CN101318127A - Composite titanium dioxide visible light catalyst and preparation method thereof - Google Patents

Composite titanium dioxide visible light catalyst and preparation method thereof Download PDF

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Publication number
CN101318127A
CN101318127A CNA2007100938587A CN200710093858A CN101318127A CN 101318127 A CN101318127 A CN 101318127A CN A2007100938587 A CNA2007100938587 A CN A2007100938587A CN 200710093858 A CN200710093858 A CN 200710093858A CN 101318127 A CN101318127 A CN 101318127A
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visible light
preparation
titanium dioxide
tio
light catalyst
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CN101318127B (en
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吴瑛
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SHANGHAI MU'ER BUILDING SCIENCE AND TECHNOLOGY Co Ltd
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SHANGHAI MU'ER BUILDING SCIENCE AND TECHNOLOGY Co Ltd
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Abstract

The invention relates to a composite titanium dioxide visible-light responsive photocatalyst and a preparation method thereof; the preparation method comprises the following steps: taking ammonium metatungstate ((NH4) 6H2W12O40 and XH2O) solution; adding water according to the corrected mass ratio of 1:6-7 between WO3 and water; adding ferric nitrate (Fe (NO3)3 and 9H2O) according to the corrected mass ratio of 5-7: 1 between the WO3 and the ferric nitrate; dissolving and regulating (Fe (NO3)3 and 9H2O) to obtain impregnation liquid; adding TiO2 powder (anatase type, BET specific surface is 80-150m <2>/g) in the impregnation liquid according to the corrected mass ratio of 1:6-7 between the WO3 and the TiO2 to mix; drying for 4-6 hours under 100 DEG C; roasting for 5 hours under 580-780 DEG C and obtaining the WO3-Fe2O3/TiO2 composite photocatalyst material; wherein, the primary crystallization grain diameter of the contained tungsten oxide is 10-80nm and the crystal structure is WO3; the crystal structure of the contained ferrite oxide is Alpha-Fe2O3.

Description

A kind of composite titanium dioxide visible light catalyst and preparation method thereof
Technical field
The present invention relates to a kind of composite titanium dioxide visible light catalyst and preparation method thereof, the visible light catalyst of gained can be used for the degraded of pollutant in the environment, belongs to field of nanometer material technology.
Technical background
Titanium dioxide (TiO 2) be the semiconductor nano photochemical catalyst, have advantages such as chemical property is stable, catalytic activity is high, oxidability is strong, nontoxic, inexpensive, in fields such as air cleaning, sewage disposal, sterilization, the energy vast market prospect is arranged.At present, TiO 2The bottleneck of photocatalytic applications is that its photoresponse scope is narrower, can only utilize the ultraviolet light of wavelength less than 387nm.And ultraviolet light only accounts for 4% of its energy of sunshine, and the sunshine medium ultraviolet light in the inlet chamber is almost nil.Visible light but accounts for 45% of solar energy.Therefore, the research and development that have the photochemical catalyst of greater activity under visible light have high economy and practical value.
The doping of metal ion is to realize nano-TiO 2Under visible light, has one of effective means of photocatalytic activity.It is generally acknowledged, metal ion is incorporated into TiO 2In the lattice, can in its forbidden band, introduce impurity energy level, reduce energy gap, after making electronics in the valence band accept the bigger optical excitation of wavelength, transit to impurity energy level earlier, by absorbing energy again, transit to conduction band by impurity energy level, reduce thus and be excited required energy, thereby realize making TiO 2The spectral response range of photochemical catalyst moves to visible region.Between the several years in past, at TiO 2Middle doping platinum group metal element Pt, Pd, Rh, Ru, Ir (the Japan Patent spy opens 2004-73910), transition metal Fe, Co, Ni, Cu, Zn, Ag, Cr, V, W, Sn (Chinese patent CN 1799692A, 1583252A, 1792425A etc.), and lanthanide series La, Ce all multi-methods such as (Chinese patent CN 1557539A) all have research paper or based on the patent documentation of result of study report.These achievements in research are at the TiO that narrows 2Band gap, expansion TiO 2Aspects such as photoresponse scope bigger progress is arranged.Particularly, platinum group metal metal ion mixing TiO wherein 2Though the visible light-responded better performances of photochemical catalyst is even the platinum group metal metal that mixes seldom also causes this type of photochemical catalyst manufacturing cost too high.Mainly contain the complex centre that becomes electronics and hole because of the metal ion that mixes based on the visible light catalyst of doped with metal elements modification preparation in the problem that solves of still needing aspect the practical application and cause catalyst active decline under ultraviolet light, and degradation under the heat endurance.
Calendar year 2001, Japanese scholar R.Asahi goes up the alternative a spot of Lattice Oxygen of report nitrogen at " Science " can make TiO 2Band gap narrow down, not reducing under the photoactive prerequisite of ultraviolet, make TiO 2Have visible light activity, started nonmetal doping TiO 2Research boom (Chinese patent CN 1775359A, 1565721A, 1827225A, 1827709A, 1506154A, 1736584A etc.).From the practical application angle, the visible light catalyst of preparations such as the doped with non-metals elemental nitrogen problem that solves of still needing at present is how to improve crystallization-stable and quantum efficiency, and simplifies production technology, equipment.
The present inventor has developed a kind of composite titanium dioxide visible light catalyst and preparation method thereof by a large amount of experimental studies.The visible light catalyst of being invented has ultraviolet catalytic activity, the good stable of good visible light catalysis activity, excellence, and production technology is simple, cheap.
Summary of the invention
The objective of the invention is with the anatase titanium dioxide is matrix, a kind of method for preparing composite photocatalysis material of titanium dioxide is provided, by to the titanium deoxide catalyst modification, promptly change particle structure and surface nature, thereby enlarge the photoresponse scope, it is compound to improve quantum efficiency to suppress carrier, improves the stability of catalysis material.
Specific embodiment of the present invention and condition are: get ammonium metatungstate ((NH4) 6H 2W 12O 40XH 20) solution is by conversion WO 3Add entry with the ratio of the mass ratio 1: 6～7 of water, again by conversion WO 3Add ferric nitrate (Fe (NO with the ratio of the mass ratio 5～7: 1 of ferric nitrate 3) 39H 2O) get maceration extract after dissolving is adjusted.Again by conversion WO 3With TiO 2The ratio of mass ratio 1: 6～7 in maceration extract, add TiO 2(Detitanium-ore-type, BET specific area were 80～150m2/g) to mix to powder, in 100 ℃ of dryings 4～6 hours.Then 580 ℃～780 ℃ roasting temperatures 5 hours.Promptly get WO 3-Fe 2O 3/ TiO 2Composite photocatalyst material, wherein, the primary crystallization particle diameter 10～80nm of the tungsten oxide that is contained, crystal structure are WO 3The crystal structure of the ferriferous oxide that is contained is α-Fe 2O 3
The present invention has following advantage:
(1) WO that makes of the present invention 3-Fe 2O 3/ TiO 2Composite photocatalyst material is compared with the photochemical catalyst of undoped and single Doped Tungsten or iron, shows better photo-catalysis capability.The WO of the compound specific lattice structure of anatase titanium dioxide 3And Fe 2O 3, be actually TiO 2The modification of particle can promote the separation of charge and the charge movement of system, expansion TiO 2Spectral response range.Gained photocatalyst granular size is even, and the photoresponse expanded range will be more widely used in fields such as the depollutions of environment.
(2) the present invention adopts the visible light catalyst preparation method of a kind of novelty of dipping and roasting combination, and preparation technology's equipment is simple, good reproducibility, and production cost is low.
Description of drawings
Fig. 1: WO 3-Fe 2O 3/ TiO 2The XRD figure of composite photocatalyst material
From XRD figure, can see that Detitanium-ore-type TiO is arranged 2, WO 3And α-Fe 2O 3Diffraction maximum, this explanation contains above-mentioned three kinds of materials in products obtained therefrom, has reached the preparation purpose.Maximum diffraction peak is TiO in 25.89 ° 2The diffraction maximum of crystal face.Calculate according to the Scherrer formula, the particle diameter of this sample is 18nm.
Fig. 2: visible light catalytic acetaldehyde decomposition run is comparison diagram as a result
Fig. 2: ultraviolet catalytic acetaldehyde decomposition run is comparison diagram as a result
The specific embodiment
Embodiment 1
Commercially available ammonium metatungstate ((NH4) 6H 2W 12O 40XH 20) solution (conversion WO 3Concentration 50wt%) 60g adds entry 200g, adds ferric nitrate (Fe (NO again 3) 39H 2O) get maceration extract after the 4.5g dissolving is adjusted.In maceration extract, add commercially available TiO again 2Powder (Detitanium-ore-type, BET specific area are 85m2/g, Millennium Chemicals Inc. product) 200g mixed, in 100 ℃ of dryings 5 hours.Then 660 ℃ of roasting temperatures 5 hours.Promptly get WO 3-Fe 2O 3/ TiO 2Composite photocatalyst material.Measure according to XRD figure, contain WO in the embodiment 1 gained sample 3Rhomboidal crystal, this WO 3Particle diameter be 47nm.
Embodiment 2
In the foregoing description 1, change use amount (the mass ratio TiO of ammonium metatungstate and ferric nitrate 2/ WO 3/ Fe 2O 3=100/23/1.0; Mol ratio Fe/W=0.12), other conditions are constant.Make WO 3-Fe 2O 3/ TiO 2Composite photocatalyst material.Measure according to XRD figure, contain WO in the embodiment 2 gained samples 3Rhomboidal crystal, this WO 3Particle diameter be 38nm.
Embodiment 3
In the foregoing description 1, to change into 760 ℃ except that sintering temperature, other conditions are constant.Make WO 3-Fe 2O 3/ TiO 2Composite photocatalyst material.Measure according to XRD figure, contain WO in the embodiment 3 gained samples 3Rhomboidal crystal, this WO 3Particle diameter be 70nm.
Embodiment 4
In the foregoing description 1, change use amount (the mass ratio TiO of ammonium metatungstate and ferric nitrate 2/ WO 3/ Fe 2O 3=100/76/2.0; Mol ratio Fe/W=0.081), other conditions are constant.Make WO 3-Fe 2O 3/ TiO 2Composite photocatalyst material.Measure according to XRD figure, contain WO in the embodiment 4 gained samples 3Rhomboidal crystal, this WO 3Particle diameter be 38nm.
Reference example 1
In the foregoing description 1, except that not adding the ferric nitrate, other conditions are constant.Make WO 3/ TiO 2Composite photocatalyst material.Measure according to XRD figure, contain WO in the embodiment 3 gained samples 3Rhomboidal crystal, this WO 3Particle diameter be 23nm.
Comparative example 1
Only adopt commercially available WO 3(Japanese Wako Pure Chemical Industries, Ltd. product).Use electron microscope observation, particle diameter reaches more than the 2000nm.
Comparative example 2
Only adopt with " embodiment 1 " in the TiO of use 2Identical commercially available TiO 2
Test example 1
Test film is madePrepared photochemical catalysts such as the foregoing description, reference example, comparative example are disperseed with ethanol respectively and, with 20g/m 2Consumption coat on the sheet glass of 140 * 110mm, be drying to obtain in 65 ℃.
Test methodTest film is placed respectively in the quartz glass system 5L reactor.Make its initial concentration reach 10ppm toward the interior acetaldehyde that injects of reactor, with light exposure experiment sheet.Change illumination condition and simulate the wave-length coverage of visible light, ultraviolet light respectively, establish the aldehydes gas concentration of spectrometry mensuration corresponding to irradiation time with gas phase.
Visible light catalytic performance test resultWith 2 of 4W fluorescent lamps, shine from the reactor outside to sheet on probation.Optical filter is affixed on the plane of illumination of reactor, makes the following all eliminations of ultraviolet ray of 420nm.The part test result as shown in Figure 2.
Ultraviolet catalytic performance test resultUse the 4W ultraviolet lamp, shine from the reactor outside to sheet on probation.Do not paste the optical filter film.The part test result as shown in Figure 4.

Claims (6)

1. composite titanium dioxide visible light catalyst and preparation method thereof is characterized in that, main preparation process is: at first at ammonium metatungstate ((NH 4) 6H 2W 12O 4OXH 2O) behind the solution thin up, add a little ferric nitrate (Fe (NO 3) 39H 2O) get maceration extract after dissolving is adjusted.In maceration extract, add titanium dioxide (TiO again 2) powder mixes, in 100 ℃ of dryings 4～6 hours.Roasting 5 hours under specified temp then promptly gets object.
2. preparation method as claimed in claim 1 is characterized in that, above-mentioned sintering temperature is 580 ℃～780 ℃.
3. preparation method as claimed in claim 2 is characterized in that, wherein used titanium dioxide has Detitanium-ore-type (Anatase) crystal structure, the BET specific area is 80～150m2/g.
4. visible light catalyst as claimed in claim 1 is characterized in that, it is a kind of WO 3-Fe 2O 3/ TiO 2Composite photocatalyst material.
5. visible light catalyst as claimed in claim 4 is characterized in that the primary crystallization particle diameter 10～80nm of the tungsten oxide that is contained, crystal structure are WO 3The crystal structure of the ferriferous oxide that is contained is α-Fe 2O 3
6. visible light catalyst as claimed in claim 5 is characterized in that, is matrix with titanium dioxide, and the content of tungstic acid is 20～50wt%, and the content of di-iron trioxide is 0.4～2.8%.
CN2007100938587A 2007-06-08 2007-06-08 Composite titanium dioxide visible light catalyst and preparation method thereof Expired - Fee Related CN101318127B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002746A (en) * 2010-11-03 2011-04-06 厦门大学 Method for preparing iron oxide nano granule modified titanium dioxide nano tube array
CN102730767A (en) * 2012-06-13 2012-10-17 湖北工业大学 Rapid preparation method of nano alpha-iron oxide powder
DE102011103504A1 (en) 2011-06-04 2012-12-06 Gmbu E.V., Fachsektion Dresden Photoactive textile material produced by coating a pre-treated textile material with a nanocrystalline titania sol containing a noble metal salt and a chelating agent, useful as photocatalyst to degrade organic substances in waste water
CN105983335A (en) * 2014-09-30 2016-10-05 首尔伟傲世有限公司 Photocatalytic filter for degrading mixed gas and manufacturing method thereof
US10213779B2 (en) 2014-09-04 2019-02-26 Seoul Viosys Co., Ltd. Photocatalytic filter, method for manufacturing the same, and method for reactivating the same
CN110841699A (en) * 2019-10-22 2020-02-28 中国石油天然气股份有限公司 Photocatalyst for improving volatile organic compound treatment efficiency and preparation method thereof
CN113877589A (en) * 2021-09-16 2022-01-04 安徽元琛环保科技股份有限公司 Method for preparing photocatalyst by regenerating and recycling waste SCR denitration catalyst and photocatalyst
CN115055188A (en) * 2022-06-10 2022-09-16 长安大学 Composite modified nano TiO for tunnel 2 Tail gas degradation material and preparation method thereof

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CN100404109C (en) * 2005-05-20 2008-07-23 清华大学 Plasma discharge catalytic air purifier
CN100357020C (en) * 2005-07-13 2007-12-26 北京化工大学 Preparation for load type nano composite photocatalyst for catalyzing oxidizing degrading organism under sun lighting

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002746A (en) * 2010-11-03 2011-04-06 厦门大学 Method for preparing iron oxide nano granule modified titanium dioxide nano tube array
CN102002746B (en) * 2010-11-03 2013-03-27 厦门大学 Method for preparing iron oxide nano granule modified titanium dioxide nano tube array
DE102011103504A1 (en) 2011-06-04 2012-12-06 Gmbu E.V., Fachsektion Dresden Photoactive textile material produced by coating a pre-treated textile material with a nanocrystalline titania sol containing a noble metal salt and a chelating agent, useful as photocatalyst to degrade organic substances in waste water
CN102730767A (en) * 2012-06-13 2012-10-17 湖北工业大学 Rapid preparation method of nano alpha-iron oxide powder
US10213779B2 (en) 2014-09-04 2019-02-26 Seoul Viosys Co., Ltd. Photocatalytic filter, method for manufacturing the same, and method for reactivating the same
US11565246B2 (en) 2014-09-04 2023-01-31 Seoul Viosys Co., Ltd. Photocatalytic filter, method for manufacturing the same, and method for reactivating the same
CN105983335A (en) * 2014-09-30 2016-10-05 首尔伟傲世有限公司 Photocatalytic filter for degrading mixed gas and manufacturing method thereof
CN110841699A (en) * 2019-10-22 2020-02-28 中国石油天然气股份有限公司 Photocatalyst for improving volatile organic compound treatment efficiency and preparation method thereof
CN110841699B (en) * 2019-10-22 2022-11-01 中国石油天然气股份有限公司 Photocatalyst for improving volatile organic compound treatment efficiency and preparation method thereof
CN113877589A (en) * 2021-09-16 2022-01-04 安徽元琛环保科技股份有限公司 Method for preparing photocatalyst by regenerating and recycling waste SCR denitration catalyst and photocatalyst
CN113877589B (en) * 2021-09-16 2024-01-19 安徽元琛环保科技股份有限公司 Method for preparing photocatalyst by regenerating and recycling waste SCR denitration catalyst and photocatalyst
CN115055188A (en) * 2022-06-10 2022-09-16 长安大学 Composite modified nano TiO for tunnel 2 Tail gas degradation material and preparation method thereof

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