CN1680023A - Light catalyst for nanometer carrier - Google Patents
Light catalyst for nanometer carrier Download PDFInfo
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- CN1680023A CN1680023A CN 200510055525 CN200510055525A CN1680023A CN 1680023 A CN1680023 A CN 1680023A CN 200510055525 CN200510055525 CN 200510055525 CN 200510055525 A CN200510055525 A CN 200510055525A CN 1680023 A CN1680023 A CN 1680023A
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- carrier
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- active carbon
- tio
- photochemical catalyst
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Abstract
The invention discloses a light catalyst for nanometer carrier, which is a titanium oxide light catalyst loaded on the carbon nanotube/active carbon compound carrier. The process comprises: mixing carbon nanotube and active carbon in a mass ratio to produce carbon nanotube/active carbon compound carrier, dissolving the butyl titanate in the absolute ethyl alcohol containing compound carrier to form colloid, scraping and painting on the cotton flax fiber cloth, drying, becoming the titanium oxide light catalyst loaded on the carbon nanotube/active carbon compound carrier for degrading the organic matter in the devil liquor by photocatalysis. The capacity of degrading organic matter by TiO2 photocatalysis carried by carbon nanotube and active carbon is obviously higher than the pure TiO2 photoelectric transformation efficiency and sorption to the organic matter in the solution, so that it improves the light catalytic rate in a large scale.
Description
Technical field
The invention belongs to range of catalysts, particularly a kind of photochemical catalyst of nano-carrier.
Background technology
The research of conductor photocatalysis method starts from the later stage seventies 20th century.Semiconductor has special electronic structure: valence band is full of, conduction band free time and forbidden band broad.Semiconductor light-catalyst can produce electronics-hole under visible light or action of ultraviolet light right, when photon energy during more than or equal to energy gap, its valence band electronics is excited, cross the forbidden band and enter conduction band, on valence band, formed simultaneously corresponding hole, thereby have stronger redox property, directly and organic matter reacts or with on every side medium (O
2Or H
2O is as electron acceptor) effect produces has highly active HO free radical, reacts the purpose that reaches degradation of organic substances with organic matter again.
In the photochemical catalyst of present broad research, Shangguan Wen Feng is at " Chinese Journal of Inorganic Chemistry ", and 17 (5) (2001): report TiO in " progress of solar photolysis water hydrogen " on 619～626
2, CdS and ZnO etc. be the most noticeable as photochemical catalyst.From Xu Chihuan at " modern chemical industry ", 1998 (5): on 17～19 " Japan to TiO
2Application of catalytic reaction under faint light ", Hu Anzheng, Tang Chaoqun is at " functional material ", 2001,32 (6): " nano-TiO on 586～589
2Catalysis material and be applied to the progress of environmental protection ", Chen Feili, Wang Liangyan, Yang Baoshan be at " solar energy journal ", 1999,20 (4): " the glass tube appendix TiO on 471～475
2Photo catalysis reactor is removed the research drink underwater micro-organic matter " and. Liu Jianhua, Liao Liling be at " Guizhou Normal University's journal (natural science edition) ", " TiO on 2004,22 (2) 115～118
2Application and the progress of photochemical catalyst in wastewater treatment " etc. report TiO in the document
2Have avirulence, chemical stability is good, and synthetic process is many, and catalytic capability is strong, but the preferred material of advantage becomes photochemical catalyst such as the organism kinds of catalytic degradation is a lot.Zhang Zhimin, Yin Xiaohua, Li Qinchuan, Cui Fuming etc. are in " Environmental Chemistry ", 1997,16 (1): reported the easy cohesion in water of suspension build photochemical catalyst and lost activity " coal slime prepare the research of active carbon and uses document " in 64～67, the penetration power of light is obstructed, and the separation of catalyst and recovery difficulty, so the more emphasis fixeds of people photochemical catalyst, carrier commonly used has glass marble, extra large sand, zeolite and active carbon etc., it is stable that active carbon has chemical property, avirulence, advantage such as adsorptivity is strong is relatively being paid attention to aspect catalyst carrier.Also bright from 1. Wang Min, Li Fengyi, " CNT-novel catalyst carrier " of Peng Niancai etc., new carbon, 2002,17 (3): 75～79.; 2. Wang Xiao peak, Wang Dazhi, " electrochemical behavior of carbon nano tube surface deposition nickel oxide and ultra-capacitor thereof " of Liang Ji etc., Journal of Inorganic Materials, 2003,18 (2), 331～336.; 3. the sage who opens, " preparation of CNT, sign and the application in electronic applications thereof " of Li Haiyan etc., Journal of Inorganic Materials, 2003,18 (3): 527～532 and 4. Chen Gui as, Xu Cailu, hair is combined strong " the deposition platinum on the CNT " that waits, Science Bulletin, 1999,44 (11): report in 1154～1156: CNT (CNTs) has particular structure, nano level size, high effective ratio area and can present property of conductor, is considered to a kind of good carrier.
This research is contrasting CNT and active carbon carries TiO as catalyst carrier
2On the multiple organic result of study of the photocatalytic degradation basis, analyzed CNT and absorbent charcoal carrier advantage separately, find with two kinds of carriers compound after, can bring into play their advantages separately.It is carrier loaded TiO that contrast is received nanotube, active carbon (AC) and CNT/active carbon complex with carbon respectively
2Photocatalysis performance, the result shows that CNT/active carbon complex is carrier loaded TiO
2The speed of photocatalysis to degrade organic matter is significantly higher than single carbon nanotube or single-activity charcoal as carrier loaded TiO
2Photocatalysis will separate organic speed.Because CNT ratio in complex carrier is less, can reach the result that cost is not significantly increased.
Summary of the invention
The photochemical catalyst that the purpose of this invention is to provide a kind of nano-carrier; It is characterized in that: the photochemical catalyst of described nano-carrier is the titania photocatalyst that is carried on CNT/activated carbon composite carrier; Its manufacture craft is to be (5～60) with the mass ratio of CNT and active carbon: (40～95) preparation CNT/activated carbon composite carrier, this complex carrier by among the corresponding 50ml absolute ethyl alcohol adding of the every gram complex carrier absolute ethyl alcohol, is mixed stirring and reached even in 1 hour.Butyl titanate is dissolved in the absolute ethyl alcohol that contains complex carrier, is mixed with the butyl titanate solution of 0.1mol/L, too violent for preventing reaction, the hydrochloric acid by every L solution adding 0.001mol in reactant liquor adds hydrochloric acid.In above-mentioned solution, add deionized water fast then; magnetic agitation 2h; regulate pH value and to reactant liquor, form colloid; colloid is through stable, centrifugal, the filtration and the impurity and the ion on flush away surface; carry out drying; then in Muffle furnace with the temperature rise of 9 ℃/min to assigned temperature (600 ℃), sintering 1h under the inert atmosphere protection, cooling naturally.Then suitably grind and disperse, obtain titania oxide supported photochemical catalyst on CNT/activated carbon composite carrier.During operating process, the consumption of reactant (butyl titanate) is (2～98) by the titanium oxide that generates and the mass ratio of composite catalyst: (98～2) are controlled; The titania photocatalyst of above-mentioned CNT/active carbon carrying, after the poly-tetrafluoro suspension mixing with the ethanol dilution, baking is while stirring blown, and treats that solvent volatilizees gradually, residue three/for the moment, blade coating is on cotton fibriia cloth, after the oven dry.Become immobilized photochemical catalyst, be used for the organic matter of photocatalytic degradation waste liquid by CNT/activated carbon composite carrier carrying.Wherein the quality of poly-tetrafluoro accounts for 5% of composite photo-catalyst quality only.
Beneficial effect of the present invention is the TiO of 1. CNTs carrying
2Semi-conductive photoelectric transformation efficiency is with respect to pure TiO
2Significantly improve, and photoelectric transformation efficiency and organic suction-operated in the solution also must be improved and strengthen, so the photocatalytic speed raising.
2. the TiO of active carbon carrying
2The ability of photocatalysis to degrade organic matter also be significantly higher than pure TiO
2Active carbon also has the carrying TiO of suction-operated and active carbon to the organic matter in the solution
2, also help TiO
2Dispersion of nano-particles, so photocatalytic speed improves.
The specific embodiment
The invention provides a kind of photochemical catalyst of nano-carrier.The photochemical catalyst of this nano-carrier is the titania photocatalyst that is carried on CNT/activated carbon composite carrier; Its manufacture craft is that the mass ratio with CNT and active carbon is 20: 80 preparation CNT/activated carbon composite carriers, among the ratio adding absolute ethyl alcohol of this complex carrier, mix stirring and reached even in 1 hour in the corresponding 50ml absolute ethyl alcohol of every gram complex carrier.Butyl titanate is dissolved in the absolute ethyl alcohol that contains complex carrier,, be mixed with the butyl titanate solution of 0.1mol/L, too violent for preventing reaction, in reactant liquor, add by) every L solution adds the hydrochloric acid of the HCl of 0.001mol.In above-mentioned solution, add deionized water fast then; magnetic agitation 2h; regulate the pH value and to reactant liquor, form colloid; colloid is through stable, centrifugal, the filtration and the impurity and the ion on flush away surface; carry out drying; then in Muffle furnace with the temperature rise of 9 ℃/min to assigned temperature (600 ℃), sintering 1h under the inert atmosphere protection, cooling naturally.Then suitably grind and disperse, obtain titania oxide supported photochemical catalyst on CNT/activated carbon composite carrier.During operating process, the consumption of reactant (butyl titanate) is to control at 80: 20 by the mass ratio of titanium oxide that generates and composite catalyst; The titania photocatalyst of above-mentioned CNT/active carbon carrying, after the poly-tetrafluoro suspension mixing with the ethanol dilution, baking is while stirring blown, and treats that solvent volatilizees gradually, residue three/for the moment, blade coating is on cotton fibriia cloth, after the oven dry.Become immobilized photochemical catalyst, be used for the organic matter of photocatalytic degradation waste liquid by CNT/activated carbon composite carrier carrying.Wherein the quality of poly-tetrafluoro accounts for 5% of composite photo-catalyst quality only.
The result shows by experiment, the TiO of CNT carrying
2Semi-conductive photoelectric transformation efficiency is with respect to pure TiO
2Significantly improve.Former because, CNT has electric conductivity, makes the photo-generated carrier that generates under the action of ultraviolet light can import in the CNT, has reduced the compounding machine meeting in electronics and hole, has improved photocatalysis efficiency, the photoelectric current test result can reflect this point.Secondly, CNT has suction-operated to the organic matter in the solution, and the adsorption experiment result can prove this point, therefore makes organic matter be enriched in the TiO that is carried
2Improved photocatalytic degradation speed on every side.The 3rd, the nano level diameter of CNT, the special construction of monodimension nanometer material and high effective specific area are to improving the TiO of institute's load
2Photocatalysis efficiency played important function.The feasible TiO that is carried of the higher specific surface area of CNT
2Particle is uniformly dispersed, and avoids mutual gathering, so TiO
2Particle surface demonstrates effectively, improved accept illumination and with solution in the contact area of reactant.The accumulation body interior detail of CNT is seen to go up and is continuous network structure, and the space between the CNT connects continuously, also helps being dispersed in TiO wherein
2The demonstration on the surface of particle and the circulation of reactive material have positive role to improving photocatalysis efficiency.Along with the raising of the ratio of the CNT in the photochemical catalyst, its specific area and pore volume all increase, to TiO
2The dispersion of nano-particles effect improves, and also increases with the attaching space of reactive material.In addition, photoelectric transformation efficiency and organic suction-operated in the solution also must be improved and strengthen, therefore, photocatalytic speed improves.
Experimental result also shows, the TiO of active carbon carrying
2The ability of photocatalysis to degrade organic matter also be significantly higher than pure TiO
2, and its photo-catalysis capability is along with active carbon and TiO
2Ratio raising and improve.Reason is as follows: at first, and the TiO of active carbon carrying
2Semi-conductive photoelectric transformation efficiency is with respect to pure TiO
2Also significantly improve, the photoelectric current test result can reflect this point, its mechanism and CNT carrying TiO
2Corresponding mechanism similar.Secondly, active carbon also has suction-operated to the organic matter in the solution, and the adsorption experiment result can prove this point.The 3rd, the carrying TiO of active carbon
2, also help TiO
2Dispersion of nano-particles.
Contrast CNT carrying TiO
2With active carbon carrying TiO
2The test experiments of the rerum natura of two kinds of photochemical catalysts found that the former photoelectric transformation efficiency is higher than the latter, and the latter's adsorption capacity is higher than the former.In addition, contrast from the structure and the specific surface characteristic of CNT and two kinds of carriers of active carbon, the former can form continuous network structure, and the space between the CNT connects mutually, helps TiO
2The demonstration on dispersion of nano-particles, surface and the circulation of reactive material, though latter's specific area is higher than the former, the micro-pore ratio is very high, active carbon carrying TiO
2(＜2nm) ratio is significantly higher than CNT carrying TiO to the micropore of photochemical catalyst
2Photochemical catalyst, the inner surface of these micro-pores to particle carrying still to solution in organic the contact all can't utilize.And active carbon is a graininess, and the inner activated carbon granule of its accumulation body is in contact with one another tightr, and the space is narrow, active carbon carrying TiO
2The pore volume of photochemical catalyst is significantly less than CNT carrying TiO
2Photochemical catalyst can illustrate this point.Thereby be unfavorable for TiO
2The abundant demonstration of particle surface and the circulation of reactive material.Therefore, though active carbon also can help to disperse TiO
2Particle, but its design feature is affected this effect.If CNT and active carbon are combined into complex carrier, may bring into play the strong point of the two.
CNT and active carbon is compound with 20: 80 mass ratio, adopt the method for reaction in-situ in the solution to prepare CNT/activated carbon composite carrier load TiO
2Semiconductor light-catalyst, the degradation rate test result of its photocatalysis to degrade organic matter shows, at TiO
2Under the condition of each mass ratio of carrier, complex carrier carrying TiO
2The speed of the photocatalysis to degrade organic matter of photochemical catalyst all is significantly higher than respectively by CNT and active carbon carrying TiO
2The speed of the photocatalysis to degrade organic matter of photochemical catalyst.Complex carrier carrying TiO is described
2What photochemical catalyst had been brought into play CNT makes the higher and stronger advantage separately of adsorb organic compound ability active carbon of photoelectric transformation efficiency.And the microscopical structure that is interconnected of the loose netted and space that can form between the CNT, can improve the internal structure of active carbon accumulation body, the inner slit of absorbent charcoal powder body is increased, test result shows complex carrier carrying TiO
2The ratio of the micropore of photochemical catalyst is carried TiO with respect to active carbon
2Photochemical catalyst significantly reduces.Therefore to disperseing TiO
2Particle and the circulation that promotes reactive material with all be useful with contacting of catalyst.
Claims (1)
1. the photochemical catalyst of a nano-carrier; It is characterized in that: the photochemical catalyst of described nano-carrier is the titania photocatalyst that is carried on CNT/activated carbon composite carrier; Its manufacture craft is to be (5～60) with the mass ratio of CNT and active carbon: (40～95) preparation CNT/activated carbon composite carrier, among the ratio adding absolute ethyl alcohol of this complex carrier in the corresponding 50ml absolute ethyl alcohol of every gram complex carrier, mix to stir and reached even in 1 hour, butyl titanate is dissolved in the absolute ethyl alcohol that contains complex carrier, be mixed with the butyl titanate solution of 0.1mol/L, too violent for preventing reaction, the HCl adding hydrochloric acid that in reactant liquor, adds 0.001mol by every L solution, in above-mentioned solution, add deionized water fast then, magnetic agitation 2 h, regulate pH value and to reactant liquor, form colloid, colloid is through stable, centrifugal, filter, and the impurity on flush away surface and ion, carry out drying, then in Muffle furnace with the temperature rise of 9 ℃/min to 600 ℃ of assigned temperatures, sintering 1h under the inert atmosphere protection, cooling naturally, then suitably grind and disperse, obtain titania oxide supported photochemical catalyst on CNT/activated carbon composite carrier; During operating process, the consumption of reactant butyl titanate is (2～98) by the titanium oxide that generates and the mass ratio of composite catalyst: (98～2) are controlled; The titania photocatalyst of above-mentioned CNT/active carbon carrying, after the poly-tetrafluoro suspension mixing with the ethanol dilution, baking is while stirring blown, treat that solvent evaporate into residue three/for the moment gradually, blade coating becomes the immobilized photochemical catalyst by CNT/activated carbon composite carrier carrying after the oven dry on cotton fibriia cloth; The organic matter that is used for the photocatalytic degradation waste liquid; Wherein the quality of poly-tetrafluoro accounts for 5% of composite photo-catalyst quality only.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510055525 CN1680023A (en) | 2004-07-15 | 2005-03-16 | Light catalyst for nanometer carrier |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410068963.1 | 2004-07-15 | ||
| CN 200410068963 CN1586713A (en) | 2004-07-15 | 2004-07-15 | Photo-catalyst of nano carrier |
| CN 200510055525 CN1680023A (en) | 2004-07-15 | 2005-03-16 | Light catalyst for nanometer carrier |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396373C (en) * | 2006-06-22 | 2008-06-25 | 厦门大学 | Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst |
| CN102101051A (en) * | 2011-01-25 | 2011-06-22 | 浙江大学 | Method for preparing carbon nano tube supported nano photocatalysis material capable of degrading nitrogen oxides |
| CN106423300A (en) * | 2016-12-02 | 2017-02-22 | 东华大学 | Fiber/carbon nanotube/Bi12TiO20 three-dimensional recycled efficient catalytic material and preparation and application thereof |
| CN106423301A (en) * | 2016-12-02 | 2017-02-22 | 东华大学 | Fiber/carbon nanotube/Bi2MoO6 three-dimensional recyclable efficient catalytic material as well as preparation method and application of catalytic material |
-
2005
- 2005-03-16 CN CN 200510055525 patent/CN1680023A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396373C (en) * | 2006-06-22 | 2008-06-25 | 厦门大学 | Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst |
| CN102101051A (en) * | 2011-01-25 | 2011-06-22 | 浙江大学 | Method for preparing carbon nano tube supported nano photocatalysis material capable of degrading nitrogen oxides |
| CN102101051B (en) * | 2011-01-25 | 2013-01-30 | 浙江大学 | Method for preparing carbon nano tube supported nano photocatalysis material capable of degrading nitrogen oxides |
| CN106423300A (en) * | 2016-12-02 | 2017-02-22 | 东华大学 | Fiber/carbon nanotube/Bi12TiO20 three-dimensional recycled efficient catalytic material and preparation and application thereof |
| CN106423301A (en) * | 2016-12-02 | 2017-02-22 | 东华大学 | Fiber/carbon nanotube/Bi2MoO6 three-dimensional recyclable efficient catalytic material as well as preparation method and application of catalytic material |
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