CN101733133A - Titanium dioxide photocatalyst with coating layer coated on surface and preparation method thereof - Google Patents
Titanium dioxide photocatalyst with coating layer coated on surface and preparation method thereof Download PDFInfo
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- CN101733133A CN101733133A CN200910155274A CN200910155274A CN101733133A CN 101733133 A CN101733133 A CN 101733133A CN 200910155274 A CN200910155274 A CN 200910155274A CN 200910155274 A CN200910155274 A CN 200910155274A CN 101733133 A CN101733133 A CN 101733133A
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Abstract
The invention provides a titanium dioxide photocatalyst with a coating layer coated on a surface, which comprises a titanium dioxide powder particle, wherein a fluoride coating layer, a fluoride-phosphate coating layer or a fluorapatite coating layer is arranged outside the titanium dioxide powder particle. Compared with an ordinary titanium dioxide powder particle, the photocatalytic speed is markedly increased. The invention also provides a preparation method of the titanium dioxide photocatalyst with the coating layer coated on the surface, which comprises the following steps of: depositing titanium dioxide as a precursor and a metal fluoride, a fluoride-phosphate mixture or fluorapatite as a coating material on the surface of the titanium dioxide powder particle by using a wet chemical method and preparing a product under the condition of not changing the crystal structure, the crystal phase composition and the average particle diameter of the titanium dioxide as the precursor. The titanium dioxide photocatalyst has low cost of the used raw materials, simple equipment and easy operation; compared with the pure titanium dioxide, the ultraviolet light catalytic activity of the obtained product is markedly improved, and meanwhile, the adsorption capacity for an organic pollutant is also enhanced.
Description
Technical field
The present invention relates to a kind of titanium deoxide catalyst and preparation method thereof, belong to catalysis technical field, more concrete is to the invention provides a kind of surface to contain metal fluoride clad, the common phosphate clad of metal fluoride or fluor-apatite clad and have nano TiO 2 powder photochemical catalyst of high catalytic activity and preparation method thereof.
Background technology
21 century, energy shortage and environmental pollution are increasingly serious, the subject matter that has become the world today and faced.Therefore, national governments, scientist and technical staff actively take measures, and are tackled.In many processing methods, the conductor photocatalysis technology is especially noticeable, it can directly utilize the ultraviolet light of the various approach that comprise sunshine, just can make various organic or inorganic pollutants that thoroughly degraded and mineralising take place at ambient temperature, thereby reach the purpose of removing environmental contaminants.This technology have energy consumption low, easy to operate, remove characteristics such as cleanliness height, especially to some special pollutants, photocatalysis technology has more the incomparable advantage of other technologies, and non-secondary pollution.At present, photocatalysis technology has become a focus in various countries' high-tech competition, is with a wide range of applications.
1972, Fujishima and Honda found, are subjected to the red schorl phase titanium dioxide monocrystalline electrode of ultraviolet excitation can water be decomposed.1976, discoveries such as Carey were subjected to the titanium dioxide of ultraviolet excitation that poisonous biphenyl and chlordiphenyl are degraded.After 1 year, Frank and Bard find the cyanide of titanium dioxide in can photocatalytic degradation water, and have proposed photocatalysis technology is applied to the suggestion of the depollution of environment.After this, curb environmental pollution and become in the conductor photocatalysis field active research direction the most.In numerous semiconductor light-catalysts, titanium dioxide is best for this reason so far photochemical catalyst, and relevant its research is in core status always.Titanium dioxide not only has advantages of high catalytic activity and stronger oxidability, and its biology, chemistry and photochemical stability height, and itself is nontoxic and inexpensive.
To the research of titanium dioxide optical catalyst, carried out 30 or 40 years, still in the ascendant at present.It is found that, the crystalline form by changing TiO 2 particles, specific surface, degree of crystallinity etc., and it is carried out anion and cation doping or finishing etc., can improve the photocatalytic activity of titanium dioxide.But the obtained efficient of optically catalytic TiO 2 can't satisfy the requirement of industrial applications at present.2000, discoveries such as Minero added sodium fluoride in the titanium dioxide water slurry of acidity, can significantly improve the photocatalytic speed of degradation of phenol in the titanium dioxide photocatalysis body system.Subsequently, other researchers are also finding similar phenomenon aspect the organic matters such as optically catalytic TiO 2 degraded chlorophenol, organic acid, benzene, amine, azo dyes, cyanuric acid.In addition, this method also can improve the efficient that optically catalytic TiO 2 selective oxidation benzene generates phenol, selective oxidation cyclohexane generation several ketone of ring and encircles important chemical reactions such as several alcohol.This shows, add fluorine ion in the titanium dioxide water slurry, is an important means that improves optically catalytic TiO 2 efficient.Yet fluorine ion is as a kind of important pollutant of water body, and there is strict emission limit set in country to it.The relevant laws and regulations regulation, the content of fluoride ion in the industrial wastewater must not be greater than 0.5mM.Therefore, fluorine ion is immobilized in the TiO 2 particles surface, make it bring into play above-mentioned effect, become the problem that needs solution.
Reference that the present invention adopts:
M.R.Hoffmann，S.T.Martin，W.Choi，D.W.Bahnemann，Chem.Rev.1995，95，69-96；
C.Minero，G.Mariella，V.Maurino，E.Pelizzetti，Langmuir?2000，16，2632-2641.；
Y.Xu，K.Lv，Z.Xiong，W.Leng，W.Du，D.Liu，X.Xue，J.Phys.Chem.C?2007，111，19024-19032；
N.Senamaud，D.Bernache-Assollant，E.Champion，M.Heughebaert，C.Ray，Solid?StateIonics?1997，101-103，1357-1362。
Summary of the invention
The titanium dioxide optical catalyst that the object of the present invention is to provide a kind of surface to be coated with coating layer with high catalytic activity.Purpose of the present invention realizes by following technical measures:
It comprises the titanium dioxide powder particle, and described titanium dioxide powder particle is provided with fluoride clad, fluoride phosphate clad or fluor-apatite clad altogether outward.
By above technical scheme, the titanium dioxide powder particle that the present invention is common relatively, photocatalytic speed significantly improves.
The present invention also aims to provide the preparation method of the titanium dioxide optical catalyst that the surface is coated with coating layer, purpose of the present invention realizes by following technical measures:
The present invention is presoma with titanium dioxide, with metal fluoride, fluoride-phosphate mixt or fluor-apatite is clad material, method by wet chemistry is deposited on the titanium dioxide powder particle surface, prepares the titanium dioxide optical catalyst that the surface is coated with coating layer under the situation of the crystal structure that does not change presoma titanium dioxide, crystalline phase composition and average grain diameter.
The cost of material that the present invention uses is cheap, and equipment is simple, easy operating; The gained photochemical catalyst is than simple titanium dioxide, and its ultraviolet catalytic is active obviously to be improved, and simultaneously the organic pollutant adsorption ability is also promoted to some extent.
Description of drawings
Fig. 1 is the structural representation of the surperficial titanium dioxide optical catalyst that is coated with coating layer;
Fig. 2 is that the X ray diffracting spectrum of embodiment 1,2 is (with pure TiO
2Relatively);
Fig. 3 is that the blue Miu Er adsorption isotherm of 1,2 pairs of organic pollutions of embodiment (2, the 4-chlorophenesic acid) is (with pure TiO
2Relatively);
Fig. 4 is that the ultraviolet degradation phenol curve of embodiment 1,2,3 is (with pure TiO
2Relatively);
Fig. 5 carries out above-mentioned light-catalyzed reaction after 2 hours for embodiment 1,2,3, fluorinion concentration in the solution (fluorine ion discharge capacity limitation standard GB in the industrial wastewater being compared with country).
The specific embodiment
With reference to accompanying drawing 1.The titanium dioxide optical catalyst that the present invention is coated with coating layer for a kind of surface, it comprises titanium dioxide powder particle 1, described titanium dioxide powder particle is provided with clad 2 outward, and described clad is metal fluoride clad, metal fluoride phosphate clad or fluor-apatite clad altogether.
This composite catalyst has the crystal structure similar with the titanium dioxide raw material, crystalline phase is formed and average grain diameter, but it has higher ultraviolet light photocatalysis activity.The present invention is at the direct coated inorganic fluoride of the titanium dioxide powder particle surface of commodity that are easy to get or artificial preparation, realized fluorine element immobilized in the titanium dioxide optical catalyst particle surface; The gained catalyst has very high photocatalytic activity, and the fluorinion concentration of stripping is lower than national limitation standard in water simultaneously; At organic catalysis and Environmental Science and Engineering field very big application potential is arranged.
The invention also discloses and a kind ofly coat one deck at the titanium dioxide powder particle surface and contain the inorganic fluorine compound clad and have the titanium dioxide powder Preparation of catalysts method of highlight catalytic active.It is presoma with titanium dioxide, method by wet chemistry is deposited on the titanium dioxide powder particle surface, with metal fluoride, fluoride-phosphate mixt, fluor-apatite is clad material, and metal fluoride, fluoride-phosphate mixt or the fluor-apatite that is insoluble in water is coated on the titanium dioxide powder particle surface.Preparation process does not change the crystalline phase of presoma titanium dioxide and forms and average grain diameter, this composite catalyst has the crystal structure similar with the titanium dioxide raw material, crystalline phase is formed and average grain diameter, but the catalyst of gained has the ultraviolet catalytic activity higher than original titanium dioxide.
The inventive method can be at the direct coated inorganic fluoride of the titanium dioxide powder particle surface of commodity that are easy to get or artificial preparation, has realized fluorine element immobilized in the titanium dioxide optical catalyst particle surface; The gained catalyst has very high photocatalytic activity, and the fluorinion concentration of stripping is lower than national limitation standard in water simultaneously; At organic catalysis and Environmental Science and Engineering field very big application potential is arranged.Technology of the present invention is simple, and lower to the equipment requirement, raw material is cheap and easy to get, and product has kept the crystal structure and the composition of matrix titanium dioxide, has improved the ultraviolet light photocatalysis activity of titanium dioxide simultaneously.
Described preparation method is specific as follows:
1 one kinds of surfaces of method are coated with the preparation method one of the titanium dioxide optical catalyst of metal fluoride clad, i.e. alkaline process may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2～100: 40;
2) under vigorous stirring, add fluorine salt aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 4～100: 120;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8～11;
4) under 60 ℃～100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the fluoride clad.
Above process is expressed as follows (M wherein
N+Be metal ion):
1) at normal temperatures, presoma titanium dioxide is scattered in the aqueous solution of villiaumite TiO
2With the fluorine ion mol ratio be 100: 4～100: 120;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3～5;
3) add a kind of metal cation salt, TiO as precipitating reagent
2With the mol ratio of this metal ion be 100: 2～100: 40, under 60 ℃～100 ℃, reacted 2 hours;
4) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the fluoride clad.
Above process is expressed as follows (M wherein
N+Be metal ion):
3 one kinds of surfaces of method are coated with metal fluoride and the phosphate preparation method one of the titanium dioxide optical catalyst of clad altogether, i.e. alkaline process may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 3～100: 20;
2) under vigorous stirring, add villiaumite and phosphate mixed aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 3～100: 57, TiO
2With the phosphate anion mol ratio be 100: 1～100: 8;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8～11;
4) under 60 ℃～100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
4 one kinds of surfaces of method are coated with metal fluoride and the phosphate preparation method two of the titanium dioxide optical catalyst of clad altogether, i.e. acid system may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in villiaumite and the phosphate mixed aqueous solution TiO
2With the fluorine ion mol ratio be 100: 3～100: 57, TiO
2With the phosphate anion mol ratio be 100: 1～100: 8;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3～5;
3) add a kind of metal cation salt, TiO as precipitating reagent
2With the mol ratio of this metal ion be 100: 3～100: 20;
4) under 60 ℃～100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
5 one kinds of surfaces of method are coated with the preparation method of the titanium dioxide optical catalyst of fluor-apatite clad, it is characterized in that it may further comprise the steps:
1) under the normal temperature, presoma titanium dioxide is scattered in the aqueous solution as the metal cation salt of precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2～100: 20;
2) under the condition of boiling, add the mixed aqueous solution that contains fluorine ion and phosphate anion, TiO
2With the phosphate anion mol ratio be 100: 1.2～100: 12, TiO
2With the fluorine ion mol ratio be 100: 0.4～100: 4.
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 7～10, under 60 ℃～90 ℃, and ageing 1 hour.
4) be cooled to room temperature after, sediment after filtration, washing and 70 ℃～120 ℃ down oven dry, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that contains the fluor-apatite clad.
Reaction equation can be expressed as (with M
N+For bivalent metal ion is an example):
In the above preparation process, selected presoma be the titanium dioxide of commodity or voluntarily the preparation titanium dioxide.
Can be selected from the soluble-salt (as calcium nitrate, lanthanum nitrate etc.) of alkaline-earth metal or lanthanide series metal as the metal ion of precipitating reagent.
Fluoride salt can be any one or two or three the mixing in potassium fluoride, sodium fluoride, the ammonium fluoride etc.
Phosphate can be selected from following any: dipotassium hydrogen phosphate, sodium hydrogen phosphate, diammonium hydrogen phosphate etc., or its mixing of any two or three.
The pH conditioning agent can be any two or three, four kind the mixing of any in dilute solution of sodium hydroxide, ammoniacal liquor weak solution, watery hydrochloric acid or the rare perchloric acid etc. or its.
Catalyst to the evaluation method of organic matter absorption property is: 50mg catalyst and 50ml concentration are 2 of 40ppm, and 4-chlorophenesic acid solution mixes, the lucifuge shaken overnight.Get the 1.5ml reactant liquor, filter, measure the concentration C of chlorophenol in the filtrate with high-efficient liquid phase chromatogram HPLC (Dionex P680) through miillpore filter (0.45 μ m)
eAccording to the change in concentration of chlorophenol before and after the absorption, calculate the adsorbance q of catalyst
eAccording to q
eWith C
eMapping, the absorption property difference of measurement different catalysts.
The evaluation method of photocatalytic activity is: (375W) is outer irradiation source with high-pressure sodium lamp, and radiation dominant wavelength 365nm, catalyst amount are 50mg, is that the phenol solution of 40ppm is mixed the lucifuge shaken overnight with 50ml concentration before the reaction.Illumination reaction carries out in the Pyrex glass container that possesses the cool cycles water leg, and reaction temperature remains on 25 ± 2 ℃.Get the 1.5ml reactant liquor at regular intervals, filter, measure phenol concentration C in the filtrate with HPLC through miillpore filter (0.45 μ m)
T.According to C
tWith the variation relation of light application time, weigh the relative photocatalytic activity of different catalysts.Meanwhile, adopt chromatography of ions (DionexISC90), detect the concentration of stripping fluorine ion in the filtrate.
Embodiment one
Get 1g commodity anatase phase oxidation titanium (AT), being scattered in 100ml concentration is that (mM is 10 to 6mM
-3Mol/L) Ca (NO
3)
2(solution S 1) places magnetic stirrer under the room temperature in the aqueous solution, slowly splashes into the NH that 100mL concentration is 12mM
4The F aqueous solution (solution S 2).By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst A (seeing A line in Fig. 1～4).TiO wherein
2With the molar ratio of Ca element, F element be 100: 4.8: 9.6.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and catalyst A and AT Pyrogentisinic Acid's degradation rate is respectively 45.71% and 38.09%.Obviously, under the same conditions, catalyst A has stronger ultraviolet catalytic activity than catalyst A T.
Embodiment two
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 5mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 3mM (NH
4)
2HPO
4With 1mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1～4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 4.0: 2.4: 0.8.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 48.70%.
Embodiment three
Experiment condition, step are with embodiment one, with Ca (NO in the solution S 1
3)
2Concentration change 9mM into, solution S 2 is replaced with 2mM (NH
4)
2HPO
4With 12mM NH
4The mixed solution of F makes calcirm-fluoride-calcium phosphate cladding titanium dioxide catalyst C (seeing C curve in Fig. 3～4) altogether.TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 7.2: 1.6: 9.6, with above-mentioned photocatalytic activity evaluation method, after 1 hour, the degradation rate of phenol is 46.59% under UV-irradiation.
Embodiment four
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 3mM
3)
2In the aqueous solution, place magnetic stirrer under the room temperature, slowly splash into the NH that 100mL concentration is 6mM
4The F aqueous solution.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 2.4: 4.8.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 42.71%.
Embodiment five
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 9mM
3)
2In the aqueous solution, place magnetic stirrer under the room temperature, slowly splash into the NH that 100mL concentration is 18mM
4The F aqueous solution.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 7.2: 14.4.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 49.00%.
Embodiment six
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 20mM
3)
2In the aqueous solution, place magnetic stirrer under the room temperature, slowly splash into the NH that 100mL concentration is 40mM
4The F aqueous solution.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 16: 32.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 42.24%.
Embodiment seven
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 50mM
3)
2(solution S 1) places magnetic stirrer under the room temperature in the aqueous solution, slowly splashes into the NH that 100mL concentration is 100mM
4The F aqueous solution (solution S 2).By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 40: 80.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 31.01%.
Embodiment eight
Experiment condition, step are with embodiment three, with Ca (NO in the solution S 1
3)
2Concentration change 6mM into, solution S 2 is replaced with 2mM (NH
4)
2HPO
4With 6mM NH
4The mixed solution of F makes calcirm-fluoride-calcium phosphate cladding titanium dioxide catalyst C (seeing C curve in Fig. 3 ~ 4) altogether.TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 4.8: 1.6: 4.8, with above-mentioned photocatalytic activity evaluation method, after 1 hour, the degradation rate of phenol is 44.60% under UV-irradiation.
Embodiment nine
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 2.5mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 1.5mM (NH
4)
2HPO
4With 0.5mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1 ~ 4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 2.0: 1.2: 0.4.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 45.88%.
Embodiment ten
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 10mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 6mM (NH
4)
2HPO
4With 2mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1 ~ 4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 8.0: 4.8: 1.6.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 48.30%.
Embodiment 11
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 20mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 12mM (NH
4)
2HPO
4With 4mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1 ~ 4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 16.0: 9.6: 3.2.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 42.70%.
Claims (10)
1. titanium dioxide optical catalyst that the surface is coated with coating layer, it is characterized in that: it comprises the titanium dioxide powder particle, and described titanium dioxide powder particle is provided with metal fluoride clad, metal fluoride phosphate clad or fluor-apatite clad altogether outward.
2. a surface is coated with the preparation method one of the titanium dioxide optical catalyst of metal fluoride clad, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2～100: 40;
2) under vigorous stirring, add fluorine salt aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 4～100: 120;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8～11;
4) under 60 ℃～100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the metal fluoride clad.
3. a surface is coated with the preparation method two of the titanium dioxide optical catalyst of metal fluoride clad, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in the aqueous solution of villiaumite TiO
2With the fluorine ion mol ratio be 100: 4～100: 120;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3～5;
3) add a kind of metal cation salt, TiO as precipitating reagent
2With the mol ratio of this metal ion be 100: 2～100: 40, under 60 ℃～100 ℃, reacted 2 hours;
4) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the metal fluoride clad.
4. a surface is coated with metal fluoride and the phosphate preparation method one of the titanium dioxide optical catalyst of clad altogether, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 3～100: 20;
2) under vigorous stirring, add villiaumite and phosphate mixed aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 3～100: 57, TiO
2With the phosphate anion mol ratio be 100: 1～100: 8;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8～11;
4) under 60 ℃～100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
5. a surface is coated with metal fluoride and the phosphate preparation method two of the titanium dioxide optical catalyst of clad altogether, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in villiaumite and the phosphate mixed aqueous solution TiO
2With the fluorine ion mol ratio be 100: 3～100: 57, TiO
2With the phosphate anion mol ratio be 100: 1～100: 8;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3～5;
3) adding is as the metal cation salt of precipitating reagent, TiO
2With the mol ratio of this metal ion be 100: 3～100: 20;
4) under 60 ℃～100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃～120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
6. a surface is coated with the preparation method of the titanium dioxide optical catalyst of fluor-apatite clad, it is characterized in that it may further comprise the steps:
1) under the normal temperature, presoma titanium dioxide is scattered in the aqueous solution as the metal cation salt of precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2～100: 20;
2) under the condition of boiling, add the mixed aqueous solution that contains fluorine ion and phosphate anion, TiO
2With the phosphate anion mol ratio be 100: 1.2～100: 12, TiO
2With the fluorine ion mol ratio be 100: 0.4～100: 4;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 7～10, under 60 ℃～90 ℃, and ageing 1 hour;
4) be cooled to room temperature after, sediment after filtration, washing and 70 ℃～120 ℃ down oven dry, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that contains the fluor-apatite clad.
7. according to the method for the surperficial titanium dioxide optical catalyst that is coated with coating layer of the described preparation of claim 2～6, it is characterized in that described metal cation salt as precipitating reagent is selected from the soluble-salt of alkaline-earth metal or lanthanide series metal.
8. the method for the titanium dioxide optical catalyst that is coated with coating layer according to the described preparation surface of claim 2～6 is characterized in that described fluoride can be any one or two or three the mixing in sodium fluoride, potassium fluoride, the ammonium fluoride.
9. according to the method for claim 4,5, the surperficial titanium dioxide optical catalyst that is coated with coating layer of 6 described preparations, it is characterized in that described phosphate can be dipotassium hydrogen phosphate, sodium hydrogen phosphate or diammonium hydrogen phosphate or its mixing of any two or three.
10. the method for the titanium dioxide optical catalyst that is coated with coating layer according to the described preparation surface of claim 2～6 is characterized in that described pH conditioning agent can be the mixing of dilute solution of sodium hydroxide, ammoniacal liquor weak solution, watery hydrochloric acid or rare perchloric acid or its any two or three or four kind.
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