CN103803545A - Method for preparing copper-doped activated carbon by utilizing complexing process - Google Patents
Method for preparing copper-doped activated carbon by utilizing complexing process Download PDFInfo
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- CN103803545A CN103803545A CN201410021852.9A CN201410021852A CN103803545A CN 103803545 A CN103803545 A CN 103803545A CN 201410021852 A CN201410021852 A CN 201410021852A CN 103803545 A CN103803545 A CN 103803545A
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Abstract
The invention relates to a method for preparing copper-doped activated carbon by utilizing a chemical complexing process, and belongs to the technical fields of chemical industry and environmental protection. The method comprises the following steps of functionalizing nitrile groups of a polyacrylonitrile copolymer serving as a raw material by using hydroxylammonium chloride to obtain a product containing a great number of amino groups and hydroxyl groups, chemically complexing the product and a copper ion aqueous solution to obtain copper-doped polyacrylonitrile, and activating copper-doped polyacrylonitrile under different conditions by using potassium hydroxide as an activator to obtain the copper-doped activated copper. The method has the advantages that polyacrylonitrile is used as the raw material, and the nitrile groups of polyacrylonitrile can be effectively and conveniently functionalized; a chemical complexing method is adopted, so that the activated carbon can be efficiently and uniformly doped with copper; in addition, the method has the advantages of simplicity in an operation process, less environmental pollution and the like; compared with an activated carbon material, the copper-doped activated carbon has high specific capacitance, and can be used for a capacitor electrode material.
Description
Technical field
The invention belongs to chemical industry and field of environment protection, be specifically related to a kind of method of utilizing complexation process to prepare the metal-doped gac of copper.
Background technology
Gac is a kind of conventional porous material, its starting material wide material sources, comprise the synthetic polymers such as nature biotechnology matter and resol, simultaneously because its specific surface area is high, chemical stability is good, easily polarized, be now widely used in electrode material for super capacitor field.The working mechanism of ultracapacitor is electrostatic double layer mechanism, in the time that active carbon electrode is applied to external voltage, corresponding positive charge or negative charge on electrode band, then attract in electrolytic solution ionic adsorption with opposite charges at electrode surface, finally formed electrostatic double layer at electrode surface.When electrode surface net charge is zero, complete process of charging one time, by this electrical condenser access external circuit, complete discharge process.Be different from the electrochemical appliances such as battery, there is not faraday reaction in ultracapacitor, just simply completes charge and discharge process by the adsorption and desorption of electric charge, have that cyclicity is good, long service life, without advantages such as chemical pollutions.
But owing to being subject to the restriction of gac specific surface area extreme value and aperture size distribution, activated carbon electrodes has very low ratio capacitance (0.15-0.4 F/m
2or 150 F/g), cannot meet the requirement in daily life.For improving this situation, many investigators start gac to carry out metal-doped.Can there is faraday's reaction (redox reaction) in the metal of doping or metal oxide, produce pseudo-capacitance value, make the electric capacity of activated carbon electrodes not only comprise that electric double layer capacitance value also comprises pseudo-capacitance value, thereby reached the object that improves activated carbon electrodes capacitance.The people such as the Meng [1], take resol as carbon raw material, adulterate into neutralized verdigris with physical mixed method, electrode capactitance value has promoted 25 %(150 F/g).The method by chemical precipitation such as [2] people by oxide-doped ruthenium dioxide enter gac, and capacitance is promoted to 350 F/g in the time that the massfraction of ruthenium dioxide oxide compound reaches 35 %.Jang[3] etc. people with chemical deposition, ruthenium dioxide oxide compound is successfully doped in gac, electrode capactitance value is promoted to 243F/g.
These adulterating methods exist certain weak point, are exactly that metal or metal oxide cannot be distributed in gac by homogeneous, or operating process more complicated (for example electroless plating), and exist the harm such as organic reagent pollution.
[1]?Qinghan?Meng,?Ling?Li,?Huaihe?Song?
Journal?of?Applied?Electrochemistry 2006,
36,?63。
[2]?Jianrong?Zhang,?Dechen?Jiang,?Bin?Chen,?Junjie?Zhu,?Liping?Jiang,?Huiqun?Fang?
Journal?of?the?Eletrochemical?Society 2001,?
148,?A1362。
[3]?Jong?H.Jang,?Sangjin?Han,?Taeghwan?Hyeon,?Seung?M.?Oh?
Journal?of?Power?Sources 2003,?
123,?79。
Summary of the invention
The object of the present invention is to provide one simple to operate, pollution-free, what cost was low utilizes complexation process to prepare the method for copper dopped activated carbon.
The method of utilizing complexation process to prepare copper dopped activated carbon provided by the invention, concrete steps comprise:
Oxammonium hydrochloride or hydroxylamine solution that preparation mass concentration is 3wt%-15wt%, with the acidity value to 7 of sodium carbonate adjusting oxammonium hydrochloride solution;
At 30-70 ℃, polyacrylonitrile raw material is added to deployed oxammonium hydrochloride or hydroxylamine solution, carry out functionalization, the reaction times is 0.5-3h, obtains functionalized products; Be placed in the cupric ion aqueous solution that stirring spends the night carries out complexing, suction filtration obtains copper ion doped polyacrylonitrile;
Then under nitrogen atmosphere, it is carried out to chemical activation, finally obtain copper dopped activated carbon.
Described reactivation process activator used is potassium hydroxide, and polyacrylonitrile/activator mass ratio is 10wt%-150wt%, and temperature rise rate is 1-5 ℃/min, and activation temperature is 500-800 ℃, and soak time is 0.5h-2h.
In the present invention, the described cupric ion aqueous solution is obtained by soluble copper salt preparation, comprises copper sulfate, cupric sulfate pentahydrate, neutralized verdigris, cupric chloride, the strong electrolyte salt that cupric nitrate etc. contain cupric ion; Or adding part to dissolve by insoluble mantoquita makes.
Beneficial effect:
Method of the present invention can make the introducing gac of metal copper ion homogeneous, can effectively improve the ratio capacitance of absorbent charcoal material, and the method is simple to operate simultaneously, there is not organic reagent contamination, and with respect to rare metal, cupric ion price lower and more easily obtain, can reduce experimental cost.
Embodiment
Comparative example: be that 1:1 mixes with activator potassium hydroxide according to mass ratio by polyacrylonitrile powder, then at 800 ℃ of nitrogen atmospheres, activate 60min, temperature rise rate is 5 ℃/min, after dilute hydrochloric acid washing, obtains gac product, and its specific surface area is 2241m
2/ g, electrode capactitance value is 208.3F/g.
Comparative example 1.1: be that 1:1 mixes with activator potassium hydroxide according to mass ratio by polyacrylonitrile powder, then at 500 ℃ of nitrogen atmospheres, activate 60min, temperature rise rate is 5 ℃/min, after dilute hydrochloric acid washing, obtains gac product, and its specific surface area is 524m
2/ g.
Comparative example 1.2: be that 1:1 mixes with activator potassium hydroxide according to mass ratio by polyacrylonitrile powder, then at 600 ℃ of nitrogen atmospheres, activate 60min, temperature rise rate is 5 ℃/min, after dilute hydrochloric acid washing, obtains gac product, and its specific surface area is 872m
2/ g.
Comparative example 1.3: be that 1:1 mixes with activator potassium hydroxide according to mass ratio by polyacrylonitrile powder, then at 700 ℃ of nitrogen atmospheres, activate 60min, temperature rise rate is 5 ℃/min, after dilute hydrochloric acid washing, obtains gac product, and its specific surface area is 1813m
2/ g.
Comparative example 1.4: be that 1:1 mixes with activator potassium hydroxide according to mass ratio by polyacrylonitrile powder, then at 900 ℃ of nitrogen atmospheres, activate 60min, temperature rise rate is 5 ℃/min, after dilute hydrochloric acid washing, obtains gac product, and its specific surface area is 1834m
2/ g.
Comparative example 1.5: be that 10:1 mixes with activator potassium hydroxide according to mass ratio by polyacrylonitrile powder, then at 800 ℃ of nitrogen atmospheres, activate 60min, temperature rise rate is 5 ℃/min, after dilute hydrochloric acid washing, obtains gac product, and its specific surface area is 410m
2/ g.
Comparative example 1.6: be that 1:1.5 mixes with activator potassium hydroxide according to mass ratio by polyacrylonitrile powder, then at 800 ℃ of nitrogen atmospheres, activate 60min, temperature rise rate is 5 ℃/min, after dilute hydrochloric acid washing, obtains gac product, and its specific surface area is 1622m
2/ g.
Comparative examples, finds that activation optimum temps is 800 ℃, and activator level optimum amount is 100wt%.Be 800 ℃ in activation temperature, when activator level is 100wt%, gac specific surface area reaches maximum value 2194 m
2/ g.
Embodiment 1: 70 ℃ of stirring reaction 0.5h in the oxammonium hydrochloride aqueous solution that is 3wt% in massfraction by polyacrylonitrile powder, decompress filter obtains functionalization polypropylene nitrile product, then in copper sulfate solution, stir to spend the night and carry out complexation process, obtain copper doping polyacrylonitrile, then be that 1:1 mixes with potassium hydroxide according to mass ratio, under nitrogen atmosphere, activate.Activation temperature is elected 800 ℃ as, and soak time is 60min, obtains copper dopped activated carbon after salt acid elution, and it is 289.7F/g than capacitance.
Embodiment 2: 30 ℃ of stirring reaction 0.5h in the oxammonium hydrochloride aqueous solution that is 3wt% in massfraction by polyacrylonitrile powder, decompress filter obtains functionalization polypropylene nitrile product, then in copper sulfate solution, stir to spend the night and carry out complexation process, obtain copper doping polyacrylonitrile, then be that 1:1 mixes with potassium hydroxide according to mass ratio, under nitrogen atmosphere, activate, activation temperature is 800 ℃, soak time is 60min, after salt acid elution, obtain copper dopped activated carbon material, it is 210.7F/g than capacitance.
Embodiment 3: 70 ℃ of stirring reaction 0.5h in the oxammonium hydrochloride aqueous solution that is 15wt% in massfraction by polyacrylonitrile powder, decompress filter obtains functionalization polypropylene nitrile product, then in copper sulfate solution, stir to spend the night and carry out complexation process, obtain copper doping polyacrylonitrile, then be that 1:1 mixes with potassium hydroxide according to mass ratio, under nitrogen atmosphere, activate, activation temperature is 800 ℃, soak time is 60min, after salt acid elution, obtain copper dopped activated carbon material,, it is 220.6F/g than capacitance.
Comparative examples and embodiment 1-3, find after oxammonium hydrochloride functionalization, functionalization polypropylene nitrile product can with copper sulfate solution in cupric ion generation complexing, thereby obtain than capacitance improve copper dopped activated carbon material.
Embodiment 4: 70 ℃ of stirring reaction 0.5h in the oxammonium hydrochloride aqueous solution that is 3wt% in massfraction by polyacrylonitrile powder, decompress filter obtains functionalization polypropylene nitrile product, then in the neutralized verdigris aqueous solution, stir to spend the night and carry out complexation process, obtain copper doping polyacrylonitrile, then be that 1:1 mixes with potassium hydroxide according to mass ratio, under nitrogen atmosphere, activate, activation temperature is 800 ℃, soak time is 60min, after salt acid elution, obtain copper dopped activated carbon material, it is 257.1F/g than capacitance.
Comparative examples and embodiment 4, find after oxammonium hydrochloride functionalization, functionalization polypropylene nitrile product can with strong electrolyte copper salt solution in cupric ion generation complexing, obtain than capacitance promote copper dopped activated carbon material.
Comparative examples and embodiment 1-4, find that oxammonium hydrochloride can carry out functionalization to polyacrylonitrile effectively, obtain functionalization polypropylene nitrile, its can with strong electrolyte copper salt solution in cupric ion generation complexation process, after activating by potassium hydroxide, can obtain copper dopped activated carbon.After cupric ion successfully mixes gac, gac capacitance is greatly improved.This doping process operation is simple and convenient in addition, the introducing of organic solvent-free, has effectively reduced environmental pollution.
Claims (2)
1. utilize chemical complexing process to prepare a method for the metal-doped gac of copper, it is characterized in that concrete steps are as follows:
Oxammonium hydrochloride or hydroxylamine solution that preparation mass concentration is 3wt%-15wt%, with the acidity value to 7 of sodium carbonate adjusting oxammonium hydrochloride solution;
At 30-70 ℃, polyacrylonitrile raw material is added to deployed oxammonium hydrochloride solution, carry out functionalization, the reaction times is 0.5-3h, obtains functionalized products; Be placed in the cupric ion aqueous solution that stirring spends the night carries out complexing, suction filtration obtains copper ion doped polyacrylonitrile;
Then under nitrogen atmosphere, it is carried out to chemical activation, finally obtain copper dopped activated carbon;
Described reactivation process activator used is potassium hydroxide, and activator/polyacrylonitrile mass ratio is 10wt%-150wt%, and temperature rise rate is 1-5 ℃/min, and activation temperature is 500-800 ℃, and soak time is 0.5h-2h.
2. the method for utilizing chemical complexing process to prepare the metal-doped gac of copper according to claim 1, is characterized in that the described cupric ion aqueous solution by soluble copper salt copper sulfate, cupric sulfate pentahydrate, neutralized verdigris, cupric chloride or cupric nitrate preparation or adds part dissolving by insoluble mantoquita obtaining.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404504A (en) * | 2018-04-26 | 2019-11-05 | 西北大学 | Cu for handling dyeing and printing sewage adulterates walnut shell active carbon and its preparation method and application |
| CN111377443A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Copper-doped activated carbon composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404504A (en) * | 2018-04-26 | 2019-11-05 | 西北大学 | Cu for handling dyeing and printing sewage adulterates walnut shell active carbon and its preparation method and application |
| CN110404504B (en) * | 2018-04-26 | 2021-09-28 | 西北大学 | Cu-doped walnut shell activated carbon for treating printing and dyeing sewage and preparation method and application thereof |
| CN111377443A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Copper-doped activated carbon composite material and preparation method thereof |
| CN111377443B (en) * | 2018-12-29 | 2022-06-07 | 中国石油化工股份有限公司 | Copper-doped activated carbon composite material and preparation method thereof |
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