CN101584983B - High-efficiency titanium dioxide-silicon oxide photocatalysis material and synthetic method thereof - Google Patents
High-efficiency titanium dioxide-silicon oxide photocatalysis material and synthetic method thereof Download PDFInfo
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- CN101584983B CN101584983B CN 200810071097 CN200810071097A CN101584983B CN 101584983 B CN101584983 B CN 101584983B CN 200810071097 CN200810071097 CN 200810071097 CN 200810071097 A CN200810071097 A CN 200810071097A CN 101584983 B CN101584983 B CN 101584983B
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- silicon oxide
- rhodamine
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Abstract
The invention relates to a high-efficiency titanium dioxide-silicon oxide photocatalysis material and a synthetic method thereof, in particular to the field of purification of colored dye in sewages. Titanic acid ester and silicon ester are formed into a composition precursor in oleic acid solution, and methylamine and the precursor are polymerized into a titanium dioxide-silicon oxide compound at 160-200 DEG C under the action of aminolysis; and after the reaction, the compound is cooled to room temperature, washed and dried. The material is a polymer which has a diameter of about 25-40nm and a specific surface area of 122m2/g, a pore volume of 0.555cm3/g and an average pore size of 15nm and consists of spheroidal particles. The photocatalysis material has high-efficiency purificationeffect of visible light and can degrade 5*10-5M rhodamine B completely within a short time of 2.5 hours; and the residual adsorption of the rhodamine B cannot be detected in the degraded catalyst.
Description
Technical field
The present invention relates to coloured dyestuff field of purification in the sewage, especially relate to the synthetic method of a kind of highly efficient titania-silica composite photocatalyst material.
Background technology
Along with society and economic fast development, the environment that the mankind depend on for existence also suffers destruction in various degree at present, and wherein the pollution of water environment is on the rise especially.According to statistics, the economic loss that China causes because of water pollution every year reaches 40,000,000,000 yuan, and the annual waste water total release in China city is about 41,500,000,000 tons, wherein industrial wastewater accounts for 70%, and printing and dyeing are the blowdown rich anies influential family in the industry, account for about 35% of whole industrial wastewater total amount, are about 14,500,000,000 tons.Therefore the improvement of industrial wastewater, direct relation China to water resource rationally, take full advantage of, directly affect the sustainable development of China's economy and society.The characteristics such as waste water from dyestuff has the content of organics height, and colourity is dark, and biodegradability is poor belong to difficult waste water.Particularly employed dyestuff is more stable in recent years, and the degree of biodegradability further reduces.At present, the method for improvement waste water from dyestuff has: physisorphtion, chemical oxidization method, microorganism treatment etc.It is low that these conventional methods exist efficient, and energy consumption is high, and thoroughly decomposing pollutant easily produces the shortcomings such as secondary pollution.Although in the past, now even all will be the predominant methods of wastewater treatment in the future a period of time.But along with the continuous anxiety of water resource and China to the improving constantly of sewage drainage standard, new sewage disposal technology must and constantly developed.Wherein, photocatalysis technology is a kind of novelty and promising method, and mainly concentrates at present the development of photochemical catalyst about the research of this respect.Titanium dioxide optical catalyst has stable chemical nature, asepsis environment-protecting, the advantage such as cheap.But the titanium dioxide that prior synthesizing method obtains exists three large shortcomings: the one, and it is not high that titanium dioxide optical catalyst exists specific area, and porosity is little and pore-size distribution is concentrated, and this is unfavorable for absorption and the mass transport process of the large molecule of Wastewater Dyes in the duct.The 2nd, in the waste water dyestuff of higher concentration, the easy inactivation of titanium dioxide optical catalyst.The 3rd, titanium dioxide optical catalyst must could be degraded to the dyestuff in the waste water under the exciting of ultraviolet light, and the degradation efficiency under the visible light condition is very limited.For this reason, it is particularly important with degradation of dye that research and development has the photochemical catalyst of visible light effect efficiently.
Summary of the invention
The present invention proposes the method for a kind of binary coupling porous nano titanium oxide-silica composite photocatalyst material.This nano-photocatalyst material is synthetic simple, need not high-temperature post-treatment.High concentrations of organic dye is had very high Visible Light Induced Photocatalytic activity, can be with 5 * 10
-5The rhodamine B of M 2.5h under the visible light condition degrades complete substantially.And this material is convenient to immobilized use, is expected to be applied to the wastewater treatment of coloured dyestuff, has a good application prospect.
The present invention adopts solvent-thermal method synthesis of nano titanium dioxide-silica composite photocatalyst material, and detailed process is as follows: under the room temperature, with oleic acid, three kinds of solvent of cyclohexane and triethylamine form clear solution.Under magnetic agitation, slowly drip butyl titanate and silicic acid four butyl ester mixtures (mol ratio is adjustable), stir evenly backward mentioned solution and drip methylamine solution, then change in the reactor.160-200 ℃ of constant temperature some hours.After the reaction, be cooled to room temperature, washing, drying.
Dyestuff light degradation experiment is take the Visible Light Induced Photocatalytic rhodamine B as example, and experimentation is as follows: preparation 5 * 10
-5The rhodamine B aqueous solution of M adds composite photo-catalyst, and the suspension that obtains places the dark place magnetic agitation to be no less than 0.5 hour, to reach rhodamine B, dissolved oxygen in the adsorption/desorption balance of catalyst surface.Then suspension is placed below the halogen light modulation of a 300W.Take a sample at regular intervals, use at last the absorption spectrum of measurement of ultraviolet-visible spectrophotometer centrifugal clear liquid.
Our diameter by the preparation of above method is about 25-40nm, appearance state of aggregation nano titanium oxide spherical in shape-silica porous catalysis material, and this material has than high-ratio surface (122m
2/ g), large pore volume (0.555cm
3/ g) and rational pore-size distribution (15nm) has very strong adsorption capacity and Visible Light Induced Photocatalytic is active to organic dyestuff, and 2.5 hours substantially can be with 5 * 10
-5The rhodamine B degraded of M fully.
Titanium dioxide of the present invention-silica porous catalysis material is controlled formation and the crystallization of titanium dioxide-silica porous catalysis material by accurate control preparation condition.Than commercial product P-25, poriferous titanium dioxide of the present invention-silica composite photo-catalyst is obviously superior to the degradation effect of rhodamine B, can visible light in the lower short time of effect (2.5 hours) reach best degradation effect, degradation rate is near 100%, and the degraded rear catalyst does not detect the remnants absorption of rhodamine B yet.Technology of preparing is simple, equipment requirement is not high, with low cost, and this material is convenient to immobilized use, is expected to be applied to the wastewater treatment of coloured dyestuff.
Description of drawings
Fig. 1 is TiO
2-SiO
2The ESEM of composite photo-catalyst (a) and transmission electron microscope (b) photo.
Fig. 2 is TiO
2-SiO
2The nitrogen adsorption of composite photo-catalyst-desorption curve, illustration are graph of pore diameter distribution
Fig. 3 is TiO
2-SiO
2The efficiency curve of composite photo-catalyst Visible Light Induced Photocatalytic rhodamine B (comparing with P-25).
The specific embodiment
Example 1: the chemical pure oleic acid of 50mL is mixed the formation clear solution with 10mL cyclohexane and 10mL triethylamine, under magnetic agitation, slowly drip 3.5mL chemical pure butyl titanate and silicic acid four butyl ester mixtures (volume ratio 2.5: 1), after continuing to stir evenly 10 minutes, solution is become brown by yellow, continue to drip 3mL methylamine (30%) aqueous solution, in the reactor of packing into after stirring.160 ℃ of constant temperature 24 hours naturally cools to room temperature, and product is washed several times, naturally dries to get faint yellow TiO
2-SiO
2Compound.
Example 2: the chemical pure oleic acid of 50mL is mixed the formation clear solution with 10mL cyclohexane and 10mL triethylamine, under magnetic agitation, slowly drip the chemical pure butyl titanate of 3.5mL and silicic acid four butyl ester mixtures (volume ratio 2.5: 1), after continuing to stir evenly 10 minutes, solution is become brown by yellow, continue to drip 3mL methylamine (30%) aqueous solution, in the reactor of packing into after stirring.200 ℃ of constant temperature 24 hours naturally cools to room temperature, and product is washed several times, and is centrifugal, naturally dries to get faint yellow TiO
2/ SiO
2Compound.
Example 3: the degraded of dyestuff is carried out at the photocatalytic reaction device of designed, designed, as substrate, estimates the activity of photochemical catalyst with rhodamine B under radiation of visible light.The concentration of the rhodamine B aqueous solution is 5 * 10
-5M, 80mL 5 * 10 in the beaker of a uncovered 100mL
-5The rhodamine B aqueous solution of M to wherein adding the 80mg photochemical catalyst, places the about 5h of dark place magnetic agitation with the suspension that obtains under the magnetic agitation, to reach rhodamine B in the adsorption/desorption balance of catalyst surface.Then suspension is placed below the halogen light modulation of a 300W.Every 15min takes out the 4mL suspension and places centrifuge tube centrifuge centrifugation (the ordinary instrument in Changsha, TG-∏ type whizzer, 9000rpm, 15min), the clarification centrifugate that obtains.Record the uv-visible absorption spectra (sweep limits 400-700nm) of clear liquid at Perkin ElmerUV WinLab Lambda 35 ultraviolet-uisible spectrophotometers.
Claims (2)
1. the synthetic method of highly efficient titania-silica composite photocatalyst material, it is characterized in that: under the room temperature, with oleic acid, three kinds of solvent of cyclohexane and triethylamine form clear solution, under magnetic agitation, slowly drip butyl titanate and silicic acid four butyl ester mixtures, butyl titanate and silicic acid four butyl ester mol ratios are adjustable, stir evenly in the backward solution and drip methylamine solution, then change in the reactor, 160-200 ℃ of constant temperature some hours after the reaction, is cooled to room temperature, washing and dry, the acquisition diameter is 25-40nm, and appearance is spherical aggregation, and specific area is 122 m
2/ g, pore volume are 0.555 cm
3/ g, average pore size is the titanium dioxide-silica composite photocatalyst material of 15 nm.
2. one kind is adopted the synthetic titanium dioxide of the described method of claim 1-silica composite photocatalyst material, and this material diameter is 25-40nm, and appearance is spherical aggregation, and specific area is 122 m
2/ g, pore volume are 0.555 cm
3/ g, average pore size is 15 nm, adopts the described method of claim 1 synthetic.
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| CN105000625B (en) * | 2015-07-16 | 2017-06-09 | 黄冈师范学院 | A kind of light catalytic treatment method of waste water from dyestuff |
| CN110586192B (en) * | 2019-09-27 | 2022-03-25 | 浙江工业大学上虞研究院有限公司 | Preparation method of dendritic mesoporous template-supported titanium dioxide photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101088606A (en) * | 2006-06-12 | 2007-12-19 | 中国科学院理化技术研究所 | Prepn process of nanometer composite titania/silica photocatalyst sol and transparent photocatalyzing film |
| CN101371980A (en) * | 2007-08-21 | 2009-02-25 | 黑龙江大学 | Process for synthesizing mesoporous silicon dioxide modified titanic oxide photocatalyst of high activity |
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| CN101088606A (en) * | 2006-06-12 | 2007-12-19 | 中国科学院理化技术研究所 | Prepn process of nanometer composite titania/silica photocatalyst sol and transparent photocatalyzing film |
| CN101371980A (en) * | 2007-08-21 | 2009-02-25 | 黑龙江大学 | Process for synthesizing mesoporous silicon dioxide modified titanic oxide photocatalyst of high activity |
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Effective date of registration: 20211231 Address after: 719054 road 2-3, B4 Road, fine chemical park, high tech Industrial Park, Yulin City, Shaanxi Province Patentee after: Shaanxi Tanwei Rixin Chemical Co.,Ltd. Address before: Fuzhou City, Fujian province 350002 Yangqiao Road No. 155 Patentee before: FUJIAN INSTITUTE OF RESEARCH ON THE STRUCTURE OF MATTER, CHINESE ACADEMY OF SCIENCES |