CN102139206B - Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate - Google Patents
Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate Download PDFInfo
- Publication number
- CN102139206B CN102139206B CN2011100220474A CN201110022047A CN102139206B CN 102139206 B CN102139206 B CN 102139206B CN 2011100220474 A CN2011100220474 A CN 2011100220474A CN 201110022047 A CN201110022047 A CN 201110022047A CN 102139206 B CN102139206 B CN 102139206B
- Authority
- CN
- China
- Prior art keywords
- solution
- preparation
- zinc
- semiconductor composite
- photochemical catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of semiconductor composite antibacterial photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate, and belongs to the technical field of the treatment of environmental pollution. The semiconductor composite antibacterial photocatalyst is prepared a uniform coprecipitation method which comprises the following steps of: preparing a mixed solution in the amount-of-substance ratio of titanium sulfate to urea to zinc ions of 1:10:0; continuously mixing the mixed solution; raising the temperature of a water bath to 60 DEG C; adding a surfactant (sodium dodecyl benzene sulfonate) into the mixed solution based on the concentration of 20mg/150ml; keeping a constant temperature for 0.5h; raising the temperature to 90-100 DEG C again; keeping the temperature for 3-6h; adding ammonia water into the solution to regulate to pH (potential of hydrogen) to be 6-8; washing and drying the obtained product; and forging the product at the temperature of 400-800 DEG C. The preparation method has the advantages of short process flow, simple equipment, simple and convenient operation, and low price of raw materials. The prepared semiconductor composite has the advantages of having good dispersibility, visible spectral response and low energy consumption, and is an environment-friendly antibacterial purification material.
Description
Technical field
The present invention is the preparation method of environmentally friendly semiconductor composite antibiosis photochemical catalyst, is specifically related to the preparation method of a kind of nitrating nanometer titanium dioxide and Zinc titanite photocatalyst, belongs to the environmental pollution treatment technology field.
Background technology
Since Fujishima and Honda since finding the photoelectrocatalysis decomposing hydrogen-production of water on the n-type semiconductor titanium dioxide single crystalline electrode, the multiphase photocatalysis technology has caused scientific worker's very big concern.The degerming of nano titanium oxide ability deodorization, decomposing pollutant, non-secondary pollution, degraded is fast, energy consumption is low, is a fast-developing in recent years new technology.But because pure titinium dioxide needs ultraviolet excitation, light induced electron and hole-recombination rate are higher, cause solar energy utilization rate low, and quantum efficiency is lower; Nano titanium oxide be prone to be reunited in addition, and heat resistance is relatively poor, is higher than 700 ℃ of crystal transfers, and crystal grain is obviously grown up, and normally is lower than 700 ℃ of products of preparation down as antiseptic, therefore to a great extent limit its commercial Application.The photocatalysis performance and the thermal stability that how effectively to utilize solar energy to improve titanium dioxide become one of focus of research, and present research shows: reducing size of microcrystal, doping, noble metal loading, semiconductor coupling etc. is effective modification approach.
Zinc oxide also is important multifunctional semiconductor material, has the energy gap close with titanium dioxide and can be with the position with staggered, and the two is compounded with anti-microbial property and the photocatalysis performance that helps improve material.Zinc titanate is a kind of composite oxides, often be used as microwave dielectric ceramic, high temperature desulfuration agent, dehydrogenation etc., but the research of its photocatalysis field seldom, the rarely seen report of Photocatalytic Performance Study of relevant titanium dioxide/zinc titanate.The zinc titanate preparation method mainly contains solid phase method, sol-gel process, direct precipitation method etc.The zinc titanate diameter of particle of solid phase method preparation is bigger, the component skewness; The zinc titanate diameter of particle of sol-gel process preparation is little, but cost is high, and mostly raw material is organic reagent, big for environment pollution; The direct precipitation method grain is through wider distribution, and is dispersed bad.Do not see at present the even coprecipitation preparation of urea of nitrating nanometer titanium dioxide/zinc titanate and the relevant report of antibiotic light catalytic purifying performance study thereof, this novel photocatalysis agent has important application prospects aspect environmental improvement.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of environmentally friendly semiconductor composite antibiosis photochemical catalyst, the i.e. preparation method of nitrating nanometer titanium dioxide and zinc titanate composite photo-catalyst.This method is to be precipitating reagent and nitrogenous source with urea; Adopt even coprecipitation; Nitrating nanometer titanium dioxide and the zinc titanate semiconductor compound photocatalyst preparing good dispersion, have visible light-responded and good antibiotic and light catalytic purifying performance can be widely used in fields such as coating, plastics, fiber, papermaking, rubber, cosmetics, antiseptic, sewage disposal, air cleaning.
Realize that technical scheme of the present invention is:
A kind of preparation method of semiconductor composite antibiosis photochemical catalyst is characterized in that, described semiconductor composite antibiosis photochemical catalyst is nitrating nanometer titanium dioxide and zinc titanate composite photo-catalyst, evenly coprecipitation preparation, and preparation process is followed successively by:
(1) prepares 0.1-1.0molL respectively
-1Titanium sulfate solution, 0.28-3.0molL
-1Aqueous solution of urea, contain zinc ion 0.01-0.5molL
-1Solution;
(2) with the titanium sulfate solution of being prepared, urea liquid, to contain zinc ion solution be titanium sulfate according to the ratio of amount of substance: urea: zinc ion=1: 10: 0.5 is mixed with mixed solution; Join in the three-neck flask that has the returned cold radiator cooler; Evenly stir; Water-bath is heated to 40-60 ℃, presses the 20mg/150ml mixed solution and adds surfactant neopelex, constant temperature 0.5h;
(3) constantly stirring progressively is warmed up to 90-100 ℃ down, and insulation 3-6h uses 0.5molL
-1Ammoniacal liquor regulator solution pH value obtains white precipitate to 6-8;
(4) deposition is used BaCl through suction filtration, washing in mother liquor
2Solution detects less than SO
4 2-Till.80 ℃ down behind the dry 2h, heat treatment 1-3h under 400-800 ℃ of temperature promptly obtains semiconductor composite antibiosis photochemical catalyst in the Muffle furnace.
Realize that optimal technical scheme of the present invention is:
A kind of preparation method of semiconductor composite antibiosis photochemical catalyst is characterized in that preparation process is followed successively by:
(1) prepares 0.1-0.5molL respectively
-1Titanium sulfate solution, 0.28-1.4molL
-1Aqueous solution of urea, contain zinc ion 0.05-0.25molL
-1Solution;
(2) with the titanium sulfate solution of being prepared, urea liquid, to contain zinc ion solution be titanium sulfate according to the ratio of amount of substance: urea: zinc ion=1: 10: 0.5 is mixed with mixed solution; Join in the three-neck flask that has the returned cold radiator cooler; Evenly stir; Water-bath is heated to 40-60 ℃, presses the 20mg/150ml mixed solution and adds surfactant neopelex, constant temperature 0.5h;
(3) constantly stirring progressively is warmed up to 90-100 ℃ down, and insulation 3-6h uses 0.5molL
-1Ammoniacal liquor regulator solution pH value obtains white precipitate to 6-8;
(4) deposition is used BaCl through suction filtration, washing in mother liquor
2Solution detects less than SO
4 2-Till.80 ℃ down behind the dry 2h, heat treatment 1-3h under 550-750 ℃ of temperature promptly obtains semiconductor composite antibiosis photochemical catalyst in the Muffle furnace.
Among the preparation method of semiconductor composite antibiosis photochemical catalyst of the present invention, the described aqueous solution that contains zinc ion solution for one or both preparations of employing zinc sulfate, zinc chloride, zinc nitrate, zinc oxide.The preferred aqueous solution that adopts the zinc sulfate preparation.
Among the preparation method of semiconductor composite antibiosis photochemical catalyst of the present invention, described step (3) is preferably and progressively is warmed up to 90-95 ℃ under the continuous stirring, and insulation 3-6h preferably is incubated 4-6h, uses 0.5molL
-1Ammoniacal liquor regulator solution pH value obtains white precipitate to 6-8.
The antibacterial action of prepared semiconductor composite antibiosis photochemical catalyst and light catalytic purifying activity are respectively through characterizing to the experiment of colibacillary inhibition zone with to the ultraviolet-visible light district degradation experiment of methyl orange solution.Experimentation is following:
(1) antibacterial experiment
Preparation beef extract-peptone-agar medium (beef extract 0.3g, peptone 1g, sodium chloride 0.5g, agar 2g, distilled water 100mL, pH 7.2～7.4,121 ℃ of autoclaving 30min.), in the superclean bench culture medium after sterilization is poured in the sterile petri dish, make it to cover whole culture dish bottom, evenly coat a certain amount of Escherichia coli bacteria liquid again, form the bacterium liquid film.Get 4mg semiconductor composite granule and pour dull and stereotyped (the about 3mm of diameter), parallel 5 parts gone up into.Between each sample center at a distance of more than the 25mm, with the culture dish periphery at a distance of more than the 15mm.Cultivate 24h down for 37 ℃, bacterial growth situation around the observation sample is measured inhibition zone.With the mean value of inhibition zone foundation as the evaluating material antibiotic property.
(2) photocatalytic degradation experiment
In the methyl orange solution of 50mL 10mg/L, add 20mg semiconductor composite granule, adjustment pH value of solution=3 after in the dark mixing, place 15 watts of fluorescent lamps or 8 watts of uviol lamp irradiations down, and light source is 10cm apart from the distance of reaction vessels.Constantly stir, timing sampling after the centrifugation, is got supernatant liquor, with the variation of spectrophotometric determination methyl orange solution concentration, according to methyl orange solution initial concentration c
0With t moment concentration c
t, utilize following formula to obtain the degradation rate η of different time methyl orange:
Semiconductor composite antibiosis photocatalyst structure characterizing method is: at the Cu target is that X-ray source, sweep speed are that the X-ray diffraction spectrogram that obtains on the x-ray diffractometer of 0.05 degree/second is confirmed crystalline phase, the estimation particle diameter; Through day island proper Tianjin UV-2550 ultraviolet-uisible spectrophotometer come the UV, visible light diffuse reflection absorption spectra of measuring samples, the energy gap (E of estimation sample
g).
Compared with prior art, the present invention has following advantage:
(1) through even coprecipitation nitrating and combined oxidation zinc in the preparation process of titanium dioxide, promptly in the generative process of titanium dioxide precursor, make zinc ion with zinc hydroxide or basic salt form deposition, in heat treatment process, generate the semiconductor composite granule.
(2) with urea be the nitrogenous source of precipitating reagent and doping, reaction condition is gentle, and the titanium dioxide precursor generates evenly, has improved the surface nature of titanium dioxide, good dispersion, and standing sedimentation is very fast, and suction filtration, washing are convenient to suitability for industrialized production easily.
(3) preparation technology's flow process is short, and equipment is simple, and is easy and simple to handle, and raw material is cheap and easy to get, and cost is low.
(4) the semiconductor composite granule of preparation has visible light-responded, good antibiotic and light catalytic purifying performance; Can effectively utilize sunshine and airborne oxygen; Energy consumption is low, is a kind of environment-friendly antibiosis scavenging material, has important practical value and wide application prospect.
Description of drawings
Fig. 1 is the XRD figure of the semiconductor compound photocatalyst of different heat treatment temperature;
Fig. 2 is the UV, visible light of nano titanium oxide, nitrating nanometer titanium dioxide and the semiconductor compound photocatalyst spectrogram that diffuses;
Fig. 3 is the inhibition zone photo (A: commercially available chemical pure titanium dioxide reagent of sample under the 650 degree heat treatments; B: nano titanium oxide; C: nitrating nanometer titanium dioxide; D: nitrating nanometer titanium dioxide and semiconductor compound photocatalyst);
Fig. 4 is the absorption curve of nitrating nanometer titanium dioxide and semiconductor compound photocatalyst photocatalytic degradation methyl orange solution;
Fig. 5 is the degradation rate curve of different system sample photocatalytic degradation methyl orange solutions under 15 watts of fluorescent lamps;
Fig. 6 is the degradation rate curve of different system sample photocatalytic degradation methyl orange solutions under 8 watts of uviol lamps.
The specific embodiment
Introduce embodiments of the invention below, but the present invention is not limited to embodiment.
In the soluble-salt of titanium, be precipitating reagent and doping nitrogen source with urea, be compound zinc source with zinc salt, through sluggish precipitation doping nitrogen and combined oxidation zinc in the preparation of titanium dioxide.To 0.1-0.5molL
-1Titanium sulfate solution in, be titanium sulfate according to the ratio of amount of substance: urea: zinc sulfate=be mixed with mixed solution 150mL at 1: 10: 0.5 places the three-neck flask that has the returned cold radiator cooler; Evenly stir; Add 20mg surfactant neopelex, water-bath is heated to 60 ℃, urea decomposition; Generate the titanium dioxide precursor, constant temperature 0.5h.Be warmed up to 90-100 ℃ then, make urea decomposition complete, pH value of solution slowly rises, carry out nitrogen mix compound with semiconductor, continue to stir be incubated 3-6h after, use 0.5molL
-1The slow regulator solution pH=6-8 of ammoniacal liquor.The white precipitate that obtains detects less than SO with BaCl2 solution in mother liquor through suction filtration, washing
4 2-Till.Behind the dry 2h, change 400-800 ℃ of following heat treatment 2h in the Muffle furnace under 80 ℃, obtain having Nano semiconductor composite granule good antibiotic and the light catalytic purifying activity.
The phase transition temperature of pure nano titanium oxide changes because of synthetic method is different, and anatase is 600～700 ℃ to the crystal transfer temperature of rutile.It is 95 ℃ that Fig. 1 is illustrated in bath temperature, and pH value of solution is adjusted to 7, the XRD figure of the following titanium dioxide that calcining heat is respectively 450 ℃, 550 ℃, 650 ℃ and 750 ℃ sample after compound with zinc oxide.On scheming, can find out that the angle of diffraction 2 θ are 25.3 ° an obvious diffraction peak is arranged, corresponding with (101) crystal face of JCPDS No.21-1272, the reference standard collection of illustrative plates is the anatase titanium dioxide of tetragonal crystal system.Along with the rising of temperature, there is very strong diffraction maximum in the diffraction maximum grow that narrows down to some extent when the angle of diffraction 2 θ are 35.4 °, corresponding with (311) crystal face of JCPDS No.39-0190, associated diffraction peak and cube ZnTiO
3Standard diagram consistent, the zinc titanate crystalline phase has appearred; The characteristic peak that does not have rutile titanium dioxide and zinc oxide shows that phase transition temperature improves, and hear resistance strengthens; Do not see nitrogen material impurity diffraction maximum yet, show nitrogen doping formation novel substance.By XRD halfwidth method (HFMW); The average grain diameter that estimates anatase titanium dioxide and zinc titanate crystal grain according to the Scherrer formula is about 10～40nm; And temperature raises; Crystallite dimension increases to some extent, but poor growth explains with zinc oxide to be that Heterogeneous Composite helps in wider temperature range, obtaining the little titanium dioxide semiconductor composite photo-catalyst of particle diameter mutually.
General pure titinium dioxide probably has more by force at the following ultraviolet region of 360nm and absorbs, and absorbs the byest force about 290nm, and visible region does not almost absorb, and light absorpting ability is stronger in the ultra-violet (UV) band for nano zinc oxide particles.Visible from the UV, visible light diffuse reflection spectrum of Fig. 2 semiconductor powder, improved the absorbing properties of the compound crystalline substance of nano titania behind the titanium dioxide combined oxidation zinc in the ultra-violet (UV) band.Because the position of valence band and conduction band is different in titanium dioxide and the zinc oxide band structure; Cause two kinds of semiconductors to form hetero-junctions and have narrower band gap; Make the light absorption of nano complex that certain red shift arranged; Have more by force with lower area about 420nm to absorb, absorption band broadens, the absorption spectrum that has improved.The energy gap theoretical value of anatase type titanium dioxide is 3.2ev, semi-conductive light absorption threshold value λ
gAnd the relation between the energy gap Eg is: λ
g(nm)=1240/E
g(ev), the energy gap that estimates titanium dioxide complex reduces to some extent, is approximately 2.95ev, thereby has improved the utilization ratio of solar energy.
A, B, C and D are respectively that nano titanium oxide, nitrating nanometer titanium dioxide and the semiconductor composite granule sample after heat treatment under 650 ℃ of temperature under commercially available chemical pure titanium dioxide reagent, the identical preparation condition is to colibacillary inhibition zone photo among Fig. 3; Average inhibition zone is respectively 0.4mm, 3.4mm, 4.6mm, 10.6mm, and antibacterial ability strengthens gradually.Wherein commercially available chemical pure titanium dioxide reagent does not almost have inhibition zone, and anti-microbial property is not obvious; And nano titanium oxide is little owing to particle diameter, and the surface can be high, strengthened antibacterial activity effectively; Nitrogen mixes and causes the titanium dioxide distortion of lattice, and there is defective in the composite granule surface, and light induced electron-hole-recombination rate descends, and has improved the titanium dioxide valence band location, and antibacterial activity strengthens; Not only brought into play the antibacterial action of zinc oxide self behind the combined oxidation zinc, and improved spectral response, excited wave band to expand to visible light, it can be with narrow down, significantly improved the anti-microbial property of semiconductor complex from ultraviolet light.
The ultraviolet-visible absorption curve of semiconductor composite nano powder photocatalytic degradation methyl orange solution when Fig. 4 is pH=3.Visible by figure, methyl orange solution maximum absorption band wavelength is 505nm, and 2 hours methyl orange solution photocatalytic degradations to 10mg/L of semiconductor composite granule are tending towards complete.Because photocatalytic degradation methyl orange needs H
+Participation, along with the carrying out of degradation process, H+ reduces gradually, the structure of methyl orange also can partly change, being reflected on the ultraviolet-visible absorption curve is exactly the blue shift of absorption peak.
Fig. 5,6 is illustrated in the prepared sample of titanium dioxide nitrating and compound front and back and compound Different Zinc Source thereof and compares in the performance of 15 watts of fluorescent lamps and 8 watts of uviol lamp photocatalytic degradation 10mg/L methyl orange solutions respectively; Semiconductor composite granule (1), (2), (3), the compound zinc source category difference of (4) expression see embodiment 2 for details.The result shows: semiconductor composite granule sample degraded obvious ratio nano titanium dioxide of methyl orange speed and nitrating nanometer titanium dioxide want fast.The degradation rate of following 3 hours semiconductor composite granules of 15 watts of fluorescent lamps reaches 60%-67%, and the degradation rate of nano titanium oxide and nitrating nanometer titanium dioxide has only 42% and 55% respectively; Degradation rate under 8 watts of uviol lamps is all high than the degradation rate under 15 watts of fluorescent lamps; Wherein 3 hours degradation rates of nano titanium oxide and nitrating nanometer titanium dioxide reach 60% and 70%; 3 hours methyl orange of nitrogen-doped nanometer titanium dioxide semiconductor complex is degraded to colourless basically, and degradation capability significantly improves behind the combined oxidation zinc.Therefore improved the photocatalysis efficiency of the ultraviolet-visible wave band of sample behind nitrating and the combined oxidation zinc.
In order to check variety classes zinc source to the composite granule Effect on Performance, except that getting zinc source category difference, the fixation reaction temperature is for being 95 ℃, and the pH value of solution value is 7, and calcining heat is 650 ℃, and other reaction condition is all identical with embodiment 1 condition.Fig. 5,6 is illustrated in and adds the prepared sample in variety classes zinc source in the precursor generative process of titanium dioxide respectively in the performance of 15 watts of fluorescent lamps and 8 watts of uviol lamp photocatalytic degradation 10mg/L methyl orange solutions relatively, and nitrating titanium dioxide/zinc titanate semiconductor complex (1), (2), (3), (4) represent that respectively compound zinc source is analytically pure zinc oxide, zinc nitrate, zinc chloride, zinc sulfate.The result shows that the prepared semiconductor composite granule photocatalytic speed of Different Zinc Source just is followed successively by: zinc sulfate＞zinc chloride＞zinc nitrate＞zinc oxide, but difference is not too big; Can know through photocatalytic degradation methyl orange experiment that the sample of the independent zinc salt preparation of mixing ratio of two kinds of zinc salts is antibiotic and will get well with photocatalysis performance.
Embodiment 3
In order to check of the influence of mixed solution concentration to the semiconductor complex performance; Change the concentration of titanium sulfate, urea, zinc solution, fixation reaction water-bath temperature is 95 ℃, and pH value of solution is adjusted to 7; Calcining heat is fixed on 650 ℃, and other experiment conditions are according to embodiment 1 method.The result shows, when titanium sulfate concentration at 0.1-1.0molL
-1, urea concentration is 0.28-3.0molL
-1, zinc solution concentration is 0.01-0.5molL
-1The time, it is less to obtain particle diameter, the anatase titania of pattern homogeneous and zinc titanate semiconductor composite granule, and have good antibiotic and photocatalytic degradation activity.The experiment optimum condition is titanium sulfate concentration 0.1-0.5molL
-1, urea concentration is 0.28-1.4molL
-1, zinc solution concentration is 0.05-0.25molL
-1
Embodiment 4
In order to check the pH value to the composite granule Effect on Performance, change the pH value of solution value, the fixation reaction temperature retention time is 6h, and calcining heat is fixed on 450 ℃, and other reaction condition is all identical with embodiment 1 condition.The result shows, when pH value of solution＞9, antibacterial effect is not good enough, but photocatalytic degradation methyl orange efficient is high; When pH＜5, Escherichia coli are had strong antibacterial action, but degraded methyl orange efficient is not as good as alkali condition; When pH was 6-8, the composite granule antibacterial effect was obvious, and photocatalytic degradation methyl orange efficient is better.
Embodiment 5
In order to check bath temperature to the composite granule Effect on Performance, change the bath temperature of experimentation, the fixation reaction temperature retention time is 6h, and the pH value of solution value is adjusted to 7, and calcining heat is 550 ℃, and other reaction condition is all identical with embodiment 1.The result shows, water bath heat preservation obtains that productive rate is higher, the semiconductor composite granule of pattern homogeneous in the time of 90-100 ℃, antibiotic preferable with photocatalysis performance; When holding temperature during less than 80 ℃, the powder productive rate is low, and photocatalytic activity is relatively poor.Optimum temperature is 90-95 ℃
In order to check the water bath heat preservation time to the composite granule Effect on Performance, except that the temperature retention time difference, fixedly titanium sulfate solution is 0.25molL
-1, be titanium sulfate according to the ratio of amount of substance: urea: zinc sulfate=be mixed with mixed solution 150ml at 1: 10: 0.5, bath temperature is 95 ℃, and the pH value of solution value is adjusted to 6.5, and calcining heat is 400 ℃, and other reaction condition is all identical with embodiment 1 condition.The result shows that water bath heat preservation time length directly influences the productive rate height, and when being incubated more than 4h, the powder productive rate is high, and less than 3h, productive rate is lower; The water-bath time is little to the crystal formation influence, and powder is mainly Detitanium-ore-type under this condition, better anti-microbial property is arranged, but photocatalytic activity is relatively poor.Testing best temperature retention time is 4-6h.
Embodiment 7
In order to check heat treatment temperature to the composite granule Effect on Performance, change the sample heat treatment temperature, the fixation reaction temperature retention time is 6h, and the pH value of solution value is adjusted to 7, and other reaction condition is all identical with embodiment 1.The result shows, when calcining heat during less than 300 ℃, obtains the amorphous semiconductor composite granule, and is antibiotic bad with photocatalysis performance; When heat treatment temperature is 550-750 ℃, obtain anatase titanium dioxide/zinc titanate composite granule, antibiotic better with photocatalysis performance; When heat treatment temperature greater than 800 ℃, antibiotic and photocatalytic degradation effect descend.
In order to check heat treatment time to the composite granule Effect on Performance, except that the heat treatment time difference, fixedly bath temperature is 95 ℃, and the pH value of solution value is 7, and calcining heat is 500 ℃, and other reaction condition is all identical with embodiment 1.The result shows, and is when sample heat treatment time in Muffle furnace obtains amorphous and small amount of anatase type semiconductor composite granule less than 1h, antibiotic bad with the photocatalytic degradation performance; When heat treatment time greater than 4h, antibacterial effect not obvious with photocatalysis performance better; When heat treatment time obtains the composite granule of anatase phase between 1-3h, antibiotic better active with photocatalytic degradation.
Embodiment 9
Through above-mentioned instance 1-8, obtain the optimum experimental condition that the present invention prepares the semiconductor composite granule and be: to 0.1-0.5molL
-1Titanium sulfate solution in, be titanium sulfate according to the ratio of amount of substance: urea: zinc sulfate=be mixed with mixed solution 150mL at 1: 10: 0.5 places the three-neck flask that has the returned cold radiator cooler; Evenly stir; Add 20mg surfactant neopelex, water-bath is heated to 60 ℃, urea decomposition; Generate the titanium dioxide precursor, constant temperature 0.5h.Be warmed up to 90-100 ℃ then, urea is decomposed fully, pH value of solution slowly rises, and carries out nitrogen doping and zinc hydroxide and coats, and continuation is used 0.5molL after stirring insulation 4-6h
-1The slow regulator solution pH=6-8 of ammoniacal liquor.The white precipitate that obtains is used BaCl through suction filtration, washing in mother liquor
2Solution detects less than SO
4 2-Till.80 ℃ change in the Muffle furnace behind the dry 2h down, and 400～800 ℃ of following heat treatment 1-3h obtain having Nano semiconductor composite granule good antibiotic and the light catalytic purifying activity.
Claims (6)
1. the preparation method of a semiconductor composite antibiosis photochemical catalyst is characterized in that, described semiconductor composite antibiosis photochemical catalyst is nitrating nanometer titanium dioxide and Zinc titanite photocatalyst, evenly coprecipitation preparation, and preparation process is followed successively by:
(1) prepares 0.1-1.0molL respectively
-1Titanium sulfate solution, 0.28-3.0molL
-1Aqueous solution of urea, contain zinc ion 0.01-0.5molL
-1Solution;
(2) with the titanium sulfate solution of being prepared, urea liquid, to contain zinc ion solution be titanium sulfate according to the ratio of amount of substance: urea: zinc ion=1: 10: 0.5 is mixed with mixed solution; Join in the three-neck flask that has the returned cold radiator cooler; Evenly stir; Water-bath is heated to 40-60 ℃, presses the 20mg/150ml mixed solution and adds surfactant neopelex, constant temperature 0.5h;
(3) constantly stirring progressively is warmed up to 90-100 ℃ down, and insulation 3-6h uses 0.5molL
-1Ammoniacal liquor regulator solution pH value obtains white precipitate to 6-8;
(4) deposition is used BaCl through suction filtration, washing in mother liquor
2Solution detects less than SO
4 2-Till, 80 ℃ down behind the dry 2h, heat treatment 1-3h under 400-800 ℃ of temperature promptly obtains semiconductor composite antibiosis photochemical catalyst in the Muffle furnace.
2. the preparation method of semiconductor composite antibiosis photochemical catalyst according to claim 1 is characterized in that preparation process is followed successively by:
(1) prepares 0.1-0.5molL respectively
-1Titanium sulfate solution, 0.28-1.4molL
-1Aqueous solution of urea, contain zinc ion 0.05-0.25molL
-1Solution;
(2) with the titanium sulfate solution of being prepared, urea liquid, to contain zinc ion solution be titanium sulfate according to the ratio of amount of substance: urea: zinc ion=1: 10: 0.5 is mixed with mixed solution; Join in the three-neck flask that has the returned cold radiator cooler; Evenly stir; Water-bath is heated to 40-60 ℃, presses the 20mg/150ml mixed solution and adds surfactant neopelex, constant temperature 0.5h;
(3) constantly stirring progressively is warmed up to 90-100 ℃ down, and insulation 3-6h uses 0.5molL
-1Ammoniacal liquor regulator solution pH value obtains white precipitate to 6-8;
(4) deposition is used BaCl through suction filtration, washing in mother liquor
2Solution detects less than SO
4 2-Till, 80 ℃ down behind the dry 2h, heat treatment 1-3h under 550-750 ℃ of temperature promptly obtains semiconductor composite antibiosis photochemical catalyst in the Muffle furnace.
3. the preparation method of semiconductor composite antibiosis photochemical catalyst according to claim 1 and 2 is characterized in that, the described aqueous solution that contains zinc ion solution for one or both preparations of employing zinc sulfate, zinc chloride, zinc nitrate, zinc oxide.
4. the preparation method of semiconductor composite antibiosis photochemical catalyst according to claim 3 is characterized in that, the described zinc ion solution that contains is for adopting the aqueous solution of zinc sulfate preparation.
5. the preparation method of semiconductor composite antibiosis photochemical catalyst according to claim 1 and 2 is characterized in that, described step (3) progressively is warmed up to 90-95 ℃ for constantly stirring down, and insulation 3-6h uses 0.5molL
-1Ammoniacal liquor regulator solution pH value obtains white precipitate to 6-8.
6. the preparation method of semiconductor composite antibiosis photochemical catalyst according to claim 1 and 2 is characterized in that, in the described step (3), and insulation 4-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100220474A CN102139206B (en) | 2011-01-20 | 2011-01-20 | Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100220474A CN102139206B (en) | 2011-01-20 | 2011-01-20 | Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102139206A CN102139206A (en) | 2011-08-03 |
| CN102139206B true CN102139206B (en) | 2012-11-07 |
Family
ID=44407138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100220474A Expired - Fee Related CN102139206B (en) | 2011-01-20 | 2011-01-20 | Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102139206B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012151407A1 (en) | 2011-05-04 | 2012-11-08 | Averett Stewart Benson | Titanium dioxide photocatalytic compositions and uses thereof |
| CN103316655B (en) * | 2013-06-25 | 2015-04-15 | 桂林理工大学 | Visible-light-responded photocatalyst BaZn2Ti4O11 and preparation method thereof |
| CN103316656A (en) * | 2013-06-25 | 2013-09-25 | 桂林理工大学 | Visible-light-responded photocatalyst Ba4ZnTi11O27 and preparation method thereof |
| CN103406135B (en) * | 2013-08-07 | 2014-12-24 | 江苏大学 | Preparation method for synthesizing N-TiO2@WSe2 photocatalyst through sol-gel method and application of N-TiO2@WSe2 photocatalyst |
| CN107098381B (en) * | 2017-05-16 | 2018-09-28 | 哈尔滨商业大学 | The preparation method of the zinc titanate catalysis material of special appearance |
| CN107349942A (en) * | 2017-07-26 | 2017-11-17 | 深圳市威勒科技股份有限公司 | A kind of fluorine tungsten codope photocatalyst and preparation method thereof |
| CN108554436B (en) * | 2018-05-14 | 2021-04-06 | 青岛科技大学 | Assembling of N-Ag-TiO2Application of-ZnO nano cage in methyl yellow degradation reaction under visible light |
| CN111558388B (en) * | 2020-03-09 | 2023-03-28 | 上海电力大学 | Zn/N double-doped titanium monoxide material and preparation method thereof |
| CN111468096B (en) * | 2020-04-09 | 2022-05-31 | 浙江工业大学 | Zn2TiO4/TiO2Composite material and preparation method and application thereof |
| CN113336264B (en) * | 2021-05-11 | 2023-08-29 | 苏州锦艺新材料科技有限公司 | Preparation method of zinc orthotitanate powder |
| CN115449437B (en) * | 2022-09-06 | 2024-01-19 | 深圳乙奇生物科技有限公司 | Concentrated nano photolysis underwear laundry detergent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005087880A (en) * | 2003-09-17 | 2005-04-07 | Toto Ltd | Photocatalyst composite material, photocatalyst particle, and coating material |
| JP2005138008A (en) * | 2003-11-05 | 2005-06-02 | National Institute For Materials Science | Visible light responding type titanium oxide composite photocatalyst and its manufacturing method |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN101301619A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Method for preparing high efficiency metallic, non-metallic ion co-doped nano-TiO2 visible-light responsive photocatalyst |
| CN101722015A (en) * | 2008-10-10 | 2010-06-09 | 北京化工大学 | Method for preparing super-strong acidified doped nano-TiO2 photocatalyst |
-
2011
- 2011-01-20 CN CN2011100220474A patent/CN102139206B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005087880A (en) * | 2003-09-17 | 2005-04-07 | Toto Ltd | Photocatalyst composite material, photocatalyst particle, and coating material |
| JP2005138008A (en) * | 2003-11-05 | 2005-06-02 | National Institute For Materials Science | Visible light responding type titanium oxide composite photocatalyst and its manufacturing method |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN101301619A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Method for preparing high efficiency metallic, non-metallic ion co-doped nano-TiO2 visible-light responsive photocatalyst |
| CN101722015A (en) * | 2008-10-10 | 2010-06-09 | 北京化工大学 | Method for preparing super-strong acidified doped nano-TiO2 photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| 徐瑛 等."二氧化钛复合微粉的抗菌性能研究".《功能材料》.2002,第33卷(第6期),第682-686页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102139206A (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102139206B (en) | Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate | |
| CN101254463B (en) | Synthetic method of visible light catalyst Bi2MoO6 | |
| CN101792117B (en) | Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder | |
| CN102974375B (en) | Multifunctional composite material with heterostructure and preparation method thereof | |
| CN104190458B (en) | A kind of low temperature preparation technology of dual element modified nano-titanium dioxide colloidal sol | |
| CN106391086A (en) | Preparation method of C3N4/SiO2 heterojunction photocatalyst | |
| CN108940332B (en) | High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst | |
| CN111604053A (en) | Ternary hydrotalcite photocatalyst and preparation method and application thereof | |
| CN102600865B (en) | Photocatalyst for degrading organic dye waste water pollutants and preparation method thereof | |
| CN110721698B (en) | Bismuth vanadate/copper vanadate composite photocatalyst and preparation method and application thereof | |
| CN101716503B (en) | Visible light catalyst BiNbO4, preparation method thereof and application thereof | |
| CN105854870B (en) | A kind of Bi2WO6Stepped recess micron ball photocatalyst and preparation method thereof | |
| CN102513090A (en) | Carbon-doped semiconductor oxide with visible light catalytic activity, and preparation method thereof | |
| CN105289579A (en) | Nanometer flake cerium-doped bismuth molybdate catalyst, as well as preparation method and application thereof | |
| CN102580720B (en) | Visible light response nano zinc oxide-bismuth oxide composite photocatalyst and preparation method thereof | |
| CN110038552A (en) | With visible light-responded bismuth stannate photochemical catalyst and preparation method thereof | |
| CN105056986A (en) | Method for preparing flake shaped bismuth oxide nitrate hydroxide photocatalyst and catalyst application | |
| CN104549222A (en) | Preparation method and application of visible-light-induced photocatalyst chromium chromate | |
| CN100453165C (en) | Nanometer titanium dioxide/selenium dioxide composition and its prepn. method | |
| CN105032440A (en) | Zinc-copper-aluminum-erbium composite oxide as well as preparation method and application thereof | |
| CN1775349B (en) | Wolfram oxide modified visible light activity nano titanium oxide photocatalyst and its method | |
| CN103787413B (en) | Hexagon hollow tubulose Bi 2o (OH) 2sO 4the preparation method of photochemical catalyst and application | |
| CN103861580B (en) | The preparation method of a kind of nanometer of spherical bismuth oxide photocatalyst and application | |
| CN107519852A (en) | A kind of method that normal temperature prepares efficient nano titanium dioxide optical catalyst | |
| Xue et al. | Construction of Cu 2+-doped CeO 2 nanocrystals hierarchical hollow structure and its enhanced photocatalytic performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121107 Termination date: 20140120 |