CN101780416B - Iron and chrome co-doped nano titanium dioxide/zeolite compound photocatalyst and preparation method thereof - Google Patents
Iron and chrome co-doped nano titanium dioxide/zeolite compound photocatalyst and preparation method thereof Download PDFInfo
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- CN101780416B CN101780416B CN 201010101536 CN201010101536A CN101780416B CN 101780416 B CN101780416 B CN 101780416B CN 201010101536 CN201010101536 CN 201010101536 CN 201010101536 A CN201010101536 A CN 201010101536A CN 101780416 B CN101780416 B CN 101780416B
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Abstract
The invention provides an iron and chrome co-doped nano titanium dioxide/zeolite compound photocatalyst and a preparation method thereof, and relates to sewage and waste gas treatment. The iron and chrome co-doped nano titanium dioxide/zeolite compound photocytalyst is characterized in that: nano TiO2 is doped with 0.5 to 2.5 weight percent of iron and chrome ions; the mass ratio of Fe3+ to Cr3+ is controlled to be 1:1-4; the Fe3+ and Cr3+ ions and Ti4+ ions with positive electricity are self-assembled on a zeolite substrate modified by negative electricity under the action of electrostatic attraction, the metal ions are combined together and then the zeolite substrate is baked to prepare the photocatalyst; and nano TiO2 crystals are mixed crystals of anatase crystals and rutile crystals. The iron and chrome co-doped nano titanium dioxide/zeolite compound photocatalyst has the advantages that: compared with the prior art, the compound material has the photocatalytic activity improved by over 40 percent, is filtered and dried for recycling, and then can still have relatively high photocatalytic activity; and the iron and chrome co-doped nano titanium dioxide/zeolite compound photocatalyst has the advantages of low cost, easy recycling, no pollution, great social and economic benefits, and good industrial application prospect.
Description
Technical field
The present invention relates to sewage and technical field of waste gas treatment.
Background technology
It is the major issue that environmental area is badly in need of solution that organic pollution in sewage and the waste gas is handled, and also is the key issue that country presses for solution.The Nano semiconductor photocatalysis technology is that sewage and exhaust-gas treatment provide a new approach, utilizes this technique almost can not have all organic pollutions of mineralising of selection, is considered to a kind of environmental contaminants advanced treating technology of environmental protection the most.TiO in the semiconductor
2Because after having illumination photoetch does not take place, resistance to acids and bases is good, chemical property is stable, and to biological nontoxic property, the source is abundant, and the photocatalytic activity advantages of higher is so be the emphasis of present research.Nano-TiO
2Shortcomings such as powder is prone to reunite owing to existing in application process, difficult recovery are so generally study its immobilized supported technology at present.With nano-TiO
2Be assembled in and prepare nano-TiO in the porous zeolite
2/ zeolite composite photocatalyst material has been realized nano-TiO
2In the time of immobilized supported, also realized the synergy of photocatalysis and absorption.At present, about nano-TiO
2The existing many reports of the research of/zeolite composite photocatalyst material; Invented a kind of nano titanium oxide/zeolite composite photocatalyst material and preparation method thereof (Chinese patent like Wang Jing etc.; Application number 200510027382.8); The zeolite molecular sieve that different skeletons are formed is immersed in the containing metal Ti ion solution; Evaporate to dryness, roasting then formed the purpose of the high photocatalysis performance of the nano titanium oxide/zeolite composite photocatalyst composite, the acquisition that reach the different crystalline phase ratios with rutile of preparation anatase through changing the matrix zeolitic frameworks, this composite have prepare easy, with low cost, catalytic activity is controlled and nontoxic; Be easy to characteristics such as recovery, and suitable large-scale production.Because TiO
2Energy gap is about 3.2eV, needs ultraviolet excitation, and the electron-hole pair that produces in addition is very easily compound, thereby causes nano-TiO
2Photocatalytic activity is not high.Through the metal ion mixing method is the effective way that addresses the above problem, through the nano-TiO of metal ion mixing
2Photochemical catalyst photoresponse scope is expanded, and photocatalytic activity improves.Choi etc. have studied 21 kinds of different metallic ion-doped nano TiO
2Photocatalytic activity, show: Fe
3+Doped Ti O
2Show higher photocatalytic activity.Fe
3+Ion substitution TiO
2Ti in the lattice
4+And the formation shallow energy level, thereby reduce the recombination probability in electronics-hole, improve the photocatalytic activity of material.Hou Tianyi etc. are with FeCl
3And TiCl
4For predecessor has prepared Fe
3+Dopen Nano TiO
2/ zeolite composite photocatalyst material shows Fe
3+Dopen Nano TiO
2/ zeolite composite photocatalyst material is than nano-TiO
2/ zeolite composite photocatalyst material photocatalytic activity increases.Researchs such as Yang show: the TiO that adopts two kinds of adulterants to mix
2The TiO that more a kind of adulterant mixes
2Visible light-responded scope is wideer, photocatalytic activity is higher.Yuan Zhongyong etc. have invented a kind of iron and nitrogen co-doped mesoporous titanium oxide photochemical catalyst material and preparation method thereof (Chinese patent, application number 200910067690.1), show that iron and nitrogen co-doped meso-porous titanium oxide have good photocatalytic activity.
Summary of the invention
The purpose of this invention is to provide siderochrome coblended nano TiO 2/zeolite compound photocatalyst and method for making thereof, this composite has photocatalytic activity height, recycle property characteristics preferably; Low, the easy recovery of cost, pollution-free has bigger economic results in society and industrial applications prospect.
One of the present invention is achieved in that a kind of siderochrome coblended nano TiO 2/zeolite compound photocatalyst, is on the carrier with the zeolite, it is characterized in that nano-TiO
2The siderochrome ion of doping 0.5wt%～2.5wt%, Fe
3+And Cr
3+Mass ratio be controlled at 1: 1～4, the Fe of positively charged
3+, Cr
3+Ion and Ti
4+Ion being self-assembled on the electronegative zeolite matrix under the effect of electrostatic attraction, combines between the metal ion together, makes through calcination process again.
Described nano-TiO
2Crystal is the mixed crystal of Detitanium-ore-type and rutile-type, and the ratio of anatase crystal and rutile crystal type is 4～2: 2.
Described self-assembling method can be: be carrier with the zeolite, with its surface modification and electronegative; With TiCl
4Solution is the Ti source, adopts the Fe of different proportion
3+, Cr
3+Ion co-doped, the Fe of positively charged
3+, Cr
3+Ion and Ti
4+Ion is self-assembled on the electronegative zeolite matrix by the effect of electrostatic attraction together.
The present invention's two is achieved in that a kind of method for making of siderochrome coblended nano TiO 2/zeolite compound photocatalyst, it is characterized in that having following steps:
A, zeolite surface negative electricity modify: with the zeolite is carrier, with the zeolite surface modification and electronegative;
B, self assembly: with TiCl
4Solution is the Ti source, adopts the Fe of different proportion and content
3+, Cr
3+Ion co-doped; Fe with positively charged
3+, Cr
3+Ion and Ti
4+Ion is self-assembled on the electronegative zeolite matrix by the effect of electrostatic attraction together, makes between the metal ion evenly to combine effectively;
C, roasting: the roasting through uniform temperature makes Fe
3+, Cr
3+Get into TiO
2The recombination probability of electron-hole pair is reduced.
Described sintering temperature is preferably 200 ℃～500 ℃, and time 1h～4h makes Fe
3+, Cr
3+Get into TiO
2In the lattice, the recombination probability of electron-hole pair is reduced.
Described nano-TiO
2Crystal is the mixed crystal of Detitanium-ore-type and rutile-type, and the ratio of anatase crystal and rutile crystal type is 4～2: 2.
Described zeolite surface negative electricity method of modifying can be: adopt mercaptopropyl trimethoxysilane coupling agent dry method modification zeolite, 100 ℃～140 ℃ of coupling agent consumption 1.0wt%～8.0wt%, modification temperatures; Adopt oxidant 30%H
2O
2/ HOAc is oxidized to sulfonic acid group with the coupling agent mercapto groups, and the oxidant consumption is 60 ℃～80 ℃ of 8～12 times of theoretical consumption, oxidizing temperature.
The described self-assembling method of electrostatic attraction effect that receives can be: electronegative zeolite is made into water: zeolite is 8～12: 1 ore pulp, pipettes TiCl
4Solution and FeCl
3And Cr (NO
3)
3Mixed solution is added dropwise in the ore pulp, regulates pH to certain limit, and the water-bath certain hour, again through ageing, filtration.
The described preferable amount that is added dropwise to the mixed solution in the ore pulp is: TiO
2The theoretical negative carrying capacity is the TiCl of 20wt%～50wt%
4Solution; Pipette FeCl
3And Cr (NO
3)
3Mixed solution, the siderochrome ion concentration is TiO
20.5wt%～the 2.5wt% of theoretical negative carrying capacity, Fe
3+And Cr
3+Mass ratio be controlled at 1: 1～4.
Described adjusting pH to certain limit does, with HCl and NH
3H
2O solution regulator solution pH is 1～4,50 ℃～90 ℃ of bath temperature controls, reaction time 2h～6h, ageing 10h～14h.
Good effect of the present invention is: compared with prior art, the photocatalytic activity of this composite can improve more than 40%, and recycle after suction filtration, drying still keeps relative higher photocatalytic activity; Low, the easy recovery of cost, pollution-free has very big economic results in society and industrial applications prospect.
Be described further below in conjunction with instance, but not as to qualification of the present invention.
Description of drawings
Fig. 1 is 400 ℃ of roasting siderochrome co-doped nano TiO
2/ zeolite compound photocatalyst XRD analysis collection of illustrative plates.
1., 2. Fig. 2 is 400 ℃ of roasting siderochrome co-doped nano TiO
2/ zeolite compound photocatalyst FESEM photo.
Fig. 3 is respectively 400 ℃ of roasting siderochrome co-doped nano TiO of static self-assembling method preparation
2400 ℃ of roasting nano-TiOs of/zeolite composite photocatalyst material, the preparation of static self-assembling method
2/ zeolite composite photocatalyst material and Zeolite support not negative electricity modification promptly do not adopt the preparation of static self-assembling method and unadulterated 400 ℃ of roasting nano-TiOs
2/ zeolite composite photocatalyst material is to the photocatalysis treatment effect of methyl orange dye waste water.
Fig. 4 is respectively 400 ℃ of roasting siderochrome co-doped nano TiO of static self-assembling method preparation
2/ zeolite composite photocatalyst material and do not adopt the static self-assembling method and unadulterated 400 ℃ of roasting nano-TiOs
2The effect of/zeolite composite photocatalyst material circular treatment methyl orange dye waste water.
The specific embodiment
Embodiment 1:
The zeolite surface negative electricity is modified: take by weighing the 25g zeolite and put into there-necked flask; Add 0.5mL mercaptopropyl trimethoxysilane coupling agent and 0.5mL absolute ethyl alcohol mixed solution (coupling agent modified amount is the 2wt% of zeolite); Oil bath is heated to 120 ℃, and heated at constant temperature stirs 30min and obtains silane coupler modified zeolite; Take by weighing the silane-modified zeolite of 10g, add oxidant 4mL 30%H
2O
2With 20mL HOAc mixed solution (mercapto groups is oxidized to 10 times of the theoretical consumption of sulfonic acid group oxidant), 50 ℃ of oxidation 2h obtain the zeolite that negative electricity is modified.
Nano-TiO
2The load of/Zeolite composite materials: take by weighing the zeolite that the 15g negative electricity is modified, add the 150mL deionized water and be made into ore pulp; Pipette the TiCl that 41.7mL concentration is 1.93mol/L
4Solution (TiO
2The TiCl that theoretical negative carrying capacity 30wt% is required
4Solution amount), take by weighing 0.0207gFeCl simultaneously respectively
36H
2O and 0.1319g Cr (NO
3)
39H
2O (Fe
3+And Cr
3+Total ion concentration is TiO
2The 1wt% of load capacity, Fe
3+And Cr
3+Mass ratio be 1: 4) be dissolved in the 10mL deionized water fully dissolving back and TiCl
4Solution mixes and is added dropwise in the ore pulp, with HCl and NH
3H
2O solution regulation system pH is 2; 70 ℃ of bath temperatures constantly stir and reaction time 4h, ageing 12h, and suction filtration, 80 ℃ of dryings obtain siderochrome co-doped nano TiO in 400 ℃ of roasting 2h again
2/ zeolite compound photocatalyst.
Material composition test shows in the table 1: siderochrome co-doped nano TiO
2TiO in the/Zeolite composite materials
2The quality percentage composition is 27.1wt%, is more or less the same with theoretical negative carrying capacity 30%, shows that the static self-assembling method realized that zeolite is to TiO
2High capacity efficient.Cr in the composite
3+Ion concentration is TiO
2The 0.74wt% of content, Fe
3+Be TiO behind the Fe impurity in the ion concentration deduction zeolite raw ore
2The 0.19wt% of content.Cr
3+With Fe
3+Content and ratio meet doping and the ratio that experiment is adopted basically.The XRD figure stave of Fig. 1 composite is bright: nano-TiO
2Crystal is the mixed crystal of Detitanium-ore-type and rutile-type, and the ratio of the two is about 3: 2.The field emission scanning electron microscope photo of Fig. 2 composite shows: nano-TiO
2Be assembled in to uniform particles in the surface and hole of zeolite.
The evaluation of material light catalysis property: the photocatalysis performance that adopts methyl orange dye waste water evaluating material.Waste strength 10mg/L, methyl orange maximum absorption wavelength 464nm.Light source is 1 40W, and dominant wavelength is the ultraviolet lamp tube of 253.7nm.Adopt the 722S ultraviolet-visible spectrophotometer to estimate the percent of decolourization of catalysis material, computing formula is: P=(A
0-A
t)/A
0* 100%.In the formula: P is the percent of decolourization of the material of preparation to waste water; A
0Absorbance for the raw wastewater that is untreated; A
tBe absorbance through t time processed waste water.400 ℃ of roasting siderochrome co-doped nano TiO of static self-assembling method preparation among Fig. 3
2400 ℃ of roasting nano-TiOs of/zeolite composite photocatalyst material, the preparation of static self-assembling method
2/ zeolite composite photocatalyst material and Zeolite support not negative electricity are modified 400 ℃ of roasting nano-TiOs that promptly do not adopt the preparation of static self-assembling method
2/ zeolite composite photocatalyst material shows the photocatalysis treatment effect of methyl orange dye waste water: the composite behind the siderochrome codope to the percent of decolourization of methyl orange dye waste water respectively than doped and compounded material not with do not adopt the composite high 26.81% and 40.69% of static self-assembling method preparation.400 ℃ of roasting siderochrome co-doped nano TiO of static self assembly preparation among Fig. 4
2/ zeolite composite photocatalyst material and 400 ℃ of roasting nano-TiOs that do not adopt the static self-assembling method to prepare
2/ zeolite composite photocatalyst material handles methyl orange dye waste water after suction filtration, dry back circular treatment methyl orange dye waste water; The result shows: drop to 45.04% through siderochrome codope composite photocatalysis decolorizing effect to methyl orange dye waste water after three circulations; But compare with adopting not static self-assembling method preparation and unadulterated composite, it is to the photocatalysis decolorizing effect still high 28.15% of methyl orange dye waste water.
Table 1 is instance 1 siderochrome co-doped nano TiO
2/ zeolite chemical composition.
Siderochrome co-doped nano TiO
2/ zeolite chemical component table 1
| Chemical composition | Na 2O | MgO | Al 2O 3 | SiO 2 | K 2O | CaO | TiO 2 | Cr 2O 3 | MnO | Fe 2O 3 |
| Zeolite | 0.8 | 0.9 | 11.7 | 66.4 | 1.85 | 3.01 | - | - | 0.06 | 1.06 |
| Composite photocatalyst material | 0.56 | 0.22 | 6.81 | 44.1 | 0.79 | 0.14 | 27.1 | 0.59 | 0.04 | 0.98 |
The proportioning of embodiment 1～13 and condition table table 2
| Embodiment | Consumption/the wt% of coupling agent | Fe 3+、Cr 3+Volume/wt% | Fe 3+、Cr 3+Ratio/wt% | Sintering temperature/℃ | Anatase and rutile ratio/% | Photocatalysis percent of decolourization/% |
| 1 | 2 | 1 | 1∶4 | 400 | 62.1∶37.9 | 92.46 |
| 2 | 2 | 1 | 1∶4 | 200 | 59.9∶40.1 | 79.26 |
| 3 | 2 | 1 | 1∶1 | 400 | 61.9∶38.1 | 89.71 |
| 4 | 2 | 1 | 1∶1 | 200 | 60.4∶39.6 | 75.38 |
| 5 | 1 | 0.5 | 1∶4 | 400 | 62.3∶37.8 | 80.32 |
| 6 | 1 | 2 | 1∶4 | 400 | 62.7∶37.3 | 89.48 |
| 7 | 4 | 1 | 1∶4 | 400 | 62.9∶37.1 | 93.70 |
| 8 | 4 | 2 | 1∶4 | 400 | 62.0∶38.0 | 90.09 |
| 9 | 6 | 1 | 1∶4 | 400 | 62.2∶37.8 | 96.35 |
| 10 | 6 | 1 | 1∶4 | 500 | 63.5∶36.5 | 88.66 |
| 11 | 8 | 1 | 1∶4 | 400 | 62.7∶37.3 | 94.19 |
| 12 | 8 | 2 | 1∶4 | 400 | 62.6∶37.4 | 91.27 |
| 13 | 8 | 2.5 | 1∶4 | 400 | 62.3∶37.7 | 90.21 |
Claims (2)
1. the method for making of a siderochrome coblended nano TiO 2/zeolite compound photocatalyst is characterized in that having following steps:
A, zeolite surface negative electricity are modified: with the zeolite is carrier; With the zeolite surface modification and electronegative; Zeolite surface negative electricity method of modifying is: adopt mercaptopropyl trimethoxysilane coupling agent dry method modification zeolite, 100 ℃ 140 ℃ of modifier consumption 1.0 wt% 8.0 wt%, modification temperatures; Adopt oxidant 30%H
2O
2/ HOAc is oxidized to sulfonic acid group with the coupling agent mercapto groups, and the oxidant consumption is 60 ℃ 80 ℃ of 8 12 times of theoretical consumption, oxidizing temperature;
B, self assembly: with TiCl
4Solution is the Ti source, adopts the Fe of different proportion and content
3+, Cr
3+Ion co-doped; Fe with positively charged
3+, Cr
3+Ion and Ti
4+Ion is self-assembled on the electronegative zeolite matrix by the effect of electrostatic attraction together; Make between the metal ion and evenly combine effectively; Receive the effect self-assembling method of electrostatic attraction to be: it is the ore pulp of 8 12 ︰ 1 that electronegative zeolite is made into Shui ︰ zeolite, pipettes TiCl
4Solution and FeCl
3And Cr (NO
3)
3Mixed solution is added dropwise in the ore pulp, regulates pH to certain limit, and the water-bath certain hour, again through ageing, filtration, with HCl and NH
3H
2O solution regulator solution pH is 14,50 ℃ 90 ℃ of bath temperature controls, reaction time 2 h 6 h, ageing 10 14h; The amount that is added dropwise to the mixed solution in the ore pulp is: TiO
2The theoretical negative carrying capacity is the TiCl of 20 wt%, 50 wt%
4Solution; FeCl
3And Cr (NO
3)
3Mixed solution, the siderochrome ion concentration is TiO
20.5 wt%, 2.5 wt% of theoretical negative carrying capacity, Fe
3+And Cr
3+Mass ratio be controlled at 1 ︰ 1～4;
C, roasting: the roasting through uniform temperature makes Fe
3+, Cr
3+Get into TiO
2The recombination probability of electron-hole pair is reduced.
2. the method for making of siderochrome coblended nano TiO 2/zeolite compound photocatalyst according to claim 1 is characterized in that described sintering temperature is 200 ℃ 500 ℃, and time 1 h 4 h make Fe
3+, Cr
3+Get into TiO
2In the lattice, the recombination probability of electron-hole pair is reduced.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103861593B (en) * | 2014-03-25 | 2016-08-17 | 陕西科技大学 | A kind of chromium silver co-doped nano TiO2photocatalyst and its production and use |
| CN104624222B (en) * | 2015-01-27 | 2017-01-18 | 天津城建大学 | Method for preparing CuO-TiO2/zeolite nanocomposite material for treating dye wastewater |
| JP6010718B1 (en) * | 2016-07-01 | 2016-10-19 | 株式会社ダイセル | Iron compound-supported titanium oxide photocatalyst |
| CN106495510B (en) * | 2016-09-29 | 2019-07-12 | 陕西科技大学 | A kind of nano-TiO with photo-catalysis function2/ Zeolite modifying cement and preparation method thereof |
| CN111768974B (en) * | 2020-06-22 | 2021-11-26 | 广西大学 | Method for preparing medium-low voltage laminated foil containing composite medium by surface self-assembly method |
| CN113174036B (en) * | 2021-04-28 | 2023-03-28 | 浙江联盛化学股份有限公司 | Rare earth doped molecular sieve catalyst, preparation method and application thereof |
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| CN1805781A (en) * | 2003-04-17 | 2006-07-19 | 约翰逊马西有限公司 | Method of decomposing nitrogen dioxide. |
| CN101072622A (en) * | 2004-10-12 | 2007-11-14 | 约翰逊马西有限公司 | Method of decomposing nitrogen dioxide |
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| CN1805781A (en) * | 2003-04-17 | 2006-07-19 | 约翰逊马西有限公司 | Method of decomposing nitrogen dioxide. |
| CN101072622A (en) * | 2004-10-12 | 2007-11-14 | 约翰逊马西有限公司 | Method of decomposing nitrogen dioxide |
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