CN101224417A - Phosphorus doped with titania photocatalyst with high thermal stability and preparing method thereof - Google Patents
Phosphorus doped with titania photocatalyst with high thermal stability and preparing method thereof Download PDFInfo
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- CN101224417A CN101224417A CNA2008100566875A CN200810056687A CN101224417A CN 101224417 A CN101224417 A CN 101224417A CN A2008100566875 A CNA2008100566875 A CN A2008100566875A CN 200810056687 A CN200810056687 A CN 200810056687A CN 101224417 A CN101224417 A CN 101224417A
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Abstract
The invention discloses a Phosphor/TiO2 photocatalyst which has high thermal stability and the corresponding preparation method. The photocatalyst can be prepared though a method comprising the following steps: 1) a solution which contains the precursor of inorganic titanium salt and phosphorated compound is prepared, then a precipitant is added into the solution which contains the precursor of inorganic titanium salt and phosphorated compound until the pH value reaches to 4-8, and a solid is obtained by aging and filtering; 2) the solid obtained form the step 1) is dried and calcined to get the phosphor/TiO2 photocatalyst; the precursor of inorganic titanium salt is the random combination of one or more of TiCl4, TiCl 3, TiOCl 2, Ti(SO4)2 and TiOSO4; the phosphorated compound is phosphorated oxy acid and/or phosphorated oxysalt. The photocatalyst of the invention has no polymorphic transformation after being calcined under high temperature, maintains high photocatalitic activity under ultraviolet and visible light, and can be used in the degeneration of the pollutant in industrial effluent and the reparation of wall paint or wall brick paint film which have antibiotic and air purifying effects.
Description
Technical field
The present invention relates to phosphor doped peptide oxide light catalyst of a kind of high thermal stability and preparation method thereof.
Background technology
TiO
2As the semi-conducting material of a kind of non-toxic inexpensive, high chemical stability and anti-photoetch, be widely used in fields such as photocatalysis, photovoltaic generation and solar cell.Its different crystal structure of two classes, anatase and rutile are widely used in photocatalysis field.Wherein, Detitanium-ore-type TiO
2Advantage is subjected to extensive concern owing to its photocatalytic activity height, photohole oxidability be strong etc.But Detitanium-ore-type TiO
2Energy gap be 3.2ev, cause it can only absorbing wavelength less than the ultraviolet light of 400nm; Only account for 3～4% at sunshine power spectrum medium ultraviolet light, can not be utilized and account for nearly half the visible light of solar energy.Therefore, the photoresponse scope with photochemical catalyst is extended to the important topic that visible region becomes photocatalysis research.The way that reduces energy gap at present has dye sensitization, semiconductor coupling connection and metal and nonmetallic doping etc.Wherein, nonmetal doping comprises N, C, B, S etc., but the rare report of the titanium oxide of phosphorus doping.
At TiO
2Two kinds of main crystalline phases in, anatase is a metastable phase, can change rutile-type (Carbon 2003,41,2619) about 600 ℃ into, photocatalytic activity sharply reduces.When ceramic surface is fired light purification film, because the required sintering temperature higher (700-1100 ℃) of fixed photocatalyst easily causes crystalline phase to transform, hard aggregation appears, not only can cause the photochemical catalyst loss of activity, more can cause the cracking of film.Therefore, a kind of photochemical catalyst with high-temperature stability of development has very important using value.People such as Dekany (Colloids Surf.A 2006,280,146) are precursor with the alkoxide of titanium, have prepared the TiO of phosphorus doping for the phosphorus source with phosphoric acid
2, but the rutile phase has appearred after 700 ℃ of roastings, and lose photocatalytic activity after 900 ℃ of roastings, can not be with the phenol mineralising.
Chinese patent (application number 200410064593.4) discloses a kind of preparation method of silica/titania composite oxide, be the titanium source promptly with butyl titanate or titanium tetrachloride, with sodium metasilicate or ethyl orthosilicate is the silicon source, adopt hydro-thermal method directly to prepare silica/titania composite oxide, these composite oxides have the outstanding heat endurance and the advantage of catalytic activity.But the inventor only points out these composite oxides and can be used as photochemical catalyst, does not provide concrete photocatalytic activity test result; On the other hand, this compound roasting to 1000 ℃ just begins to have faint rutile crystal type to occur, but does not also point out whether also have photocatalytic activity this moment.Chinese patent (application number 200410015914.1) is a raw material with titaniferous double salt anhydrous slufuric acid oxygen titanium ammonium, and thermal decomposition obtains the anatase phase titanium dioxide nano-powder in 600-800 ℃ of air.But this powder begins to occur the rutile phase at 800 ℃, and does not provide corresponding photocatalytic activity test result.So far, do not see relevant for reaching under visible light, all to keep highlight catalytic active to have the titania photocatalyst of superior heat-stability and the bibliographical information of synthetic method simultaneously at ultraviolet light.
Summary of the invention
The purpose of this invention is to provide a kind of phosphor doped peptide oxide light catalyst and preparation method thereof with superior heat-stability and highlight catalytic active.
The preparation method of phosphor doped peptide oxide light catalyst provided by the present invention comprises the steps:
1) preparation contains the solution of Ti-inorganic salt precursor and phosphorus-containing compound, and dropping precipitating reagent to pH value is 4-8 in the solution of the inorganic salts precursor of titaniferous and phosphorous compound then, and ageing filters and obtains solid;
2) step 1) is obtained solid oven dry, roasting obtains phosphor doped peptide oxide light catalyst;
Described Ti-inorganic salt precursor is TiCl
4, TiCl
3, TiOCl
2, Ti (SO
4)
2And TiOSO
4In one or more any combinations; Described phosphorus-containing compound is the oxyacid of phosphorus and/or the oxysalt of phosphorus.
In the described method, the oxyacid of described phosphorus is one or more any combinations in phosphorous acid, phosphoric acid, metaphosphoric acid, pyrophosphoric acid and the tripolyphosphate, and the oxysalt of described phosphorus is ammonium salt, alkali metal normal salt or the acid salt of the oxyacid of described phosphorus or more than one any combinations in them.
In the described method, described precipitating reagent is ammoniacal liquor, urea, NaOH solution, Na
2CO
3Solution, NaHCO
3Solution, (NH
4)
2CO
3Solution and NH
4HCO
3Any combination of in the solution one or more.
In the described method, in the described step 1), P elements and Ti-inorganic salt mol ratio are 0.001-0.1 in the described solution that contains Ti-inorganic salt precursor and phosphorus-containing compound: 1.
In the described method, in the described step 1), the concentration of Ti-inorganic salt precursor is 0.1-4.0mol/L described in the described solution that contains Ti-inorganic salt precursor and phosphorus-containing compound.
In the described method, in the described step 1), described preparation contains the solution of Ti-inorganic salt precursor and phosphorus-containing compound, and the temperature that drips precipitating reagent is 0-40 ℃.
In the described method, in the described step 1), the temperature of described ageing is 15-80 ℃, and the time of described ageing is 1-3 days.
In the described method, described step 2) in, described sintering temperature is 500-1100 ℃, described roasting time is 1-8 hour.
Comprise also in the described method that the solid that described step 1) aging step is obtained washs with deionized water and/or ethanol.
Photochemical catalyst of the present invention is the prepared phosphor doped peptide oxide light catalyst of said method.
The phosphorus source of method utilization cheapness of the present invention and the inorganic salts of titanium have synthesized phosphor doped peptide oxide light catalyst for raw material.
The analysis of XRD crystalline phase shows that phosphor doped peptide oxide light catalyst of the present invention has excellent heat endurance, has effectively stoped phase transformation and the grain growth in the heat treatment process, makes photochemical catalyst have characteristics such as particle size is little, specific surface is big.The ultraviolet-visible diffuse reflection spectrum shows that the doping of phosphorus has reduced the energy gap of titania photocatalyst, to the visible light generation response of wavelength greater than 400nm.The phosphorus that mixes mainly exists with+5 valency forms, form the Ti-O-P key with titanium oxide, and this is exactly the main cause that this phosphor doped peptide oxide has visible light catalysis activity probably.
Experiment showed, that phosphor doped peptide oxide light catalyst of the present invention makes through 500-1100 ℃ of roasting, have excellent heat endurance, 900 ℃ of roastings still kept anatase phase in 4 hours, and all had higher activity under ultraviolet light, visible light and sunshine; The speed of titania photocatalyst of the present invention degradation of methylene blue under ultraviolet light and visible light substantially exceeds commercialization photochemical catalyst P-25 commonly used at present, especially more than 800 ℃ after the roasting, the activity of P-25 reduces greatly and catalyst activity of the present invention is almost constant.
Raw material used in the present invention mostly is inorganic salts (titanium tetrachloride, titanium trichloride, titanium sulfate etc.), and cheap, technology is simple, and the photocatalyst granular size that makes is little, and specific area is big; Industrial wastewater treatment of waste gas, antibiotic wall brick film and aspect such as ceramic industry has bigger application prospect.
The specific embodiment
Method among the following embodiment if no special instructions, is conventional method.
Percentage composition described in the following embodiment if no special instructions, is the quality percentage composition.
Embodiment 1, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
The 5mol/L H that in the 200mL of 2 ℃ of ice-water baths deionized water, adds 0.16mL
3PO
4Solution drips 20mL TiCl under the electromagnetic agitation
4(0.18mol).Add and continue to stir after 2 hours, beginning to drip concentrated ammonia liquor (15mol/L) is 6.0,50 ℃ of ageings 1 day until the pH of solution value, suction filtration, and spend deionised water for several times, until filter liquor 0.1mol/L AgNO
3Solution does not detect Cl
-Ion.Leach thing after will washing and in 80 ℃ of baking ovens, dry, take out and grind, the powder roasting in 800 ℃ of Muffle furnaces that obtains was obtained phosphor doped peptide oxide in 2 hours.
According to the method described above, replace H with deionized water
3PO
4Solution prepares the pure zirconia titanium.
The XRD spectra of the phosphor doped peptide oxide of above-mentioned preparation turns out to be pure anatase crystal, and grain size is 15.6nm; N
2Physical absorption characterizes and records its specific area is 92m
2/ g; The phosphor doped peptide oxide (energy gap is 3.09eV) that the ultraviolet-visible diffuse reflection spectrum can be seen above-mentioned preparation has tangible red shift than the pure zirconia titanium (energy gap is 3.22eV) of above-mentioned preparation.
2, the compliance test result of phosphor doped peptide oxide light catalyst
Utilize the photocatalytic degradation of methylene blue to be model reaction, investigate the photocatalytic activity of phosphor doped peptide oxide catalyst under ultraviolet light and radiation of visible light of step 1 preparation.Be contrast with commercialization photochemical catalyst P-25 simultaneously.
Volume is that the reactor top of 250mL is outstanding a light source (visible light source is made up of 150W tungsten sodium lamp and 400nm optical filter, the mercury lamp of ultraviolet source usefulness 6W dominant wavelength 365nm).Methylene blue concentration is 1.2 * 10 in the reaction
-5Mol/L, catalyst (the phosphor doped peptide oxide catalyst or the commercialization photochemical catalyst P-25 of step 1 preparation) consumption is 0.25g/L, and reaction solution is 200mL, and control magnetic agitation speed makes catalyst be suspended in the solution.Place the darkroom certain hour to guarantee that after the adsorption equilibrium, just light-catalyzed reaction is carried out in the source of turning on the light reaction system.Sampling in the certain hour interval in course of reaction, centrifugation is got supernatant liquor and is measured its absorbance at the 665nm place with ultraviolet-visible spectrophotometer.Experiment finds that the photocatalytic degradation process of methylene blue meets the first-order kinetics equation, i.e. ln (c
0/ c)=and kt, wherein c is the instantaneous concentration of methylene blue solution, c
0Be the methylene blue solution concentration (initial concentration) after the adsorption equilibrium of catalyst darkroom, k is the apparent speed constant of reaction, and t is the reaction time.By ln (c
0/ the straight slope that c) time t mapping obtained can be obtained apparent first order reaction speed constant.
The result shows that the UV-irradiation apparent first order rate constant of degraded methylene blue solution down is 51 * 10
-3Min
-1, be commercialization photochemical catalyst P-25 speed constant (22 * 10
-3Min
-1) twice more than.The radiation of visible light apparent first order rate constant of degraded methylene blue solution down is 16 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 2 hours in 700 ℃ of Muffle furnaces of this catalyst, corresponding speed constant does not almost change (49 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 2 hours in 700 ℃ of Muffle furnaces, corresponding speed constant is reduced to 12 * 10
-3Min
-1
Embodiment 2, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
The 5mol/L H that in the 250mL of 2 ℃ of ice-water baths deionized water, adds 0.15mL
3PO
4Solution drips 20mL TiCl under the electromagnetic agitation
4(0.18mol).Add and continue to stir after 2 hours, beginning to drip 4mol/L NaOH solution is 5.8,50 ℃ of ageings 1 day until the pH of solution value, suction filtration, and spend deionised water for several times, until cleaning solution 0.1mol/L AgNO
3Solution does not detect Cl
-Ion.After oven dry in the solid after the washing and the 90 ℃ of baking ovens, take out grinding, the powder roasting in 800 ℃ of Muffle furnaces that obtains was obtained phosphor doped peptide oxide in 4 hours.
XRD spectra shows that the above-mentioned phosphor doped peptide oxide that obtains is pure anatase crystal, and grain size is 28.9nm; N
2Physical absorption characterizes and records its specific area is 54m
2/ g.
2, the compliance test result of phosphor doped peptide oxide light catalyst
According to the method for the step 2 of embodiment 1 phosphor doped peptide oxide light catalyst of step 1 preparation being carried out photocatalytic activity measures.
The result shows, degrade under the UV-irradiation apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 58 * 10
-3Min
-1, be commercialization photochemical catalyst P-25 speed constant (22 * 10
-3Min
-1) twice more than.Degrade under the radiation of visible light apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 17 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 4 hours in 700 ℃ of Muffle furnaces of this catalyst, corresponding speed constant does not almost change (57 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 4 hours in 700 ℃ of Muffle furnaces, corresponding speed constant is reduced to 10 * 10
-3Min
-1
Embodiment 3, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
The 5mol/L H that in the 250mL of 5 ℃ of ice-water baths deionized water, adds 0.15mL
3PO
3Solution, the TiCl of dropping 20mL 20% under the electromagnetic agitation
3Solution (0.024mol).Add and continue to stir after 2 hours, begin to drip 6mol/L NH
4HCO
3Solution is 7.0 until the pH of solution value, room temperature ageing 1 day, and suction filtration, and spend deionised water for several times, until using 0.1mol/L AgNO
3Solution does not detect Cl
-Ion.After the oven dry, take out and grind in 90 ℃ of baking ovens, the powder 900 ℃ of roastings in Muffle furnace that obtain were obtained phosphor doped peptide oxide in 1 hour.XRD spectra shows that it is pure anatase crystal.
2, the compliance test result of phosphor doped peptide oxide light catalyst
According to the method for the step 2 of embodiment 1 phosphor doped peptide oxide light catalyst of step 1 preparation being carried out photocatalytic activity measures.
The result shows, degrade under the UV-irradiation apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 25 * 10
-3Min
-1, still than the speed constant (22 * 10 of commercialization photochemical catalyst P-25
-3Min
-1) height; Degrade under the radiation of visible light apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 7.1 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 4 hours in 800 ℃ of Muffle furnaces of this catalyst, corresponding speed constant does not almost change (25 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 4 hours in 800 ℃ of Muffle furnaces, corresponding speed constant is reduced to 3.1 * 10
-3Min
-1
Embodiment 4, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
Take by weighing 53.2gTiOSO
4Solid (0.33mo1) is dissolved in it in 500mL water, adds the 2mol/L H of 0.25mL
4P
2O
7Solution, electromagnetic agitation began to drip 6mol/L (NH after 2 hours
4)
2CO
3Solution is 5.2,60 ℃ of ageings 1 day until the pH of solution value, suction filtration, and spend deionised water for several times, until using 0.1mol/LBa (NO
3)
2HNO
3Solution does not detect SO
4 2-Ion.After the oven dry, take out and grind in 110 ℃ of baking ovens, the powder 800 ℃ of roastings in Muffle furnace that obtain were obtained phosphor doped peptide oxide in 1 hour.XRD spectra shows that it is pure anatase crystal.
2, the compliance test result of phosphor doped peptide oxide light catalyst
According to the method for the step 2 of embodiment 1 phosphor doped peptide oxide light catalyst of step 1 preparation being carried out photocatalytic activity measures.
The result shows, degrade under the UV-irradiation apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 52 * 10
-3Min
-1, than the speed constant (22 * 10 of commercialization photochemical catalyst P-25
-3Min
-1) high a lot; Degrade under the radiation of visible light apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 15 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 4 hours in 700 ℃ of Muffle furnaces of this catalyst, corresponding speed constant does not almost change (50 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 4 hours in 700 ℃ of Muffle furnaces, corresponding speed constant is reduced to 3.1 * 10
-3Min
-1
Embodiment 5, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
Take by weighing 48.0g Ti (SO
4)
2Solid (0.20mol) is dissolved in it in 400mL water, adds the 5mol/L H of 0.45mL
3PO
3Solution, electromagnetic agitation are after 2 hours, and beginning to drip the 2mol/L urea liquid is 7.0,30 ℃ of ageings 3 days until the pH of solution value, suction filtration, and spend deionised water for several times, until using 0.1mol/L Ba (NO
3)
2Solution does not detect SO
4 2-Ion.After the oven dry, take out and grind in 110 ℃ of baking ovens, the powder roasting in 500 ℃ of Muffle furnaces that obtains was obtained phosphor doped peptide oxide in 6 hours.XRD spectra shows that it is pure anatase crystal.
2, the compliance test result of phosphor doped peptide oxide light catalyst
According to the method for the step 2 of embodiment 1 phosphor doped peptide oxide light catalyst of step 1 preparation being carried out photocatalytic activity measures.
The result shows, degrade under the UV-irradiation apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 45 * 10
-3Min
-1, than the speed constant (22 * 10 of commercialization photochemical catalyst P-25
-3Min
-1) high a lot; Degrade under the radiation of visible light apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 11 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 4 hours in 700 ℃ of Muffle furnaces of this catalyst, corresponding speed constant does not almost change (45 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 4 hours in 700 ℃ of Muffle furnaces, corresponding speed constant is reduced to 3.1 * 10
-3Min
-1
Embodiment 6, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
Take by weighing 48.0g Ti (SO
4)
2Solid (0.20mol) is dissolved in it in 400mL water, adds 0.45mL2mol/L NaH
2PO
4Solution, electromagnetic agitation are after 2 hours, and beginning to drip 4mol/L NaOH solution is 6.0,30 ℃ of ageings 3 days until the pH of solution value, suction filtration, and spend deionised water for several times, until filter liquor 0.1mol/LBa (NO
3)
2Solution does not detect SO
4 2-Ion.After the oven dry, take out and grind in 110 ℃ of baking ovens, the powder roasting in 600 ℃ of Muffle furnaces that obtains was obtained phosphor doped peptide oxide in 4 hours.XRD spectra shows that it is pure anatase crystal.
2, the compliance test result of phosphor doped peptide oxide light catalyst
According to the method for the step 2 of embodiment 1 phosphor doped peptide oxide light catalyst of step 1 preparation being carried out photocatalytic activity measures.
The result shows, degrade under the UV-irradiation apparent first order rate constant of tetrachlorophenol solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 39 * 10
-3Min
-1, than the speed constant (22 * 10 of commercialization photochemical catalyst P-25
-3Min
-1) high a lot; Degrade under the radiation of visible light apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 13 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 4 hours in 700 ℃ of Muffle furnaces of this catalyst, corresponding speed constant does not almost change (38 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 4 hours in 700 ℃ of Muffle furnaces, corresponding speed constant is reduced to 3.1 * 10
-3Min
-1
Embodiment 7, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
Take by weighing 48.0g Ti (SO
4)
2Solid (0.20mol) is dissolved in it in 400mL water, adds 0.45mL2mol/L NH
4H
2PO
4Solution, electromagnetic agitation are after 2 hours, and beginning to drip concentrated ammonia liquor (15mol/L) is 5.6 until the pH of solution value, room temperature ageing 3 days, and suction filtration, and spend deionised water for several times, until filter liquor 0.1mol/LBa (NO
3)
2Solution does not detect SO
4 2-Ion.After the oven dry, take out and grind in 110 ℃ of baking ovens, the powder roasting in 800 ℃ of Muffle furnaces that obtains was obtained phosphor doped peptide oxide in 3 hours.XRD spectra shows that it is pure anatase crystal.
2, the compliance test result of phosphor doped peptide oxide light catalyst
According to the method for the step 2 of embodiment 1 phosphor doped peptide oxide light catalyst of step 1 preparation being carried out photocatalytic activity measures.
The result shows, degrade under the UV-irradiation apparent first order rate constant of tetrachlorophenol solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 55 * 10
-3Min
-1, than the speed constant (22 * 10 of commercialization photochemical catalyst P-25
-3Min
-1) high a lot; Degrade under the radiation of visible light apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 11 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 2 hours in 900 ℃ of Muffle furnaces of this catalyst, corresponding speed constant just slightly reduces (41 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 2 hours in 900 ℃ of Muffle furnaces, corresponding speed constant is reduced to 2.0 * 10
-3Min
-1
Embodiment 8, phosphor doped peptide oxide light catalyst and compliance test result thereof
1, the preparation of phosphor doped peptide oxide light catalyst
The 5mol/L H that in the 200mL of 15 ℃ of ice-water baths deionized water, adds 2.0mL
3PO
4Solution drips 30mL 5mol/L TiOCl under the electromagnetic agitation
2Solution.Add and continue to stir after 2 hours, beginning to drip concentrated ammonia liquor (15mol/L) is 4.0,80 ℃ of ageings 1 day until the pH of solution value, suction filtration, and spend deionised water for several times, until filter liquor 0.1mol/L AgNO
3Solution does not detect Cl
-Ion.Leach thing after will washing and in 80 ℃ of baking ovens, dry, take out and grind, the powder roasting in 500 ℃ of Muffle furnaces that obtains was obtained phosphor doped peptide oxide in 8 hours.XRD detects spectrogram and shows that the phosphor doped peptide oxide of above-mentioned preparation is pure anatase crystal.
2, the compliance test result of phosphor doped peptide oxide light catalyst
According to the method for the step 2 of embodiment 1 phosphor doped peptide oxide light catalyst of step 1 preparation being carried out photocatalytic activity measures.
The result shows, degrade under the UV-irradiation apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 35 * 10
-3Min
-1, than the speed constant (22 * 10 of commercialization photochemical catalyst P-25
-3Min
-1) high a lot; Degrade under the radiation of visible light apparent first order rate constant of methylene blue solution of the phosphor doped peptide oxide light catalyst of step 1 preparation is 14 * 10
-3Min
-1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.With the roasting 4 hours in 700 ℃ of Muffle furnaces of this catalyst, corresponding speed constant does not almost change (36 * 10 under the UV-irradiation
-3Min
-1); And P-25 roasting 4 hours in 700 ℃ of Muffle furnaces, corresponding speed constant is reduced to 3.1 * 10
-3Min
-1
Claims (10)
1. the preparation method of a phosphor doped peptide oxide light catalyst comprises the steps:
1) preparation contains the solution of Ti-inorganic salt precursor and phosphorus-containing compound, and dropping precipitating reagent to pH value is 4-8 in the solution of the inorganic salts precursor of titaniferous and phosphorous compound then, ageing, and filtration obtains solid;
2) step 1) is obtained solid oven dry, roasting obtains phosphor doped peptide oxide light catalyst;
Described Ti-inorganic salt precursor is TiCl
4, TiCl
3, TiOCl
2, Ti (SO)
4And TiOSO
4In one or more any combinations; Described phosphorus-containing compound is the oxyacid of phosphorus and/or the oxysalt of phosphorus.
2. method according to claim 1, it is characterized in that: the oxyacid of described phosphorus is one or more any combinations in phosphorous acid, phosphoric acid, metaphosphoric acid, pyrophosphoric acid and the tripolyphosphate, and the oxysalt of described phosphorus is ammonium salt, alkali metal normal salt or the acid salt of the oxyacid of described phosphorus or more than one any combinations in them.
3. method according to claim 2 is characterized in that: described precipitating reagent is ammoniacal liquor, urea, NaOH solution, Na
2CO
3Solution, NaHCO
3Solution, (NH
4)
2CO
3Solution and NH
4HCO
3Any combination of in the solution one or more.
4. method according to claim 3 is characterized in that: in the described step 1), P elements and Ti-inorganic salt mol ratio are 0.001-0.1 in the described solution that contains Ti-inorganic salt precursor and phosphorus-containing compound: 1.
5. method according to claim 4 is characterized in that: the concentration of Ti-inorganic salt precursor is 0.1-4.0mol/L described in the described solution that contains Ti-inorganic salt precursor and phosphorus-containing compound.
6. method according to claim 5 is characterized in that: in the described step 1), described preparation contains the solution of Ti-inorganic salt precursor and phosphorus-containing compound, and the temperature that drips precipitating reagent is 0-40 ℃.
7. method according to claim 6 is characterized in that: in the described step 1), the temperature of described ageing is 15-80 ℃, and the time of described ageing is 1-3 days.
8. method according to claim 7 is characterized in that: described step 2), described sintering temperature is 500-1100 ℃, and described roasting time is 1-8 hour.
9. according to any described method among the claim 1-8, it is characterized in that: comprise also in the described method that the solid that described step 1) aging step is obtained washs with deionized water and/or ethanol.
10. the phosphor doped peptide oxide light catalyst of any described method preparation among the claim 1-9.
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| CN105102400A (en) * | 2013-04-12 | 2015-11-25 | 瓦林格光催化股份有限公司 | A method of applying NOx degrading composition on concrete element |
| CN106268763A (en) * | 2016-09-14 | 2017-01-04 | 南京林业大学 | A kind of vanadium modifying titanium dioxide preparation method adapting to tunnel illumination condition |
| CN108620102A (en) * | 2018-06-08 | 2018-10-09 | 龙蟒佰利联集团股份有限公司 | A kind of phosphorus doping mesoporous TiO 2 method for preparing catalyst |
| CN108671946A (en) * | 2018-05-11 | 2018-10-19 | 南京理工大学 | Phosphorus doping cerium titanium catalyst, preparation and its application in selective-catalytic-reduction denitrified |
| GB2579654A (en) * | 2018-12-10 | 2020-07-01 | Kastus Tech Dac | P-doped surface coatings and process of preparation thereof |
| CN113272390A (en) * | 2018-12-10 | 2021-08-17 | 克斯塔斯科技有限公司 | Phosphorus-doped surface coating and preparation method thereof |
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2008
- 2008-01-23 CN CNA2008100566875A patent/CN101224417A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527418A (en) * | 2010-12-28 | 2012-07-04 | 日挥触媒化成株式会社 | Titaniferous powder, exhaust-gas disposal catalyst, and method for making titaniferous powder |
| CN105102400A (en) * | 2013-04-12 | 2015-11-25 | 瓦林格光催化股份有限公司 | A method of applying NOx degrading composition on concrete element |
| CN106268763A (en) * | 2016-09-14 | 2017-01-04 | 南京林业大学 | A kind of vanadium modifying titanium dioxide preparation method adapting to tunnel illumination condition |
| CN106268763B (en) * | 2016-09-14 | 2018-03-30 | 南京林业大学 | A kind of vanadium modifying titanium dioxide preparation method for adapting to tunnel illumination condition |
| CN108671946A (en) * | 2018-05-11 | 2018-10-19 | 南京理工大学 | Phosphorus doping cerium titanium catalyst, preparation and its application in selective-catalytic-reduction denitrified |
| CN108620102A (en) * | 2018-06-08 | 2018-10-09 | 龙蟒佰利联集团股份有限公司 | A kind of phosphorus doping mesoporous TiO 2 method for preparing catalyst |
| GB2579654A (en) * | 2018-12-10 | 2020-07-01 | Kastus Tech Dac | P-doped surface coatings and process of preparation thereof |
| CN113272390A (en) * | 2018-12-10 | 2021-08-17 | 克斯塔斯科技有限公司 | Phosphorus-doped surface coating and preparation method thereof |
| CN113272390B (en) * | 2018-12-10 | 2023-02-17 | 克斯塔斯科技有限公司 | Phosphorus-doped surface coating and preparation method thereof |
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