteristics of HMP with ionic crystal and simple crystalline structure, and its electricity and magnetic properties and metallographic phase are seemingly.The fusing point of wolfram varbide is 2870 ± 50 ℃, hardness 16～22GPa, tensile strength 300GPa, compressive strength 5GPa (20 ℃), breaking tenacity 28MPa.These unique physical and chemical properties of wolfram varbide make it in materialogy, be widely used.
After Levy in 1973 and Boudart (R.B.Levy, M.Boudart, Science, 181 (1973) 547) disclosed wolfram varbide and the similarity of platinum aspect catalytic performance first, the catalytic property of wolfram varbide caused the great interest of scientific circles.Up to now, wolfram varbide has been had experiment and theoretical investigation widely as Application of Catalyst, the result shows that it has good catalytic performance in the reaction of a series of precious metal catalysts.Because the precious metal reserves are few, expensive, and the source metal reserves of carbide are abundant, therefore, replacing precious metal effectively with carbide is research highly significant.At the fuel cell catalytic field, existing bibliographical information wolfram varbide carrier as the cathode and anode catalyzer in Proton Exchange Membrane Fuel Cells have Study of Synergistic Effect work.
The traditional preparation process technology of wolfram varbide is inherited in metallurgical industry, is metal, metal hydride or MOX and a certain proportion of carbon direct reaction in reducing atmosphere, and temperature of reaction is usually above 1200 ℃.The product of gained than great, granularity is big, this Industrial materials have very low specific surface area, are not suitable for as catalyzer or carrier.The catalysis of discovering wolfram varbide is relevant with its surface tissue and composition with absorption property, and its surface tissue and composition receive preparation technology's influence.
Charcoal-aero gel is the nanometer porous property of an a kind of novel light amorphous carbon cellulosic material, is developed at first in 1989 by Pekala (R.W.Pekala, US Patent 4873218,1989) research group.It is big to have specific surface area; Characteristics such as the aperture is wide and conduct electricity very well are compared with gac, and the specific conductivity of charcoal-aero gel is very high by (about 25～100S/cm); And (50～300K) remain unchanged basically in a very wide TR; Its porosity is 80%～98%, typical pore dimension＜50nm, network colloidal solid size 3～20nm.As unique gas gel with conduction property, its electrochemical energies such as fuel cell, electric chemical super capacitor, lithium ion battery store with the application in conversion field more and more widely.
And these two kinds of materials is compound, makes the matrix material that obtains possess advantage separately, is having under the situation of good catalytic, has strengthened the mass transfer effect of three phase boundary, in heterogeneous catalysis field wide application prospect is arranged especially.
Microwave heating technique is because its unique type of heating and a series of advantage have caused increasing concern; The purpose of this invention is to provide a kind of technology of utilizing intermittent microwave to add hot preparation wolfram varbide/carbon aerogel composite material, carbonization and calking obtain wolfram varbide/carbon aerogel composite material at short notice.
Summary of the invention
The objective of the invention is to be to overcome the deficiency that existing preparation tungsten carbide composite method exists, provide a kind of convenience, controlled and microwave heating fast to prepare the method for wolfram varbide/carbon aerogel composite material.The method of utilizing microwave method to prepare wolfram varbide/carbon aerogel composite material of the present invention is characterized in that comprising the steps:
(1) tungsten source presoma, carbon source precursor body and additive are dissolved in the water according to this, stir.
(2) reaction soln is put into encloses container and obtains gel product in baking oven thermal treatment for some time, let gel dry naturally again or dry after pulverize.
(3) the exsiccant powder is put into microwave oven heating carbonization and formed wolfram varbide.
The above-mentioned microwave method of utilizing prepares in the method for wolfram varbide/carbon aerogel composite material, and the weight ratio of tungsten source presoma described in the step (1) and carbon source precursor body is 1: 1～1: 10, is generally 1: 2～1: 9, is preferably 1: 5～1: 8.
The above-mentioned microwave method of utilizing prepares in the method for wolfram varbide/carbon aerogel composite material, and the tungsten source presoma described in the step (1) is one or more the mixture in sodium wolframate, ammonium metawolframate and the wolframic acid.
The above-mentioned microwave method of utilizing prepares in the method for wolfram varbide/carbon aerogel composite material; Carbon source precursor body described in the step (1) is two kinds of organism, comprises one or more the mixture in Phloroglucinol monomethyl ether, trimeric cyanamide, Resorcino and formaldehyde, the furfural.
The above-mentioned microwave method of utilizing prepares in the method for wolfram varbide/carbon aerogel composite material; Additive described in the step (1) is co-catalyst or the promotor as reaction, is one or more mixture of yellow soda ash, salt of wormwood, sodium hydroxide, sodium hydrogencarbonate and calcium hydroxide.
The above-mentioned microwave method of utilizing prepares in the method for wolfram varbide/carbon aerogel composite material, and thermal treatment temp is 40 ℃～90 ℃ described in the step (2), is generally 50 ℃～80 ℃, is preferably 60 ℃～70 ℃.
The above-mentioned microwave method of utilizing prepares in the method for wolfram varbide/carbon aerogel composite material, and heat treatment time is 10～96 hours described in the step (2), is generally 12～72 hours, is preferably 18～36 hours.
The above-mentioned microwave method of utilizing prepares in the method for wolfram varbide/carbon aerogel composite material; Microwave oven heating carbonization described in the step (3) is to carry out through the method for intermittent microwave heating; Promptly alternately heat/stop, be 35～60S general heat-up time, and stand-by time is 5～15S; Repeat repeatedly, total time is 10-20min.
Compared with prior art, the present invention is owing to use the microwave even heating, rather than heats through thermal conduction, so have that rate of heating is fast, carbonization time short, simple to operate, characteristics such as reaction in formation that can realize wolfram varbide and charcoal-aero gel.
Description of drawings
Fig. 1 is the XRD figure under the 20min for the matrix material of the present invention's preparation at the intermittent microwave heat treatment time.
Embodiment
Below in conjunction with embodiment further explain is done in practical implementation of the present invention, but enforcement of the present invention is not limited thereto.
Embodiment 1
With quality is that the sodium wolframate of 0.42 gram and the Resorcino of 1.1 grams are dissolved in the 20ml water, adds 15ml formaldehyde then after 40 ℃ of stirring in water bath, adds 0.01 gram yellow soda ash, puts into encloses container then at 60 ℃ of baking oven internal reaction 24h, obtains the reddish-brown gel.Treat that gel dries naturally, inserting power after pulverizing is ground is 1000W, and frequency is in the microwave oven of 2.45GHz, replaces (heating in 35 seconds, 5 seconds intermittences) microwave carbon and bathes and heat 20min, just obtains wolfram varbide/carbon aerogel composite material powder after the cooling.Its XRD figure such as Fig. 1 have wherein shown the characteristic three strongest ones peak of wolfram varbide.
Embodiment 2
With quality is that the ammonium metawolframate of 3.26 grams and the Resorcino of 2.2 grams are dissolved in the 20ml water, adds 25ml formaldehyde then after 45 ℃ of stirring in water bath, adds 0.008 gram salt of wormwood catalyzer and puts into encloses container at 70 ℃ of baking oven internal reaction 36h, obtains reddish brown gel.Treat that gel dries naturally, inserting power after pulverizing is ground is 1000W, and frequency is in the microwave oven of 2.45GHz, replaces (heating in 60 seconds, 15 seconds intermittences) microwave carbon and bathes and heat 10min, just obtains wolfram varbide/carbon aerogel composite material powder after the cooling.
Embodiment 3
With quality is that the sodium wolframate of 0.329 gram and the Phloroglucinol monomethyl ether of 3.12 grams are dissolved in the 30ml water, adds the 20ml furfural then after 40 ℃ of stirring in water bath, adds 0.05 gram calcium hydroxide catalyzer and puts into encloses container at 80 ℃ of baking oven internal reaction 48h, obtains gel.Treat the gel oven dry, inserting power after pulverizing is ground is 1000W, and frequency is in the microwave oven of 2.45GHz, replaces (heating in 40 seconds, 10 seconds intermittences) microwave carbon and bathes and heat 15min, just obtains wolfram varbide/carbon aerogel composite material powder after the cooling.
Embodiment 4
With quality is that the sodium wolframate of 0.64 gram and the trimeric cyanamide of 2.1 grams are dissolved in the 20ml water, adds 25ml formaldehyde then after 40 ℃ of stirring in water bath, adds 0.01 gram sodium hydrogencarbonate catalyzer and puts into encloses container at 50 ℃ of baking oven internal reaction 72h, obtains gel.After treating that gel drying fully, inserting power after pulverizing is ground is 1000W, and frequency is in the microwave oven of 2.45GHz, replaces (heating in 45 seconds, 15 seconds intermittences) microwave carbon and bathes and heat 20min, just obtains wolfram varbide/carbon aerogel composite material powder after the cooling.
Embodiment 5
With quality is that the Phloroglucinol monomethyl ether that 0.7 gram wolframic acid and 3.43 restrains is dissolved in the 20ml water, adds 25ml formaldehyde then after 40 ℃ of stirring in water bath, adds 0.017 gram sodium hydroxide catalyst and puts into encloses container at 90 ℃ of baking oven internal reaction 10h, obtains reddish brown gel.Treat that gel dries naturally, inserting power after pulverizing is ground is 1000W, and frequency is in the microwave oven of 2.45GHz, replaces (heating in 40 seconds, 10 seconds intermittences) microwave carbon and bathes and heat 15min, just obtains wolfram varbide/carbon aerogel composite material powder after the cooling.
Embodiment 6
With quality is that the wolframic acid of 2.49 grams and the Resorcino of 2.21 grams are dissolved in the 30ml water, adds 25ml formaldehyde then after 45 ℃ of stirring in water bath, adds 0.012 gram sodium carbonate catalyst and puts into encloses container at 40 ℃ of baking oven internal reaction 96h, obtains reddish brown gel.Treat the gel oven dry, inserting power after pulverizing is ground is 1000W, and frequency is in the microwave oven of 2.45GHz, replaces (heating in 50 seconds, 10 seconds intermittences) microwave carbon and bathes and heat 10min, just obtains wolfram varbide/carbon aerogel composite material powder after the cooling.
Claims (6)
1. utilize intermittent microwave to add the method for hot preparation wolfram varbide/carbon aerogel composite material; It is characterized in that comprising the steps: that (1) mix tungsten source presoma, carbon source precursor body and additive dissolving, stir, said additive is as the co-catalyst or the promotor of reaction; Described tungsten source presoma is one or more the mixture in sodium wolframate, ammonium metawolframate and the wolframic acid; Described carbon source precursor body is one or more the mixture in Phloroglucinol monomethyl ether, trimeric cyanamide, Resorcino and formaldehyde, the furfural; Described additive is one or more a mixture of yellow soda ash, salt of wormwood, sodium hydroxide, sodium hydrogencarbonate and calcium hydroxide; (2) mixing solutions is put into encloses container and obtains gel product in baking oven thermal treatment, let gel dry naturally again or dry after pulverize; (3) dried powder of pulverizing is put into microwave carbon and bathe alternately that heating obtains said wolfram varbide/carbon aerogel composite material; Said alternately heating refers to alternately heat/stops, and specifically be to be heat-up time 35～60S, stand-by time is 5～15S, repeats repeatedly, total time is 10-20min.
2. method according to claim 1, the weight ratio that it is characterized in that tungsten source presoma described in the step (1) and carbon source precursor body is 1: 1～1: 10.
3. method according to claim 2, the weight ratio that it is characterized in that described tungsten source presoma and carbon source precursor body is 1: 5～1: 8.
4. method according to claim 1 is characterized in that thermal treatment temp described in the step (2) is 40 ℃～90 ℃, and heat treatment time is 10～96 hours.
5. method according to claim 1 is characterized in that thermal treatment temp described in the step (2) is 60 ℃～70 ℃, and heat treatment time is 18～36 hours.
6. method according to claim 5, the power that it is characterized in that said microwave oven is 1000W, frequency is 2.45GHz.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101944597B (en) * | 2010-08-26 | 2012-11-21 | 合肥工业大学 | Method for preparing carbon aerogel cladded LiMnPo4/C |
| CN102674352B (en) * | 2012-04-18 | 2014-04-16 | 北京科技大学 | Method for preparing tungsten-carbide powder through low-temperature combustion synthesis |
| CN104353478B (en) * | 2014-12-01 | 2016-09-28 | 吉林大学 | The cobalt tungsten bimetallic carbide of a kind of carbon cladding, preparation method and applications |
| CN104607116A (en) * | 2015-01-12 | 2015-05-13 | 朱秀榕 | Universal preparation method of high-specific surface area rare earth element-doped carbon gas gel |
| CN106654280A (en) * | 2017-01-11 | 2017-05-10 | 安徽工业大学 | W2C@onion-shaped carbon/amorphous carbon nanometer composite and preparing method and application thereof |
| CN113072070A (en) * | 2021-03-26 | 2021-07-06 | 华东理工大学 | Preparation method of high-specific-surface-area carbon-coated transition metal carbide material |
| CN114678547B (en) * | 2022-03-31 | 2023-12-08 | 浙江工业大学 | Tungsten-oxygen-carbon/carbon aerogel composite electrode and preparation method thereof |
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| CN1834010A (en) * | 2006-04-07 | 2006-09-20 | 北京科技大学 | Method of microwave synthetizing nano powder of tungsten carbide |
| CN101181690A (en) * | 2007-12-14 | 2008-05-21 | 中山大学 | Microwave induction catalytic preparation method of nano tungsten carbide |
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| CN1834010A (en) * | 2006-04-07 | 2006-09-20 | 北京科技大学 | Method of microwave synthetizing nano powder of tungsten carbide |
| CN101181690A (en) * | 2007-12-14 | 2008-05-21 | 中山大学 | Microwave induction catalytic preparation method of nano tungsten carbide |
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