CN101028602A - High-activity phosphor doped peptide oxide light catalyst, its production and use - Google Patents

High-activity phosphor doped peptide oxide light catalyst, its production and use Download PDF

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Publication number
CN101028602A
CN101028602A CNA2007100652895A CN200710065289A CN101028602A CN 101028602 A CN101028602 A CN 101028602A CN A2007100652895 A CNA2007100652895 A CN A2007100652895A CN 200710065289 A CN200710065289 A CN 200710065289A CN 101028602 A CN101028602 A CN 101028602A
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preparation
solution
activity
phosphor doped
light catalyst
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CN100493708C (en
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朱月香
林莉
郑仁垟
谢有畅
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Peking University
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Peking University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

A P doped titanium oxide photocatalyst with high activity used for environment protection, solar energy conversion, catalytic photoelectric device, etc is prepared through mixing the inorganic salt of Ti with hypophosphorous acid dripping precipitant, regulating pH=4-8, ageing, washing, and calcining.

Description

A kind of high-activity phosphor doped peptide oxide light catalyst and preparation method thereof and application
Technical field
The present invention relates to a kind of highly active phosphor doped peptide oxide light catalyst and synthetic method and application, prepared Detitanium-ore-type catalyst is no matter still all have higher photocatalytic activity at ultraviolet light under visible light, can be used for the degraded of pollutant in the industrial wastewater, belong to catalyst class field of new.
Background technology
At various light-catalysed semi-conducting material, the Detitanium-ore-type TiO of being used for 2Become present most widely used photochemical catalyst with its highlight catalytic active, anti-chemistry and photoetch and advantage such as cheap.But because Detitanium-ore-type TiO 2Energy gap be 3.20eV, TiO like this 2General only have activity at ultraviolet region; Less than 5%, it is nearly 43% that visible light then accounts at sunshine power spectrum medium ultraviolet luminous energy (below the 400nm), therefore develops the important topic that highly active visible-light-responsive photocatalyst becomes present photocatalysis research.Studies show that, to Detitanium-ore-type TiO 2Carrying out suitable doping (metal or nonmetal) can be with TiO 2Effective excitation wavelength move on to visible region from the ultra-violet (UV) band, thereby effectively utilize the visible light in the solar energy.Wherein, the nonmetal of doping comprises N, C, B, S etc., but the rare report of the titanium oxide of phosphorus doping.For the titanium oxide of phosphorus modification, { Chem.Mater., the titanium oxide that 15 (2003) 2280} adopt phosphoric acid to make phosphorylation have active preferably under ultraviolet light people such as Yu, but its energy gap even bigger than pure zirconia titanium does not have visible light catalysis activity.
Summary of the invention
The purpose of this invention is to provide phosphor doped peptide oxide that under ultraviolet light and visible light, all has highlight catalytic active and preparation method thereof.
The preparation method of high-activity phosphor doped peptide oxide light catalyst of the present invention is that Ti-inorganic salt is mixed in water with hypophosphorous acid, drips precipitating reagent again and regulates pH between the 4-8, and ageing is after washing, roasting obtain described high-activity phosphor doped peptide oxide light catalyst.
Wherein, Ti-inorganic salt is the raw material of industry cheap and easy to get, preferentially selects TiCl for use 4, TiCl 3, Ti (SO 4) 2And TiOSO 4In one or more; In the preparation process, the mol ratio of hypophosphorous acid and Ti-inorganic salt is 0.001-0.1: 1; Precipitating reagent can be selected various alkali commonly used, and commonly used have ammoniacal liquor, urea, NaOH solution, a Na 2CO 3Solution, NaHCO 3Solution, (NH 4) 2CO 3Solution, NH 4HCO 3In the solution one or more.
In preparation process of the present invention, the temperature of ageing is 15-60 ℃, and the time is 1-3 days.Washing is to wash 2-8 time with deionized water and ethanol respectively.The temperature of roasting is 300-900 ℃, and the time is 1-6 hour.
Another object of the present invention provides the purposes of high-activity phosphor doped peptide oxide light catalyst of the present invention.
High-activity phosphor doped peptide oxide light catalyst of the present invention all has higher photocatalytic activity under ultraviolet light and radiation of visible light; photocatalytic degradation is reflected under ultraviolet light, visible light or the sunshine and carries out; can be widely used in light degradation air, the industrial wastewater in the field such as organic pollution; especially; its light degradation methylene blue and tetrachlorophenol active even be much higher than commodity photochemical catalyst P-25 commonly used at present, this catalyst also belongs to protection scope of the present invention in the application of light degradation methylene blue and tetrachlorophenol.
The present invention utilizes hypophosphorous acid and inorganic titanium salt to synthesize the titania photocatalyst of phosphorus doping for raw material first.Ultraviolet-diffuse reflection absorption spectrum shows that the doping of phosphorus has reduced the energy gap of titania photocatalyst, and, the doping of phosphorus can improve the heat endurance of titanium oxide greatly, has effectively stoped phase transformation and the grain growth in the heat treatment process, and prepared catalyst is Detitanium-ore-type TiO 2, characteristics such as it is little to have particle size, and specific area is big all have higher photocatalysis performance under ultraviolet and radiation of visible light.The kinds of experiments evidence shows that the phosphorus of doping mainly exists with+5 valency forms, form the Ti-O-P key with titanium oxide, and this is exactly this phosphorus titanium oxide doped main cause with photocatalytic activity disastrously probably.In addition, the introducing of reproducibility hypophosphorous acid may produce a small amount of Ti 3+Or other lattice defects, and this also can make catalyst that light is responded to some extent, introduces TiCl 3Also can make photoresponse type photochemical catalyst.
The raw material that the present invention prepares titanium oxide mostly is inorganic salts (titanium tetrachloride, titanium trichloride, titanium sulfate etc.), cheap, technology is simple, the photocatalyst granular size that makes is little, specific area is big, under ultraviolet light and radiation of visible light, all has higher photocatalytic activity, its photocatalytic degradation methylene blue and tetrachlorophenol active even be much higher than commodity photochemical catalyst P-25 commonly used at present.This catalyst has bigger application prospect in environmental protection, conversion of solar energy, catalysis and optoelectronic device.
The specific embodiment
Embodiment 1,
In the 250mL deionized water, add 0.20mLH 3PO 2, drip 20mLTiCl under the electromagnetic agitation 4Add and continue to stir after 2 hours, it is near neutral until the pH of solution value to begin to drip concentrated ammonia liquor, 25 ℃ of room temperature ageings 2 days, and suction filtration, and spend the deionised water several, until using 0.5mol/LAgNO 3Solution does not detect Cl -Ion.After the oven dry, take out and grind in 80 ℃ of baking ovens, the powder 600 ℃ of roastings in Muffle furnace that obtain were obtained phosphor doped peptide oxide in 2 hours.
XRD spectra shows that it is pure anatase crystal, and grain size is 14nm; N 2Physical absorption characterizes and records its specific area is 154m 2/ g; The ultraviolet-visible diffuse reflection spectrum can see that phosphor doped peptide oxide (does not add H than pure zirconia titanium 3PO 2, all the other preparation conditions are identical) and tangible red shift arranged.
Utilize the photocatalytic degradation of methylene blue to be model reaction, investigate the photocatalytic activity of institute's controlling catalyst under ultraviolet light and radiation of visible light.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, ultraviolet source with the mercury lamp of 8W dominant wavelength 365nm), with super constant temperature trough to the recirculated water of logical 30 ℃ of reactor fuel factor with the elimination light source.Methylene blue concentration is 1.2 * 10 in the reaction -5Mol/L, catalyst amount are 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.The UV-irradiation apparent first order rate constant of degraded methylene blue solution down is 53 * 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 15 * 10 -3Min -1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.
Embodiment 2
In the 250mL deionized water, add 0.15mLH 3PO 2, drip 20mLTiCl under the electromagnetic agitation 4Add and continue to stir after 2 hours, begin to drip 7mol/LNaOH solution until the nearly neutrality of the pH of solution value, ageing is 1 day under 40 ℃ of water bath condition, suction filtration, and spend deionised water for several times, until using 0.5mol/LAgNO 3Solution does not detect Cl -Ion.After the oven dry, take out and grind in 80 ℃ of baking ovens, the powder 600 ℃ of roastings in Muffle furnace that obtain were obtained phosphor doped peptide oxide in 2 hours.XRD spectra shows that it is pure anatase crystal, and grain size is 15nm; N 2Physical absorption characterizes and records its specific area is 144m 2/ g.
The photocatalytic activity assay method is with embodiment 1, and the UV-irradiation apparent first order rate constant of degraded methylene blue solution down is 54 * 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.
Embodiment 3
In the 250mL deionized water, add 0.15mLH 3PO 2, drip 15mLTiCl under the electromagnetic agitation 4And 5mLTiCl 3Add and continue to stir after 2 hours, begin to drip 6mol/LNa 2CO 3Solution is near neutral until the pH of solution value, and ageing is 1 day under 40 ℃ of water bath condition, suction filtration, and spend deionised water for several times, until using 0.5mol/LAgNO 3Solution does not detect Cl -Ion.After the oven dry, take out and grind in 80 ℃ of baking ovens, the powder 300 ℃ of roastings in Muffle furnace that obtain were obtained phosphor doped peptide oxide in 4 hours.XRD spectra shows that it is pure anatase crystal.
The photocatalytic activity assay method is with embodiment 1, and the UV-irradiation apparent first order rate constant of degraded methylene blue solution down is 40 * 10 -3Min -1, than the speed constant (22 * 10 of commercialization photochemical catalyst P-25 -3Min -1) high a lot; The radiation of visible light apparent first order rate constant of degraded methylene blue solution down is 12 * 10 -3Min -1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.
Embodiment 4
Take by weighing 61.2gTi (SO 4) 2Solid is dissolved in it in 500mL water, adds 0.40mLH 3PO 2, electromagnetic agitation is after 2 hours, and it is near neutral until the pH of solution value to begin to drip 4mol/LNaOH solution, 25 ℃ of room temperature ageings 2 days, suction filtration, and spend deionised water for several times is until with 0.5mol/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 550 ℃ of roastings in Muffle furnace that obtain were obtained phosphor doped peptide oxide in 3 hours.XRD spectra shows that it is pure anatase crystal.
The photocatalytic activity assay method is with embodiment 1, and the UV-irradiation apparent first order rate constant of degraded tetrachlorophenol solution down is 16 * 10 -3Min -1, than the speed constant (5 * 10 of commercialization photochemical catalyst P-25 -3Min -1) high a lot; The radiation of visible light apparent first order rate constant of degraded methylene blue solution down is 14 * 10 -3Min -1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.
Embodiment 5
Take by weighing 48.9gTi (SO 4) 2Solid is dissolved in it in 500mL water, adds 0.40mLH 3PO 2, electromagnetic agitation began to drip 6mol/L (NH after 2 hours 4) 2CO 3Solution is near neutral until the pH of solution value, 25 ℃ of room temperature ageings 2 days, and suction filtration, and spend deionised water for several times is until with 0.5mol/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 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.
The photocatalytic activity assay method is with embodiment 1, and the UV-irradiation apparent first order rate constant of degraded tetrachlorophenol solution down is 12 * 10 -3Min -1, than the speed constant (5 * 10 of commercialization photochemical catalyst P-25 -3Min -1) high a lot; The radiation of visible light apparent first order rate constant of degraded methylene blue solution down is 11 * 10 -3Min -1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.
Embodiment 6
At the 0.25mol/L of 500mL TiOSO 4In the aqueous solution, add 0.36mLH 3PO 2, electromagnetic agitation is after 2 hours, and it is near neutral until the pH of solution value to begin to drip 1.25mol/L NaOH solution, 25 ℃ of room temperature ageings 3 days, suction filtration, and spend deionised water for several times is until with 0.5mol/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 500 ℃ of roastings in Muffle furnace that obtain were obtained phosphor doped peptide oxide in 2 hours.XRD spectra shows that it is pure anatase crystal.
The photocatalytic activity assay method is with embodiment 1, and the UV-irradiation apparent first order rate constant of degraded methylene blue solution down is 39 * 10 -3Min -1, than commercialization photochemical catalyst P-25 speed constant (22 * 10 -3Min -1) high a lot; The radiation of visible light apparent first order rate constant of degraded methylene blue solution down is 10 * 10 -3Min -1, and the photocatalytic activity of commercialization photochemical catalyst P-25 is very low.

Claims (10)

1, the preparation method of high-activity phosphor doped peptide oxide light catalyst is that Ti-inorganic salt is mixed in water with hypophosphorous acid, drips precipitating reagent again and regulates pH between the 4-8, and ageing is after washing, roasting obtain described high-activity phosphor doped peptide oxide light catalyst.
2, preparation method according to claim 1 is characterized in that: described Ti-inorganic salt is selected from TiCl 4, TiCl 3, Ti (SO 4) 2And TiOSO 4In one or more.
3, preparation method according to claim 1 is characterized in that: the mol ratio of described hypophosphorous acid and Ti-inorganic salt is 0.001-0.1: 1.
4, preparation method according to claim 1 is characterized in that: described precipitating reagent is selected from ammoniacal liquor, urea, NaOH solution, Na 2CO 3Solution, NaHCO 3Solution, (NH 4) 2CO 3Solution, NH 4HCO 3In the solution one or more.
5, preparation method according to claim 1 is characterized in that: the temperature of described ageing is 15-60 ℃, and the time is 1-3 days.
6, preparation method according to claim 1 is characterized in that: described washing is washed 2-8 time with deionized water and ethanol respectively.
7, preparation method according to claim 1 is characterized in that: the temperature of described roasting is 300-900 ℃, and the time is 1-6 hour.
8, the preparation-obtained high-activity phosphor doped peptide oxide light catalyst of the arbitrary described preparation method of claim 1-7.
9, the application of the described high-activity phosphor doped peptide oxide light catalyst of claim 8 organic pollution in light degradation air, industrial wastewater.
10, application according to claim 9 is characterized in that: described organic pollution is methylene blue and tetrachlorophenol.
CNB2007100652895A 2007-04-10 2007-04-10 High-activity phosphor doped peptide oxide light catalyst, its production and use Expired - Fee Related CN100493708C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102029168B (en) * 2009-09-28 2013-05-15 长沙市友爱实验器材有限公司 Nano titanyl pyrophosphate photocatalyst and preparation method thereof
CN103342402A (en) * 2013-07-04 2013-10-09 浙江科技学院 Method for degrading methylene blue by using nitrogen-doped oxygen vacancy type TiO2 catalyst
CN104096540A (en) * 2014-07-17 2014-10-15 同济大学 Preparation method of adsorption and catalysis material for removing heavy metals and organic pollutants in municipal sludge
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
CN108906014A (en) * 2018-08-03 2018-11-30 西南科技大学 A kind of high temperature resistant visible-light-responsive photocatalyst and preparation method 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
CN113511712A (en) * 2021-05-25 2021-10-19 中国人民解放军陆军勤务学院 Application of titanium trichloride and treatment method of high algae-laden water containing copper green microcystis

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102029168B (en) * 2009-09-28 2013-05-15 长沙市友爱实验器材有限公司 Nano titanyl pyrophosphate photocatalyst and preparation method thereof
CN103342402A (en) * 2013-07-04 2013-10-09 浙江科技学院 Method for degrading methylene blue by using nitrogen-doped oxygen vacancy type TiO2 catalyst
CN104096540A (en) * 2014-07-17 2014-10-15 同济大学 Preparation method of adsorption and catalysis material for removing heavy metals and organic pollutants in municipal sludge
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
CN108906014A (en) * 2018-08-03 2018-11-30 西南科技大学 A kind of high temperature resistant visible-light-responsive photocatalyst and preparation method 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
CN113511712A (en) * 2021-05-25 2021-10-19 中国人民解放军陆军勤务学院 Application of titanium trichloride and treatment method of high algae-laden water containing copper green microcystis

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