CN101850268A - Nano titanium dioxide thin film and preparation method and application thereof - Google Patents

Nano titanium dioxide thin film and preparation method and application thereof Download PDF

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Publication number
CN101850268A
CN101850268A CN201010203495A CN201010203495A CN101850268A CN 101850268 A CN101850268 A CN 101850268A CN 201010203495 A CN201010203495 A CN 201010203495A CN 201010203495 A CN201010203495 A CN 201010203495A CN 101850268 A CN101850268 A CN 101850268A
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iron
nano
titanium dioxide
mass ratio
gel
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CN101850268B (en
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廖禹东
赵风英
郭忠
钟金莲
邱春兰
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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
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention relates to technology of a preparation for purifying water and degrading pharmaceutical wastewater, in particular to a nano titanium dioxide thin film and a preparation method and application thereof. The nano titanium dioxide thin film is prepared from 3.33 to 9.09 mass percent of iron ion-doped nano titanium dioxide and 90.91 to 96.67 mass percent of agarose gel and the iron ions account for 0.05 percent of the mass of the nano titanium dioxide. During the degradation of the pharmaceutical wastewater, the removing rate of the chemical oxygen demand (COD) in the same time is increased by over 39 percent compared with that of the thin film with a glass carrier; and just like the thin films with other carriers, the COD removing rate can reach over 99 percent after continuous degradation.

Description

A kind of nano-titanium dioxide film and preparation method and application
Technical field
The present invention relates to purify waste water and the degrade technology of pharmacy waste water preparation, particularly a kind of nano-titanium dioxide film and preparation method and application.
Background technology
Great majority are with TiO in the research in past 2Handle with waste water formation suspended state, but because the loss of suspension photocatalytic agent active component is big, easily cohesion, difficulty reclaim in water, and TiO 2Powder and moisture from expense height, particularly repeat usage also lower, moreover because TiO 2Photochemical catalyst band-gap energy (3.2ev) broad in principle can only absorbing wavelength be shorter than the ultraviolet light of 387nm, and photoresponse narrow range, light induced electron and hole are easily compound, and photo-quantum efficiency is lower, has limited TiO 2The practical application of catalysis material and development.
For overcoming suspended state TiO 2Easily cohesion in the water, difficult recovery, active component are lost shortcomings such as big, and people turn to sight to TiO 2Carry out the fixing research of load.Used carrier of photocatalyst mainly contains category of glass, metal species, absorption class, ceramic-like and cation exchange column, high molecular polymer etc. both at home and abroad at present.Glass surface is very smooth, to nano-TiO 2The absorption property relative mistake, and unstable, easily come off, cause to recycle rate variance; Metal species is metal price costliness and load difficulty then; The material of absorption class itself often is a fine granularity, and directly using in the aqueous solution still needs to carry out with suspension system, still has the filtering photochemical catalyst after the reaction; Photocatalytic activity had shortcomings such as reduction in various degree after other then had existence preparation worker complex process, cost height even the photochemical catalyst load is arranged, therefore, seek to realize that catalyst is immobilized, the carrier that can keep original photocatalytic activity again is the focus of research work.
Summary of the invention
The object of the invention provides a kind of nano titanium oxide Ago-Gel film of loaded iron doped ion, also comprises its preparation method and application.
Technical solution of the present invention: a kind of nano-titanium dioxide film comprises nano titanium oxide, the Ago-Gel of iron-doped iron.
The nano titanium oxide mass ratio of iron-doped iron is 3.33%-9.09.%, and the Ago-Gel mass ratio is that the nano titanium oxide mass ratio that 90.91%-96.67%, iron ion account for iron-doped iron is 0.05%.
The nano titanium oxide mass ratio of iron-doped iron is 9.09%, and the Ago-Gel mass ratio is 90.91%.
Adopt sol-gel process to prepare the nano titanium oxide of iron-doped iron.
Prepare a kind of nano-titanium dioxide film method, carry out according to the following steps:
A adopts the sol-gel process preparation to mix Fe 3+Nano-TiO 2
With butyl titanate, glacial acetic acid, absolute ethyl alcohol, ferric nitrate is raw material, and butyl titanate, glacial acetic acid, absolute ethyl alcohol three's volume ratio is 1: 1.2: 5, and wherein 1/3 absolute ethyl alcohol is made preparation iron nitrate solution usefulness, will prepare mass ratio at 0.01%-0.1%Fe 3+The ferric nitrate ethanolic solution place dropping funel, add entry, the volume ratio of water and ferric nitrate ethanolic solution is 1: 2, under constantly stirring, dropwise join in the mixed liquor of butyl titanate, glacial acetic acid and absolute ethyl alcohol, after dropwising, continue to stir 1 hour until generating faint yellow colloidal sol, placed 2-3 days, behind the gel to be formed, place 110 ℃ of constant temperature vacuum drying, pulverize again, and, obtain the Fe of Detitanium-ore-type and rutile-type mixing crystal formation at 550-600 ℃ of roasting temperature 3+/ TiO 2Nanometer powder;
B prepares the nano titanium oxide Ago-Gel film of loaded iron doped ion
Place 80-85 ℃ of water-bath to heat the conical flask that fills distilled water, conical flask should seal during heating, adding mass ratio when the distilled water water temperature reaches 45 ℃ is the 1%-10% agarose, and constantly jolting, and adding mass ratio after agarose melts fully is 0.1-0.5%Fe 3+/ TiO 2, constantly jolting is poured solution in the mould into to thick liquid, promptly gets Fe after the cooling 3+/ TiO 2The Ago-Gel film.
A kind of nano-titanium dioxide film is used, with ultraviolet source or visible light direct irradiation solution, i.e. and photocatalytic degradation pharmacy waste water or surface water, the reaction temperature of degraded is 10 ℃-40 ℃, and lasting bubbling air is kept the concentration of dissolved oxygen.
Good effect of the present invention: (1) crystal formation of the present invention does not change, and still for mixing crystal formation, promptly catalytic activity does not become; Moreover agglomeration of the present invention obviously reduces, thereby catalytic activity has raising.(2) photochemical catalyst of the present invention preparation and Ago-Gel form high-intensity bonding, difficult drop-off, in the process that recycles, its efficient remains unchanged basically.(3) the present invention joins in the surface water such as general running water, well water and mountain spring water, under ultraviolet source or direct irradiation of sunlight, and not only sterilizing fully, and TiO 2Photocatalysis can be converted into CO with organic pollution effectively 2, H 2O, PO 4 3-, SO 4 2-, NO 3 -, inorganic molecules material such as halide ion, thereby reach the purpose of complete inorganicization, the material that can also remove many difficult degradations effectively or be difficult to remove with additive method, as chloroform, Polychlorinated biphenyls, organic phosphorus compound, polycyclic aromatic hydrocarbon etc., improve the oxygen content in the water, reach the purpose of purifying waste water fully.(4) during degradation biological pharmacy waste water of the present invention, its COD (chemical oxygen consumption (COC)) clearance improves more than 39% than the film of glass carrier in the identical time, the same with the film of other carriers through continuous degradation, the COD clearance can reach more than 99%, reach the purpose of last elimination, and the time of its elimination shortens over half.The present invention and powder, glass film are degraded certain pharmaceutical factory's pharmacy waste water to such as table one:
Table one
Nanometer Fe 3+/TiO 2 The clearance of 2 hours COD of degraded Continue the activity of degraded Reuse effect
Powder ??25.3％ Do not change after 2 hours Treated, can re-use once
Glass film ??27.3％ Do not change after 3 hours Treated, can re-use 2 times
The Ago-Gel film ??66.3％ Continue more than 4 hours Treated, can use more than 4 times
From the dissimilar nanometer Fe of equal in quality 3+/ TiO 2The result of degraded same amount waste water is as can be known: nano-titanium dioxide film photocatalytic activity of the present invention improves more than 39% at the nano titanium oxide of identical other type of time ratio, the activity that continues degrading waste water doubles, and regeneration rate improves 2 times, thus this film can purify waste water and degrading waste water in worthly preferentially select for use.
The specific embodiment
A adopts the sol-gel process preparation to mix Fe 3+Nano-TiO 2, see Table two
Table two
Sequence number The consumption of butyl titanate The consumption of glacial acetic acid The consumption of absolute ethyl alcohol Ferric nitrate ethanolic solution quality is consumption when The consumption of water Sintering temperature Nanometer Fe 3+/TiO 2Crystal formation
??1 ??6mL ??7.2mL ??20mL ??0.01％，10mL ??5mL ??550℃ Mix crystal formation
??2 ??6mL ??7.2mL ??20mL ??0.1％，10mL ??5mL ??580℃ Mix crystal formation
??3 ??8.1mL ??9.72mL ??27mL ??0.05％，13.5mL ??6.75mL ??600℃ Mix crystal formation
Show that by a large amount of experiments sequence number 3 listed preparations mixes 0.05%Fe in the table two 3+Nano-TiO 2, catalytic activity the best, mass ratio described in the table is a mass ratio under the solution state.
B prepares the nano titanium oxide Ago-Gel film of loaded iron doped ion, sees Table three
Table three
Sequence number Agarose consumption (mass ratio) Mix 0.05%Fe 3+Nano-TiO 2, consumption (mass ratio) The consumption of water The temperature of water
??1 ??2g(1％) ??0.2g(0.1％) ??197.8mL ??80℃
??2 ??2g(5％) ??0.2(0.5％) ??37.8mL ??83℃
??3 ??2g(10％) ??0.05g(0.25％) ??17.9mL ??85℃
Sequence number 1,2 listed preparation films be difficult for to produce suspended state phenomenon, particularly sequence number 2 listed preparation films and continue more than 4 hours, reuse the mensuration that does not all produce suspended state 4 times and influence its degradation efficiency in the table three.Sequence number 1,2 listed preparation film qualities are respectively 6.6g and 2.2g, in the corresponding film nano titanium oxide mass ratio of iron-doped iron be respectively 3.33% and 9.09.%, Ago-Gel mass ratio be respectively 96.67% and 90.91%, mass ratio described in the table is a mass ratio under the solution state.
The present invention has overcome suspended state TiO 2Easily cohesion in the water, difficult recovery, active component loss are greatly, and instability such as category of glass, metal species, absorption class, easily come off, cause the rate of recycling low, cost an arm and a leg, load difficulty, complex process, even shortcomings such as photocatalytic activity reduces in various degree after the photochemical catalyst load are arranged.Can be used for low concentration pollutant and administer, the carrier Ago-Gel itself among the present invention simultaneously also can classification isolated cell particle, virus etc.Utilize these characteristics to adopt photocatalytic method realization universalness to purify waste water, effectively degrading waste water improves water oxygen level.

Claims (6)

1. a nano-titanium dioxide film is characterized in that: the nano titanium oxide, the Ago-Gel that comprise iron-doped iron.
2. according to the described a kind of nano-titanium dioxide film of claim 1, it is characterized in that: the nano titanium oxide mass ratio of iron-doped iron is 3.33%-9.09.%, the Ago-Gel mass ratio is 90.91%-96.67%, and the nano titanium oxide mass ratio that iron ion accounts for iron-doped iron is 0.05%.
3. according to the described a kind of nano-titanium dioxide film of claim 2, it is characterized in that: the nano titanium oxide mass ratio of iron-doped iron is 9.09.%, and the Ago-Gel mass ratio is 90.91%.
4. according to claim 1 or 2 or 3 described a kind of nano-titanium dioxide films, it is characterized in that: adopt sol-gel process to prepare the nano titanium oxide of iron-doped iron.
5. prepare claim 1 or 2 or 3 described a kind of nano-titanium dioxide film methods, it is characterized in that carrying out according to the following steps:
A adopts the sol-gel process preparation to mix Fe 3+Nano-TiO 2
With butyl titanate, glacial acetic acid, absolute ethyl alcohol, ferric nitrate is raw material, and butyl titanate, glacial acetic acid, absolute ethyl alcohol three's volume ratio is 1: 1.2: 5, and wherein 1/3 absolute ethyl alcohol is made preparation iron nitrate solution usefulness, will prepare mass ratio at 0.01%-0.1%Fe 3+The ferric nitrate ethanolic solution place dropping funel, add entry, the volume ratio of water and ferric nitrate ethanolic solution is 1: 2, under constantly stirring, dropwise join in the mixed liquor of butyl titanate, glacial acetic acid and absolute ethyl alcohol, after dropwising, continue to stir 1 hour until generating faint yellow colloidal sol, placed 2-3 days, behind the gel to be formed, place 110 ℃ of constant temperature vacuum drying, pulverize again, and, obtain the Fe of sharp too ore deposit type and rutile-type melange type at 500-600 ℃ of roasting temperature 3+/ TiO 2Nanometer powder;
B prepares the nano titanium oxide Ago-Gel film of loaded iron doped ion
Place 80-85 ℃ of water-bath to heat the conical flask that fills distilled water, conical flask should seal during heating, adding mass ratio when the distilled water water temperature reaches 45 ℃ is the 1%-10% agarose, and constantly jolting, and adding mass ratio after agarose melts fully is 0.1-0.5%Fe 3+/ TiO 2, constantly jolting is poured solution in the mould into to thick liquid, promptly gets Fe after the cooling 3+/ TiO 2The Ago-Gel film.
6. a nano-titanium dioxide film is used, and directly shines solution with ultraviolet source or visible light, i.e. photocatalytic degradation pharmacy waste water or surface water, and the reaction temperature of degraded is 10 ℃-40 ℃, and lasting bubbling air is kept the concentration of dissolved oxygen.
CN201010203495XA 2010-06-17 2010-06-17 Nano titanium dioxide thin film and preparation method and application thereof Expired - Fee Related CN101850268B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515271A (en) * 2011-12-22 2012-06-27 东北大学秦皇岛分校 TiO2 powder with visible light catalytic activity and preparation method thereof
CN106211527A (en) * 2016-07-21 2016-12-07 陈芷寒 Automatic regulation type classroom lighting system
CN115216325A (en) * 2022-07-13 2022-10-21 中国矿业大学 High-sulfur petroleum coke efficient desulfurization process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007042862A1 (en) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Modified titanium dioxide
CN101628236A (en) * 2009-08-03 2010-01-20 浙江理工大学 Preparation method of kieselguhr load type compound photocatalyst with iron ions doped titanium dioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007042862A1 (en) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Modified titanium dioxide
CN101628236A (en) * 2009-08-03 2010-01-20 浙江理工大学 Preparation method of kieselguhr load type compound photocatalyst with iron ions doped titanium dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《Chem. Mater.》 20080520 Xingdong Wang et. al. Gold Nanoparticle Incorporation into Porous Titania Networks Using an Agarose Gel Templating Technique for Photocatalytic Applications 3917-3926 1-6 第20卷, 第12期 2 *
《应用化工》 20070831 郭忠 等 Fe3+改性TiO2 薄膜的制备、表征及光催化性能研究 第793页 1-6 第36卷, 第8期 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515271A (en) * 2011-12-22 2012-06-27 东北大学秦皇岛分校 TiO2 powder with visible light catalytic activity and preparation method thereof
CN106211527A (en) * 2016-07-21 2016-12-07 陈芷寒 Automatic regulation type classroom lighting system
CN115216325A (en) * 2022-07-13 2022-10-21 中国矿业大学 High-sulfur petroleum coke efficient desulfurization process
CN115216325B (en) * 2022-07-13 2023-09-08 中国矿业大学 High-efficiency desulfurization process for high-sulfur petroleum coke

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