CN100377778C - Titanium oxide photocatalyst stimulated by visible light and synthesis method thereof - Google Patents
Titanium oxide photocatalyst stimulated by visible light and synthesis method thereof Download PDFInfo
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- CN100377778C CN100377778C CNB2004100160134A CN200410016013A CN100377778C CN 100377778 C CN100377778 C CN 100377778C CN B2004100160134 A CNB2004100160134 A CN B2004100160134A CN 200410016013 A CN200410016013 A CN 200410016013A CN 100377778 C CN100377778 C CN 100377778C
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Abstract
The present invention relates to a titanium oxide photocatalyst excited by visible light and a synthesis method thereof. The present invention uses thiourea, lanthanum nitrate or lanthanum, and polyethyleneglycol or polyvinyl alcohol as raw material; the raw material and a TiCl4 water solution are mixed to synthesize a visual light catalyst by a hydrothermal method; the visual light catalyst uses titanium dioxide as a basal body with 1.0 to 3.0 at% of sulfur content and 1.0 to 2.5 at% of lanthanum content; the visual light catalyst can effectively degrade the organic industrial dye of methylene blue under the light of visual light, and the degradation rate can reach 98.4%. the visual light catalyst can be used for removing pollutants in environment and converting and catalyzing solar energy and can be used in photoelectric conversion apparatuses.
Description
Technical field
The present invention relates to a kind of titania photocatalyst and synthetic method thereof of excited by visible light, the prepared catalyst harmful substance in the environment that can be used for degrading belongs to the photocatalyst material field.
Technical background
Photochemical catalyst is one of most active research field of international academic community in recent years.Photocatalysis technology has broad application prospects at aspects such as environmental protection, solar energy utilization and new functional material exploitations, is the new and high technology with substantial economics and social benefit.Developed countries such as present America and Europe have all injected capital into and have carried out the research and development of photocatalysis technology with research effort, and new high-tech industry based on this forms.At present mostly be n type semi-conducting material, as TiO at the photochemical catalyst that photocatalysis field adopted
2, ZnO, Fe
2O
3, SnO
2, CdS, WO
3Deng, nano-TiO wherein
2Since have anti-chemistry and photoetch, stable in properties, nontoxic, catalytic activity is high, advantage such as inexpensive and being paid attention to most, have broad application prospects.Under greater than its band-gap energy illumination condition, TiO
2The harmful organic substance that photochemical catalyst can not only be degraded in the environment fully generates CO
2And H
2O, and can remove the oxynitride NO of low concentration in the atmosphere
xWith sulfide H
2S, SO
2Deng toxic gas.At present mainly concentrate on environmental pollution improvement, water treatment, air cleaning, sterilization, anticancer, automatically cleaning, the energy and be used for photocatalysis Decomposition water generates hydrogen and oxygen, thereby the clean energy resource of free of contamination effective, harmless is provided about the application study of titania photocatalyst.
TiO
2It is a kind of n type semi-conducting material, oxidisability and reproducibility are strong, anatase is arranged, three kinds of crystal structures of rutile and brockite, energy gap between its valence band (VB) and the conduction band (CB) is 3.0～3.2eV, be equivalent to the photon energy that wavelength is 387.5nm, when less than this wavelength photon irradiation to TiO
2When surface, the electronics that is in valence band will be excited on the conduction band, thereby produces highly active hole (h+) and electronics (e+) respectively on valence band and conduction band, and electronics separates under effect of electric field and migrates to the surface.When catalyst exist suitable when capturing agent and blemish attitude, the compound of electronics and hole is inhibited, will be before compound at catalyst surface generation oxidation-reduction reaction, most of photocatalysis oxidation reactions are direct and indirect energy of oxidations that utilize the hole.After the particle nanometer of photochemical catalyst, the energy level of generation moves, the space of convergence surface, optical excitation position, separation of charge diminishes and effect such as surface area increase can effectively improve quantum yield, is beneficial to light-catalyzed reaction.
The titanium oxide photochemical catalyst technology has obtained development faster at last decade, but its wide industrial is used and is subjected to very big restriction, the subject matter that exists comprises at present: quantum yield low (about 4%), and overall reaction rate is slower, is difficult to handle a large amount of and high industrial waste gas and the waste water of concentration; TiO
2Light absorption wavelength narrow (mainly in the ultra-violet (UV) band), its absorption spectrum only accounts for a very little part in the solar spectrum, and solar energy utilization ratio is low.Therefore, development has high quantum production rate, can is the emphasis and the focus of a difficult problem in the current solution photocatalysis technology by the high efficiency semiconductor photochemical catalyst of the excited by visible light in the solar spectrum.All have a large amount of documents and monograph to deliver in every year aspect its photocatalysis performance of raising, people such as Choi are with chloroform oxidation and CCl
4Be reduced to example, the preparation method adopts titanium tetraisopropylate ground sol gel process, has studied and Ti
+Close 21 metal ion species of radius are to quantization TiO
2The effect (Choi, the W. that mix; Termin, A.; Hoffmann, M.R.J.Phys.Chem.1994,98,13669.), the doping of relevant metal cation subsequently utilizes the alkoxide of titanium to be a lot of researchs (Dvoranova, D.; Brezova, V.; Mazur, M.; Malati, M.A.Appl.Cataly.B:Environ.2002,37,9); Anionic doping research comprises doping (Sakthivel, the S. of carbon; Kisch, H.Angew.Chem.Int.Ed.2003,42,4908.), nitrogen adulterated TiOx powder (Yin, S.; Zhang, Q.; Saito, F.; Saito, T.Chem.Lett.2003,32,358) and nitrogen to doping (Irie, the H. of thin film of titanium oxide; Washizuka, S.; Yoshino, N.andHashimoto, K.Chem.Commun., 2003,1298-1299.), anionic doping such as sulphur.Existing studies show that, the doping of sulphion have been adopted method ((a) Umebayashi, the T. of titanium disulfide anneal oxidation; Yamaki, T.; Itoh, H.; Asai, K.Appl.Phys.Lett.2002,81,454. (b) T.Umebayashi, T.Yamaki, S.Tanaka, K.Asai, Chem.Lett.2003,32,330.), but this mixes the crystalline phase that the sulphur method must just can obtain adulterated TiOx through the method for high-temperature calcination, and high-temperature calcination often makes the visible light catalysis activity of titanium oxide reduce.
Metal ion mixing major part in the past all can not make the catalytic performance of nano-titanium oxide have big performance to improve at visible region, because often becoming the complex centre in electronics and hole, metal ion reduces catalytic performance, metal ion mixing descends the heat endurance of catalyst in addition, the research of at present relevant anion doped aspect, at visible region tangible absorption is arranged after mixing, but also do not make the degraded of organic dyestuff methylene blue reach the report more than 95% with regard to its catalytic performance.
Summary of the invention
The objective of the invention is to prepare the titania photocatalyst that can be used in excited by visible light, the improvement of pollutant is the final radiation energy that requires with the sunshine, is conversion of solar energy that chemical energy is used.Because sunshine is inexhaustible for the mankind, nexhaustible, therefore greatly reduce processing cost, be a kind of power-saving technology.
Concrete steps of the present invention are:
1, with thiocarbamide, lanthanum nitrate (or lanthanum chloride) and surfactant polyethylene (or polyvinyl alcohol) are dissolved in distilled water and mix;
2, preparation 1～5mol/L TiCl
4The aqueous solution, preferred solution preparation condition is under ice-water bath;
3, above-mentioned steps 1 and 2 gained solution are mixed and be made into final solution, make that thiocarbamide and titanium tetrachloride mol ratio are 1: 0.2～2; Lanthanum nitrate (or lanthanum chloride) content is 0.01～1.5mol%; Surfactant polyethylene (or polyvinyl alcohol) content is 0.5～3mol%, and preferred solution preparation condition is under ice-water bath;
4, final solution being placed liner is the autoclave of polytetrafluoroethylene (PTFE), and liquor capacity is the about 60～80% of cumulative volume, and the hydrothermal treatment consists temperature can be 150 ℃～250 ℃, and the time is 0.5～5 hour;
5, the precipitation that obtains with distilled water washing hydro-thermal is removed until chlorion wherein, then with alcohol washing and dry;
Adopt above method and the titanium oxide catalyst powder that makes of prescription be rutile mutually, pattern is a corynebacterium, and powder is through ICP constituent analysis and XPS Surface Quantitative Analysis, and sulfur content is about 1.0～3.0at%, because lanthanum is in the enrichment on surface, it is 1.0～2.5at% that the surface contains the lanthanum amount;
Light-catalyzed reaction is carried out in self-control reactor (see figure 1), reactor is three layers of concentric circles tubular glass container, the middle outstanding 300W medium pressure mercury lamp that has, logical recirculated cooling water in the inner sleeve, inner sleeve pastes the filter plate of one deck 400nm outward, making and have only wavelength can see through filter plate greater than the visible light of 400nm, is reactor in the middle of the interior overcoat;
Under magnetic agitation with TiO
2Powder and 20～50mg/L methylene blue solution, adopt powerful the stirring to keep particle to be uniformly dispersed, uviol lamp is clock reaction after preheating, from the reactor bottom gas distribution pipe with the certain flow aerating oxygen, with the residue percentage of methylene blue after reaction a period of time, promptly reaction back methylene blue concentration C and initial concentration CO's recently weighs the particle photocatalytic activity.Centrifugal elimination TiO
2Particle is analyzed the methylene blue solution change in concentration.
The synthetic visible light catalyst of this method not only can be applicable to the processing of pollutant in the environment, also can be used in conversion of solar energy, catalysis and the photoelectric conversion device.
Characteristics of the present invention are:
(1) adopts original position synthetic water heat treatment method to mix, make uniform doping.
(2) rear-earth-doped amount is few, has reduced industrial synthetic cost.
(3) realized under the radiation of visible light degraded to the industrial dye methylene blue, sulphur lanthanum two mix effect makes visible light catalysis activity reach 98.4%.
Description of drawings
Fig. 1 is self-control jacket type visible light catalytic reactor.
Fig. 2 singly mixes the X ray diffracting spectrum of lanthanum and the lanthanum co-doped powder of sulphur for undoping, singly mix sulphur, shows among the figure that crystalline phase is the rutile phase.
(A) unadulterated rutile titanium oxide, (B) the rutile titanium oxide of sulfur doping, (C) the rutile titanium oxide that mixes of lanthanum, (D) the rutile titanium oxide mixed altogether of sulphur lanthanum.
Fig. 3 is the uv-visible absorption spectra of various adulterated powders, and the absorption spectrum ABSORPTION EDGE after mixing has as can be seen from Figure had red shift.
(A) the rutile titanium oxide mixed altogether of sulphur lanthanum, (B) the rutile titanium oxide of sulfur doping, (C) the rutile titanium oxide that mixes of lanthanum, (D) unadulterated rutile titanium oxide.
Fig. 4 is the transmission electron microscope photo of the codope visible light catalyst of 150 ℃ of-200 ℃ of hydrothermal treatment consists, picture shows that morphology microstructure is a corynebacterium, the crystalline size of 200 ℃ of (Fig. 4 c) hydrothermal treatment consists is greater than 150 ℃, and (Fig. 4 a) and the powder of 180 ℃ of (Fig. 4 b) hydrothermal treatment consists, illustrate that temperature is high more, crystal is grown up fast more, and crystal property is good more.
Fig. 5 is that the methylene blue degradation rate is over time under each powder radiation of visible light.Sulphur lanthanum co-doped (200 ℃) is the fastest to the degradation speed of methylene blue as can be seen, and the degradation amount maximum illustrates that its catalytic activity is the highest.
(A) (B) lanthanum doping (200 ℃ of hydro-thermals) of lanthanum doping (180 ℃ of hydro-thermals), (C) sulfur doping (180 ℃ of hydro-thermals), (D) sulfur doping (200 ℃ of hydro-thermals), (E) sulphur lanthanum co-doped (150 ℃ of hydro-thermals), (F) sulphur lanthanum co-doped (180 ℃), (G) sulphur lanthanum co-doped (200 ℃).
Fig. 6 is the comparison of the codope visible light catalyst of 200 ℃ of hydrothermal treatment consists to industrial dye methylene blue degraded front and back.Can find out the degradation effect of sulphur lanthanum co-doped (200 ℃) intuitively to organic dyestuff.
The specific embodiment
Further specify feature of the present invention and effect with following non-limiting embodiment.
Thiocarbamide 3.65g, lanthanum nitrate 0.0213g and surfactant polyethylene (M=4000) 7.18g are dissolved in 88 milliliters of the distilled water, and magnetic agitation mixes it.Analyze pure TiCl
4Arrive 3mol/L with distilled water diluting under ice-water bath, magnetic agitation mixes it.TiCl with 32 milliliters 3mol/L
4In the above-mentioned mixed solution during aqueous solution adding is stirred.Ice-water bath stirred 1 hour down, and component is all dissolved.Then mixed solution being placed liner for each 60 milliliters is the stainless steel autoclave of polytetrafluoroethylene (PTFE) (capacity is 100 milliliters), carries out hydro-thermal 2 hours under 200 ℃ of temperature.The precipitation that hydro-thermal is obtained is removed (checking with silver nitrate) with distilled water washing 8-10 time until chlorion wherein, washs three times 60 ℃ of vacuum drying 4 hours then with alcohol.Adopting above method is rutile (Fig. 2) mutually with the titanium oxide powder that prescription makes, and pattern is corynebacterium (Fig. 4 c).Prepared powder is carried out the uv-visible absorption spectra analysis, and the later powder ABSORPTION EDGE of mixing has red shift phenomenon (Fig. 3).
Adopt above method and the titanium oxide powder that makes of prescription be rutile mutually, pattern is a corynebacterium, powder is through ICP constituent analysis and XPS Surface Quantitative Analysis, sulfur content is about 1.7at% because lanthanum is in the enrichment on surface, it is 1.69at% that the surface contains the lanthanum amount;
Light-catalyzed reaction is carried out in self-control reactor (Fig. 1), reactor is three layers of concentric circles tubular glass container, the middle outstanding 300W medium pressure mercury lamp that has, logical recirculated cooling water in the inner sleeve, inner sleeve pastes the filter plate of one deck 400nm outward, making and have only wavelength can see through filter plate greater than the visible light of 400nm, is reactor in the middle of the interior overcoat.Under magnetic agitation with TiO
2Join the methylene blue solution of 450ml initial concentration CO=20mg/L, catalyst powder bulk concentration 1.5g/L, adopt powerful the stirring to keep particle to be uniformly dispersed, uviol lamp is clock reaction after preheating, from the reactor bottom gas distribution pipe with the certain flow aerating oxygen, oxygen flow is 10mL/min, and with the residue percentage of methylene blue after reaction a period of time, promptly reaction back methylene blue concentration C and initial concentration CO's recently weighs the particle photocatalytic activity.Concrete grammar for ease of the concentration of test methylene blue, dilutes 5 times, centrifugal elimination TiO for got 4ml solution every 1 hour
2Particle is analyzed methylene blue solution concentration rate, i.e. curve map 5G over time.The lanthanum co-doped catalyst visible light catalysis activity of the sulphur of 200 ℃ of hydrothermal treatment consists is the highest, finally reaches percent 98.4% (Fig. 6).
The presoma proportioning is same as embodiment 1, and processing procedure is also identical with embodiment 1, and treatment temperature is 180 ℃.The morphology microstructure that obtains is shown in Fig. 4 (b).To the degradation curve of organic dyestuff methylene blue shown in Fig. 5 F.
The presoma proportioning is same as embodiment 1, and processing procedure is also identical with embodiment 1, and treatment temperature is 150 ℃.The morphology microstructure that obtains also has agglomeration as can be seen between the powder shown in Fig. 4 (a), its degree of crystallinity is poorer than the powder of 180 ℃ and 200 ℃ processing, and crystallite dimension is also little.Shown in Fig. 5 E, it is to effective not as embodiment 1 and embodiment 2 of degradation rate of methylene blue to the degradation curve of organic dyestuff methylene blue.
Claims (4)
1. the titania photocatalyst of excited by visible light is characterized in that with titanium dioxide being matrix, and sulfur content is 1.0～3.0at%, and containing the lanthanum amount is 1.0～2.5at%, and crystalline phase is the rutile phase, and photochemical catalyst exists with the powder form, and morphology microstructure is a corynebacterium.
2. the synthetic method of the titania photocatalyst of an excited by visible light as claimed in claim 1 is characterized in that may further comprise the steps:
(1) with thiocarbamide, lanthanum nitrate or lanthanum chloride, polyethylene glycol or polyvinyl alcohol are dissolved in distilled water and mix;
(2) preparation 1～5mol/L TiCl
4The aqueous solution;
(3) above-mentioned steps (1) and (2) gained solution are mixed and are made into final solution, make that thiocarbamide and titanium tetrachloride mol ratio are 1: 0.2～2, lanthanum nitrate or lanthanum chloride content are 0.01～1.5mol%, and polyethylene glycol or polyvinyl alcohol content are 0.5～3mol%;
(4) final solution is placed 150 ℃～250 ℃ hydrothermal treatment consists of autoclave obtained precipitation in 0.5～5 hour;
(5) remove chlorion with the distilled water washing precipitation, then with alcohol washing and dry.
3. press the synthetic method of the titania photocatalyst of the described excited by visible light of claim 2, it is characterized in that TiCl
4The aqueous solution and final solution preparation condition are under ice-water bath.
4. the titania photocatalyst of excited by visible light as claimed in claim 1 is used for removing the pollutant of environment or is used for conversion of solar energy, catalysis or is used for photoelectric conversion device.
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| CN1311900C (en) * | 2005-01-27 | 2007-04-25 | 浙江大学 | Water heating preparation of phthalocyanin sennsitized nano cobalt dioxide powder |
| CN1311901C (en) * | 2005-01-28 | 2007-04-25 | 浙江大学 | Supersonic preparation of phthalocyanin sensitized nano cobalt dioxide powder |
| CN100404127C (en) * | 2006-06-23 | 2008-07-23 | 华中科技大学 | Artificial anitibody type composite photocatalyst and its prepn. method |
| CN102079858B (en) * | 2010-12-23 | 2012-07-25 | 陕西科技大学 | Photodegradation rate-controllable polycarbonate material and preparation method thereof |
| CN102091643A (en) * | 2010-12-29 | 2011-06-15 | 湖南大学 | Nano composite photochemical catalyst and application thereof |
| CN108911019A (en) * | 2018-08-01 | 2018-11-30 | 湖南七纬科技有限公司 | A kind for the treatment of of dyeing/printing wastewaters and preparation method thereof |
| CN111905687A (en) * | 2019-05-08 | 2020-11-10 | 浙江理工大学 | Flexible carbon fiber cloth @ CoMnNi multi-hydroxide composite material and preparation method thereof |
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| CN1422176A (en) * | 2000-03-22 | 2003-06-04 | 塞缪尔·E·斯皮尔 | Photolytic and photocatalytic reaction enhancement device |
| JP2003334453A (en) * | 2002-02-18 | 2003-11-25 | It Co Ltd | Photocatalytic interior material |
| JP2004010682A (en) * | 2002-06-04 | 2004-01-15 | National Institute Of Advanced Industrial & Technology | Photocatalytic composite material for building material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1422176A (en) * | 2000-03-22 | 2003-06-04 | 塞缪尔·E·斯皮尔 | Photolytic and photocatalytic reaction enhancement device |
| JP2003334453A (en) * | 2002-02-18 | 2003-11-25 | It Co Ltd | Photocatalytic interior material |
| JP2004010682A (en) * | 2002-06-04 | 2004-01-15 | National Institute Of Advanced Industrial & Technology | Photocatalytic composite material for building material |
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