CN100400155C - Method for preparing photocatalyst of titanium dioxide carried by active carbon - Google Patents
Method for preparing photocatalyst of titanium dioxide carried by active carbon Download PDFInfo
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- CN100400155C CN100400155C CNB2005100493692A CN200510049369A CN100400155C CN 100400155 C CN100400155 C CN 100400155C CN B2005100493692 A CNB2005100493692 A CN B2005100493692A CN 200510049369 A CN200510049369 A CN 200510049369A CN 100400155 C CN100400155 C CN 100400155C
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Abstract
The present invention relates to a preparation method of photocatalysts using active carbon to carry titanium dioxide. The method adopts a vapor phase deposition method in metal organic chemistry and comprises the following steps of treating active carbon carriers by nitric acid, carrying heated titanium precursors to a quartz reactor holding active carbon by inert gas, depositing TiO2 onto the surface of the active carbon and calcining the titanium precursors under the protection of the inert gas. The present invention omits the steps of saturation, dryness, degradation, reduction, etc. in the traditional preparation method of TiO2 catalysts, and has the advantages of simple preparation process, low cost and easy industrialization. The grain diameter of prepared catalysts is small, and TiO2 is mainly deposited on the outer surface of the active carbon. The prepared catalysts with high catalytic activity can be repeatedly used, and can be especially suitable for the photocatalytic degradation of organic pollutants.
Description
Technical field
The present invention relates to a kind of preparation method of load type titania photocatalyst, especially the preparation method of absorbent charcoal loading titanium dioxide photocatalyst.
Background technology
Japanese Fujishima in 1972 and Honda report titanium dioxide (TiO
2) after the hydrolysis of monocrystalline electrode, organic research becomes the research focus gradually in the conductor photocatalysis water.TiO
2Inexpensive with it, non-secondary pollution, spectrochemical property is stable, and effectively characteristics such as nearly all organic pollution are subjected to researcher's attention in the photochemical catalytic oxidation water.Use TiO at present
2Usually adopt suspension system during degradation of contaminant: with nano level TiO
2Superfines (that the most frequently used is Degussa P25) is sneaked in the reactant liquor, and in ventilation, stirring, the condition of illumination simultaneously is issued to the organic purpose of mineralising.Though this method makes nano-TiO
2Fully contact with pollutant, but reclaim very difficulty of catalyst.If with nano-TiO
2Be fixed on the pelleted substrate (as active carbon) TiO
2Recovery become simple and easy to do.And a large amount of active carbons of discovering can be enriched to catalyst surface with the target contaminant in the solution, at TiO
2The surface produces a substrate enrichment environment, thereby has improved mineralization velocity, and intermediate product also is attracted to catalyst surface and is decomposed, and has avoided the generation of secondary pollution.Therefore, with TiO
2Be fixed on the active carbon, both can improve light-catalysed efficient, separable again recovery photochemical catalyst.At present, prepare activated carbon supported TiO
2The most frequently used method of photochemical catalyst is infusion process, sol-gel process and the precipitation method.These methods usually can be with TiO
2Be distributed in the hole of carrier, make TiO
2Extremely difficult by optical excitation, therefore, the TiO of load
2Activity can reduce greatly.And these method complex process, preparation cost is higher.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technology, and cost is lower, can be in the preparation method of active carbon outer surface loaded titanium dioxide photocatalyst.
The preparation method of absorbent charcoal loading titanium dioxide photocatalyst provided by the invention, employing be Metalorganic Chemical Vapor Deposition, may further comprise the steps:
1) 40~60 order granular active carbons is put into the HNO that concentration is 1-10mol/L
3In the solution, under the 373-573K temperature, boil 0.5-2h, generate oxygen-containing functional group, spend deionised water after the cooling at activated carbon surface;
2) active carbon of step 1) gained is put into quartz reactor, feed inert gas in reactor, gas flow is 50-200ml/min, is heated to 373-573K then and keeps 15-60 minute, continues heating and also remains on 673-1073K;
3) the titanium precursor thing being heated to 323-523K, is carrier gas with the inert gas, and the titanium precursor thing is downloaded in the quartz reactor, and gas flow is 100-800ml/min, at activated carbon surface depositing Ti O
2, behind the deposition 1-20h, stop to be written into the titanium precursor thing;
4) logical inert gas is calcined 1-3h to remove residual part titanium precursor thing under inert gas shielding in reactor.
Among the present invention, said inert gas is nitrogen, argon gas or their mixed gas.The titanium precursor thing is isopropyl titanate or butyl titanate.
Beneficial effect of the present invention is:
1) the present invention has omitted traditional TiO
2Steps such as saturated in the method for preparing catalyst, dry, aging, reduction have been simplified catalyst preparation process greatly.
2) because metal organic chemical vapor deposition (MOCVD) adopts the gas phase predecessor, the TiO of this feasible deposition
2Particle has smaller particle size, and TiO
2Major sedimentary is at the outer surface of active carbon, thereby helps to improve TiO
2Photocatalytic activity, reusable.
3) equipment is simple, is easy to industrialization.
Description of drawings
Fig. 1 is the X-ray diffractogram of the catalyst of the inventive method preparation;
Fig. 2 is the SEM figure of the catalyst of the inventive method preparation;
Fig. 3 is the TEM figure of the catalyst of the inventive method preparation;
Fig. 4 is TiO
2Surface concentration and the graph of a relation of load capacity;
Fig. 5 is activated carbon supported TiO
2The comparison of photochemical catalyst and powder photocatalyst reusability is among the figure
◆ represent activated carbon supported TiO
2When using for the 1st time, removes by photochemical catalyst the degradation curve of methyl orange,
The TiO that ▲ expression is activated carbon supported
2When using, photochemical catalyst the 5th removes the degradation curve of methyl orange,
■ represents activated carbon supported TiO
2When using for the 10th time, removes by photochemical catalyst the degradation curve of methyl orange,
◇ represents powder TiO
2(Degussa P25) removes the degradation curve of methyl orange when using for the 1st time,
△ represents powder TiO
2When using, (Degussa P25) the 5th removes the degradation curve of methyl orange,
represents powder TiO
2(Degussa P25) removes the degradation curve of methyl orange when using for the 10th time.
The specific embodiment
The present invention can describe in detail by embodiment, but is not that the present invention is done any restriction.
Embodiment 1
40~60 order granular active carbons are put into the HNO that concentration is 6mol/L
3In the solution, under the 373K temperature, boil 1h, generate oxygen-containing functional group, spend deionised water after the cooling at activated carbon surface; Above-mentioned gained active carbon is put into quartz reactor, feed nitrogen in reactor, control nitrogen flow 100ml/min is heated to 423K then and kept 60 minutes; Again reactor is heated to 873K; Butyl titanate is heated to 523K, and as carrier gas, gas flow is 400ml/min with nitrogen, and butyl titanate is downloaded in the reactor, and butyl titanate decomposes the back at activated carbon surface depositing Ti O
2, behind the deposition 12h, close the butyl titanate valve, logical nitrogen is calcined 3h to remove residual part predecessor under nitrogen protection in reactor, makes absorbent charcoal loading titanium dioxide photocatalyst.
40~60 order granular active carbons are put into the HNO that concentration is 10mol/L
3In the solution, under the 573K temperature, boil 2h, generate oxygen-containing functional group, spend deionised water after the cooling at activated carbon surface; Above-mentioned gained active carbon is put into quartz reactor, feed nitrogen in reactor, control nitrogen flow 200ml/min is heated to 523K then and kept 15 minutes; Again reactor is heated to 773K; Isopropyl titanate is heated to 323K, and as carrier gas, gas flow is 400ml/min with nitrogen, and isopropyl titanate is downloaded in the reactor, and isopropyl titanate decomposes the back at activated carbon surface depositing Ti O
2, behind the deposition 6h, close the isopropyl titanate valve, logical nitrogen is calcined 3h to remove residual part predecessor under nitrogen protection in reactor, makes absorbent charcoal loading titanium dioxide photocatalyst.
Embodiment 3
40~60 order granular active carbons are put into the HNO that concentration is 1mol/L
3In the solution, under the 373K temperature, boil 0.5h, generate oxygen-containing functional group, spend deionised water after the cooling at activated carbon surface; Above-mentioned gained active carbon is put into quartz reactor, feed argon gas in reactor, control argon flow amount 50ml/min is heated to 323K then and kept 30 minutes; Again reactor is heated to 1073K; Isopropyl titanate is heated to 423K, and as carrier gas, gas flow is 800ml/min with argon gas, and isopropyl titanate is downloaded in the reactor, and isopropyl titanate decomposes the back at activated carbon surface depositing Ti O
2, behind the deposition 10h, close the isopropyl titanate valve, logical argon gas is calcined 3h to remove residual part predecessor under argon shield in reactor, makes absorbent charcoal loading titanium dioxide photocatalyst.
Adopt the supported titanium of the present invention's preparation
2Photochemical catalyst is through the TiO of characterization methods such as XRD, SEM, TEM, XPS proof institute load
2Be anatase, and be evenly distributed that grain (is seen Fig. 2, Fig. 3) in the scope of size at 10-50nm.Fig. 1 is the X-ray diffractogram of the catalyst of preparation, and sample the diffraction maximum of anatase occurs at 2 θ=25.3 places, proves the TiO of load
2Crystal formation be anatase.As can be seen from Figure 4, at the TiO of active carbon outer surface
2Concentration be much higher than load capacity, illustrate the deposition TiO
2Basic load is at the outer surface of active carbon.As can be seen from Figure 5, activated carbon supported TiO
2Using after 10 times, activity is constant substantially, shows TiO
2Combine very firm with active carbon.
Claims (3)
1. the preparation method of absorbent charcoal loading titanium dioxide photocatalyst is characterized in that described method may further comprise the steps:
1) 40~60 order granular active carbons is put into the HNO that concentration is 1-10mol/L
3In the solution, under the 373-573K temperature, boil 0.5-2h, generate oxygen-containing functional group, spend deionised water after the cooling at activated carbon surface;
2) active carbon of step 1) gained is put into quartz reactor, feed inert gas in reactor, gas flow is 50-200ml/min, is heated to 373-573K then and keeps 15-60 minute, continues heating and also remains on 673-1073K;
3) the titanium precursor thing being heated to 323-523K, is carrier gas with the inert gas, and the titanium precursor thing is downloaded in the quartz reactor, and gas flow is 100-800ml/min, at activated carbon surface depositing Ti O
2, behind the deposition 1-20h, stop to be written into the titanium precursor thing;
4) logical inert gas is calcined 1-3h to remove residual part titanium precursor thing under inert gas shielding in reactor.
2. the preparation method of absorbent charcoal loading titanium dioxide photocatalyst according to claim 1 is characterized in that said inert gas is nitrogen, argon gas or their mixed gas.
3. the preparation method of absorbent charcoal loading titanium dioxide photocatalyst according to claim 1 is characterized in that said titanium precursor thing is isopropyl titanate or butyl titanate.
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CN100371261C (en) * | 2006-06-16 | 2008-02-27 | 浙江大学 | Method for treating wastewater through catalysis of connected load type Ti02 of plasma in liquid phase |
CN101905154B (en) * | 2010-08-20 | 2013-01-02 | 中国林业科学研究院林产化学工业研究所 | Method for improving efficiency of visible light response doping-type M-TiO2/AC photocatalyst |
CN102078807B (en) * | 2011-01-05 | 2013-01-16 | 吉林大学 | Er<3+>:YAlO3/TiO2-loaded photocatalyst and preparation method thereof |
CN102211033A (en) * | 2011-04-15 | 2011-10-12 | 中国林业科学研究院林产化学工业研究所 | Method for preparing platinum and nitrogen codoped active carbon supported titanium dioxide photocatalyst |
CN102698729A (en) * | 2012-06-11 | 2012-10-03 | 遵义医学院 | Method for enhancing adhesiveness of nano TiO2 on surface of active carbon |
CN102744052A (en) * | 2012-07-31 | 2012-10-24 | 遵义医学院 | Method for improving nanometer TiO2/AC photochemical catalyst activity |
CN103088648B (en) * | 2013-01-25 | 2015-01-07 | 中国科学院新疆生态与地理研究所 | Preparation method for carbon fiber material with composite nano structure |
CN103785371B (en) * | 2014-03-04 | 2016-01-13 | 湘潭大学 | A kind of porous carbon microspheres TiO 2composite and its preparation method and application |
CN104319040B (en) * | 2014-09-30 | 2017-04-12 | 盐城申源塑胶有限公司 | Coated type insulation composite material and preparation method thereof |
CN109529953A (en) * | 2018-12-13 | 2019-03-29 | 四川农业大学 | A kind of collagen TiO2Composite catalyst and preparation method thereof |
CN111468092B (en) * | 2020-04-14 | 2023-04-18 | 西安近代化学研究所 | Carbon-based titanium dioxide composite combustion catalyst for propellant and preparation method thereof |
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GB2327090A (en) * | 1997-07-09 | 1999-01-13 | British Aerospace | CVD manufacturing a multilayer optical mirror using ultra-violet light |
CN1454708A (en) * | 2002-04-30 | 2003-11-12 | 中国人民解放军63971部队 | Method of preparing composite photocatalytic material for air purification |
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