CN101721985A - Method for preparing sulfur and nitrogen co-doped titanium dioxide with visible light catalytic activity - Google Patents
Method for preparing sulfur and nitrogen co-doped titanium dioxide with visible light catalytic activity Download PDFInfo
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Abstract
The invention provides a method for preparing sulfur and nitrogen co-doped titanium dioxide with visible light catalytic activity, which adopts a sol-gel method and comprises the following steps: hydrolyzing titanium ester and introducing sulfur and nitrogen sources to obtain a titanium dioxide sol, wherein the sulfur and nitrogen sources are from thiourea solution; in a sol system, dropwise adding 1 to 5 percent saturated aqueous solution of thiourea to perform the hydrolysis reaction to obtain the sol; then performing aging and volatilizing a diluent to obtain a titanium dioxide gel; drying the titanium dioxide gel and grinding into powders; performing heat treatment on the solid powder; and calcinating to obtain sulfur and nitrogen co-doped titanium dioxide nano powder. In the method, the thiourea is used as the raw materials of the nitrogen and sulfur sources, the sulfur and the nitrogen are simultaneously introduced in the process of the hydrolysis reaction of the sol to achieve synergistic effect and improve the reaction efficiency, raw material consumption is less, the process is simplified, the absorption range of visible light is effectively improved, the wavelength of the visible light is expanded to about 650nm, and the sulfur and nitrogen co-doped titanium dioxide has obvious visible light activity in the photocatalytic degradation reaction of organic pollutant molecules.
Description
Technical field:
The present invention relates to a kind of titanium dioxide (TiO
2) preparation method of photochemical catalyst, particularly have the preparation method of the sulfur and nitrogen co-doped titanium dioxide of visible light catalysis activity.
Background technology:
Problem of environmental pollution has also become a focal issue that threatens human survival, and use the photocatalysis technology of semiconductor light-catalyst to solve environmental pollution, because it has high photochemistry conversion efficiency, high stability and to the non-selectivity of all kinds of organic pollutions, particularly the unique advantage that can directly utilize solar energy to carry out photochemical transformation is subjected to scientist's great attention.The successful application and the various organic pollutions of elimination of semiconductor light-catalyst at present, as: alkane, fuel, alkene, fatty alcohol, aliphatic carboxylic acid, simple aromatic compound and pesticide residue etc.In the light-catalysed research of environment, being regarded as best semi-conducting material is titanium dioxide (TiO
2) photochemical catalyst, but owing to its forbidden band broad (Eg=3.2eV), can only be excited less than the light in the 387.5nm interval by the sunshine medium wavelength, and this interval luminous energy only accounts for about 4% of solar energy, so TiO
2Photochemical catalyst is to the visible light difference in response, is greatly limited directly utilizing solar energy to carry out using aspect the photocatalysis environmental pollution improvement.
People such as calendar year 2001 Japan scientist R.Asahi have reported nitrogen doping type titanium dioxide (TiO first on Science
2-xN
x) having visible light catalysis activity, its preparation method is that titanium dioxide anatase powder 600 ℃ of sintering in NH3/Ar atmosphere were obtained target sample in 3 hours.In addition about the anion doped many in addition reports of titanium dioxide, comprising doping (Sakthivel, the S. of carbon; Kisch, H.Angew Chem.Int.Ed.2003,42,4908.), the doping of fluorine (J.C.Yu, J.Yu, W.Ho, Z.Jiang, L.Zhang, Chem.Mater.2002,14,3808.), the doping (T.Umebayashi of sulphur, T.Yamaki, H.Itoh, K.Asai, Appl.Phys.Lett.2002,82,454.).But below all belong to the doping of single ion, simultaneously, above-mentioned anionic doping method often needs methods such as ion injection, metal organic chemical vapor deposition and injection pyrolytic, requires high to experimental facilities and reaction condition.Sol-gal process is owing to characteristics such as the particle purity height of its preparation, good dispersion, narrow diameter distribution are widely applied to the preparation nano-powder.
Chinese patent CN1562461A, disclosing name is called: the nano oxidized titanium catalyst and the synthetic method of sulphur and the codope of nitrogen anion, this patent adopts hydro-thermal to synthesize and the ammonia nitrogenize prepares the method for sulfur and nitrogen co-doped titanium dioxide powder, owing to adopted dangerous and the big NH of contaminative
3, have the safety issue of technology; It is a kind of that Chinese patent CN1850618A (publication number) proposes: " having the nitrogen of long-wave absorbing function and sulfur two-component doped nano titanium dioxide and preparation method thereof ", this method adopts sol-gel process, by in the titanate esters hydrolytic process, introduce nitrogenous source and sulphur source and prepare sulfur and nitrogen co-doped titanium dioxide, wherein nitrogenous source is from urea, and the sulphur source is from thiocyanation amine.Add sulphur source urea and nitrogenous source thiocyanation amine in the ethanolic solution of butyl titanate respectively according to a certain percentage, hydrolysis, drying make the sulfur and nitrogen co-doped titanium dioxide powder, this method sulphur source, nitrogenous source are from different compounds, raw material type is many, increased the complexity of technology, and only by sulphur source and nitrogenous source are added in the colloidal sol, sulphur nitrogen element is doped in titanium dioxide surface by absorption, doping elements easily runs off, the sulphur nitrogen content is on the low side, and (sulfur content is at 0.6%-1.12%, nitrogen content is at 0.65%-1.62%), make to absorb band edge expansion limited (preferably reaching about 600nm).
Summary of the invention
The invention provides a kind of method for preparing sulfur and nitrogen co-doped titanium dioxide.This method can improve the doping of nitrogen and sulphur, and sulphur nitrogen can be mixed in titanium dioxide crystal lattice, make itself and Ti element that orbital hybridization take place, thereby further reduce the energy gap of titanium dioxide, improve the TiO 2 visible light photocatalytic activity, and raw material is simple, and hydrolysis process is simplified.
The preparation method of the sulfur and nitrogen co-doped titanium dioxide that the present invention proposes, adopt sol-gel process, comprise the titanate esters hydrolysis, and introduce sulphur and nitrogenous source obtains TiO 2 sol, wherein sulphur source and nitrogenous source are from a kind of raw material--thiourea solution, with the colloidal sol weight percent meter, titanate esters with 1-15%, the hydrolyst of 1-5%, the diluent of 75-95% stirs, drip the thiocarbamide saturated aqueous solution of 1-5%, the reaction that is hydrolyzed obtained colloidal sol in 1-3 hour, then through ageing, and the volatilization diluent obtains titania gel, grind into powder after super-dry is heat-treated pressed powder again, and calcining obtains the sulfur and nitrogen co-doped titanium dioxide nano-powder under the air atmosphere of 450-650 ℃ of temperature.
In the said method, be conventional condition to the dry run of titania gel, temperature is controlled at 30-150 ℃, in preferred 50-100 ℃ the air atmosphere dry 1-3 hour, obtains pressed powder after the grinding;
The present invention adopts thiourea solution as sulphur source and nitrogenous source, and in the sol-hydrolysis course of reaction, sulphur and nitrogen are introduced simultaneously, and cooperative effect improves reaction efficiency, and consumption of raw materials is few, and the preferred dripping quantity of thiourea solution is the 2-3% of sol system by weight percentage.
The phthalate ester that the present invention adopts is known hydrolyzable butyl titanate, metatitanic acid n-propyl, isopropyl titanate or tetraethyl titanate.
The hydrolyst that the present invention adopts is acetic acid, hydrochloric acid, nitric acid or the sulfuric acid of using always; Diluent is absolute ethyl alcohol, absolute methanol, anhydrous isopropyl alcohol or polyvinyl alcohol.
In the method for the present invention, the pressed powder process of thermal treatment is temperature-rise period and temperature-fall period gradually preferably, and the thiocarbamide that is adsorbed on the titanium dioxide is decomposed gradually, and sulphur nitrogen mixes titanium dioxide crystal lattice, at room temperature, programming rate is 1～20 ℃/minute, rises to 450-650 ℃, and temperature retention time is 0.5～5 hour, cooling gradually then, cooling rate is 15-40 ℃/minute, reduces to room temperature, obtains the titanium dioxide optical catalyst of codope.
Effect of the present invention: the present invention uses a kind of raw material thiocarbamide as nitrogenous source and sulphur source, in the sol-hydrolysis course of reaction, sulphur and nitrogen are introduced simultaneously, and cooperative effect improves reaction efficiency, consumption of raw materials is few, simplify technology, and obviously improved the doping content of sulphur and nitrogen, the content of sulphur reaches 2.42%, the content of nitrogen reaches 2.79%, and then has improved the TiO 2 visible light photocatalytic activity; By adopting suitable Technology for Heating Processing that thiocarbamide is decomposed, sulphur nitrogen element not only is adsorbed on titanium dioxide surface, and with the Ti element orbital hybridization has taken place, be doped into titanium dioxide crystal lattice, the synergy of sulphur and nitrogen, make the band gap of titanium dioxide narrow down, effectively improved the scope of visible absorption, visible wavelength is expanded to the 650nm, make titanium dioxide have absorbability to visible light, improved the efficient of degradable organic pollutant, the sulfur and nitrogen co-doped titanium dioxide that makes with the inventive method carries out the photocatalysis test, organic pollution such as degraded penicillin etc. shows good photocatalytic activity under excited by visible light, has effectively improved the direct utilization to the sunshine energy; The powder hard aggregation content that the inventive method is synthesized is few, can keep very high sintering activity; The easy uniform many group members powder of synthetic ingredient, cost is low, easy to operate.
The sulfur and nitrogen co-doped titanium dioxide that method of the present invention makes carries out the photocatalysis test, be in a Photoreactor, use the 40W fluorescent lamp as light source, dominant wavelength is 465nm, and light source is 15-20cm apart from the solution distance, magnetic agitation, catalyst amount is 1.0g/L, and the initial COD of degraded is the penicillin solution of 300mg/L in 2 hours, monitors the variation of solution C OD with HACH COD tester, under radiation of visible light 2 hours, the degradation rate of penicillin solution reached 50-70%.
Description of drawings:
Fig. 1 does not mix and the X ray diffracting spectrum of sulfur and nitrogen co-doped titanium dioxide powder of the present invention, (shows among the figure that crystalline phase is the anatase phase.) a is the sulfur and nitrogen co-doped nano titanium oxide curve of the present invention among the figure, b is unadulterated titanium dioxide curve.
Fig. 2 does not mix and the XPS of sulfur and nitrogen co-doped titanium dioxide of the present invention composes entirely, and a is the sulfur and nitrogen co-doped nano titanium oxide curve of the present invention among the figure, and b is unadulterated titanium dioxide curve
The N1s spectrum of Fig. 3 sulfur and nitrogen co-doped titanium dioxide of the present invention
The S2p spectrum of Fig. 4 sulfur and nitrogen co-doped titanium dioxide of the present invention
Fig. 5 sulfur and nitrogen co-doped titanium dioxide powder of the present invention and the uv-visible absorption spectra of doped titanium dioxide powder not, abscissa is a wavelength, ordinate is an absorptance.A is the sulfur and nitrogen co-doped nano titanium oxide of the present invention among the figure, and b is unadulterated titanium dioxide curve.
The specific embodiment:
Embodiment 1: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide: the raw material proportioning (percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 88%, acetic acid (analyzing pure) 5%, thiocarbamide (analyzing pure) 2%, according to the above ratio with butyl titanate, absolute ethyl alcohol, acetic acid places reaction bulb, under 15 ℃ temperature, stirred 30 minutes, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 450 ℃ with the speed of 2 ℃/min, 450 ℃ of calcinings 2 hours down, reduce to room temperature get final product target product, color sample is a glassy yellow.Wherein sulfur content is 2.42%, and nitrogen content is 2.79%.Adopting above method is anatase (Fig. 1) mutually with the titanium dioxide powder that prescription makes, and XPS tests demonstration, and sulphur atom and nitrogen-atoms are doped to (Fig. 3, Fig. 4) in the titanium dioxide lattice.The sulfur and nitrogen co-doped titanium dioxide powder that makes is carried out the uv-visible absorption spectra analysis, and the later powder ABSORPTION EDGE of mixing has obvious red shift phenomenon (Fig. 3).The sulfur and nitrogen co-doped titanium dioxide powder that use makes carries out light-catalyzed reaction in the self-control reactor, the degradation rate of penicillin solution reaches 70% after 2 hours.
Comparative Examples 1: Prepared by Sol Gel Method is not titania-doped, raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 90%, acetic acid (analyzing pure) 5% is according to the above ratio with butyl titanate, absolute ethyl alcohol, acetic acid places reaction bulb, and reaction is 2 hours under 15 ℃ temperature, obtains TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 450 ℃, calcined 2 hours, reduce to room temperature with the speed of 2 ℃/min, get final product target product, color sample is a pure white.The titanium dioxide powder that makes is anatase phase (Fig. 1), and XPS tests demonstration, does not have element sulphur or nitrogen element (Fig. 2 in the titanium dioxide lattice.The not doped titanium dioxide powder that makes is carried out the uv-visible absorption spectra analysis, and the later powder that mixes only has absorption (Fig. 5) at ultraviolet region.The not doped titanium dioxide powder that use makes carries out light-catalyzed reaction in the self-control reactor, the degradation rate of penicillin solution reaches 15% after 2 hours.
Embodiment 2: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide, raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 88%, acetic acid (analyzing pure) 5%, thiocarbamide (analyzing pure) 1%, according to the above ratio with butyl titanate, absolute ethyl alcohol, acetic acid places reaction bulb, stirs 30 minutes under 15 ℃ temperature, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 450 ℃, calcined 2 hours, reduce to room temperature with the speed of 2 ℃/min, get final product the target product sample, color sample is a khaki.Wherein sulfur content is 2.22%, and nitrogen content is 2.51%.The sulfur and nitrogen co-doped titanium dioxide powder that use makes carries out light-catalyzed reaction in the self-control reactor, the degradation rate of penicillin solution reaches 51% after 2 hours.
Embodiment 3: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide, raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 88%, acetic acid (analyzing pure) 5%, thiocarbamide (analyzing pure) 3%, according to the above ratio with butyl titanate, absolute ethyl alcohol, acetic acid places reaction bulb, stirs 30 minutes under 15 ℃ temperature, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 450 ℃, calcined 2 hours, reduce to room temperature with the speed of 2 ℃/min, get final product target product.Wherein sulfur content is 2.61%, and nitrogen content is 2.96%.Carry out light-catalyzed reaction with the sulfur and nitrogen co-doped titanium dioxide powder that makes, the degradation rate of penicillin solution reaches 71% after 2 hours.
Embodiment 4: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide, raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 88%, acetic acid (analyzing pure) 5%, thiocarbamide (analyzing pure) 5%, according to the above ratio with butyl titanate, absolute ethyl alcohol, acetic acid places reaction bulb, stirs 30 minutes under 15 ℃ temperature, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 450 ℃, calcined 2 hours, reduce to room temperature with the speed of 2 ℃/min, get final product target product.The sulfur and nitrogen co-doped titanium dioxide powder that use makes carries out light-catalyzed reaction, and the degradation rate of penicillin solution reaches 45% after 2 hours.
Embodiment 5: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide, raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 91%, concentrated hydrochloric acid (36.5%) 2%, thiocarbamide (analyzing pure) 2%, according to the above ratio with butyl titanate, absolute ethyl alcohol, concentrated hydrochloric acid places reaction bulb, stirs 30 minutes under 15 ℃ temperature, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 450 ℃, calcined 2 hours, reduce to room temperature with the speed of 2 ℃/min, get final product target product.The sulfur and nitrogen co-doped titanium dioxide powder that use makes carries out light-catalyzed reaction, and the degradation rate of penicillin solution reaches 55% after 2 hours.
Embodiment 6: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide, raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): titanium propanolate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 92%, nitric acid (analyzing pure) 1%, thiocarbamide (analyzing pure) 2%, according to the above ratio with titanium propanolate, absolute ethyl alcohol, nitric acid places reaction bulb, stirs 30 minutes under 15 ℃ temperature, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 450 ℃, calcined 2 hours, reduce to room temperature with the speed of 2 ℃/min, get final product target product.Carry out light-catalyzed reaction with the sulfur and nitrogen co-doped titanium dioxide powder that makes, the degradation rate of penicillin solution reaches 58% after 2 hours.
Embodiment 7: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide, raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 88%, acetic acid (analyzing pure) 5%, thiocarbamide (analyzing pure) 2%, according to the above ratio with butyl titanate, absolute ethyl alcohol, acetic acid places reaction bulb, stirs 30 minutes under 15 ℃ temperature, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding, at room temperature, be warming up to 550 ℃, calcined 2 hours, reduce to room temperature with the speed of 2 ℃/min, get final product the target product sample, color sample is a khaki.The sulfur and nitrogen co-doped titanium dioxide powder that use makes carries out light-catalyzed reaction in the self-control reactor, the degradation rate of penicillin solution reaches 55% after 2 hours.
Embodiment 8: the Prepared by Sol Gel Method sulfur and nitrogen co-doped titanium dioxide:
Raw material proportioning (the percentage by weight of synthesis of titanium dioxide colloidal sol, gross weight is 50 grams): butyl titanate (analyzing pure) 5%, absolute ethyl alcohol (analyzing pure) 88%, acetic acid (analyzing pure) 5%, thiocarbamide (analyzing pure) 2%, according to the above ratio with butyl titanate, absolute ethyl alcohol, acetic acid places reaction bulb, under 15 ℃ temperature, stirred 30 minutes, then thiourea solution is added in the reactant liquor, continue reaction 2 hours, obtain TiO 2 sol.Solvent flashing obtains gel, and gel drying under 100 ℃ air atmosphere was obtained the solid drying thing in 2 hours.The solid drying thing is ground, puts into Muffle furnace after the grinding,, at room temperature, be warming up to 550 ℃ with the speed of 2 ℃/min, calcine 2 hours, reduce to room temperature, calcined 2 hours down at 650 ℃, reduce to room temperature, get final product the target product sample, color sample is light yellow.The sulfur and nitrogen co-doped titanium dioxide powder that use makes carries out light-catalyzed reaction in the self-control reactor, the degradation rate of penicillin solution reaches 42% after 2 hours.
Claims (6)
1. preparation method with sulfur and nitrogen co-doped titanium dioxide of visible light catalysis activity, adopt sol-gel process, comprise the titanate esters hydrolysis, and introduce the sulphur source and nitrogenous source obtains TiO 2 sol, it is characterized in that, sulphur source and nitrogenous source come From Thiourea, with the colloidal sol weight percent meter, with the titanate esters of 1-15%, the hydrolyst of 1-5%, the diluent of 75-95% stirs, drip the thiocarbamide saturated aqueous solution of 1-5%, hydrolysis 1-3 hour, obtain colloidal sol, through the ageing and the diluent that volatilizees, obtain titania gel, grind into powder after super-dry is heat-treated pressed powder again, and calcining obtains the sulfur and nitrogen co-doped titanium dioxide nano-powder under the air atmosphere of 450-650 ℃ of temperature.
2. according to the preparation method of claim 1, it is characterized in that described dry run temperature was controlled in 50-100 ℃ the air atmosphere dry 1-3 hour.
3. according to the preparation method of claim 1, it is characterized in that, in the described sol-gel system, drip the thiocarbamide saturated aqueous solution of 2-3%.
4. according to the preparation method of claim 1, it is characterized in that described phthalate ester is butyl titanate, metatitanic acid n-propyl, isopropyl titanate or tetraethyl titanate.
5. according to the preparation method of claim 1, it is characterized in that described hydrolyst is acetic acid, hydrochloric acid, nitric acid or sulfuric acid; Diluent is absolute ethyl alcohol, absolute methanol, anhydrous isopropyl alcohol or polyvinyl alcohol.
6. according to the preparation method of claim 1, it is characterized in that, the heat treated calcine technology of described pressed powder adopts temperature-rise period gradually, at room temperature, programming rate is 1～20 ℃/minute, rises to 450-650 ℃, and temperature retention time is 0.5～5 hour, be cooled to room temperature then gradually, cooling rate is 15-40 ℃/minute.
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