CN101716531A - Polyethylene film loading type iron nitrogen co-doping titanium dioxide photocatalyst and preparation method thereof - Google Patents
Polyethylene film loading type iron nitrogen co-doping titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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- CN101716531A CN101716531A CN200910228598A CN200910228598A CN101716531A CN 101716531 A CN101716531 A CN 101716531A CN 200910228598 A CN200910228598 A CN 200910228598A CN 200910228598 A CN200910228598 A CN 200910228598A CN 101716531 A CN101716531 A CN 101716531A
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Abstract
The invention relates to the field of titanium dioxide photocatalyst, in particular to the field of a film loading type iron nitrogen co-doping titanium dioxide photocatalyst. The invention provides a preparation method for a flexible carrier (LDPE) film loading type iron nitrogen co-doping TiO2 catalyst. The catalyst contains an active constituent and a carrier. The iron nitrogen co-doping titanium dioxide, as the active constituent of the loading catalyst, is loaded on a low density polyethylene film carrier. The preparation method for photocatalyst is the sol-gel method. The loading method for catalyst is the dipping sediment-thermal treatment method. The invention has excellent photocatalysis oxidability under visible lights, has simple preparation process and can be reused.
Description
Technical field
The present invention relates to the nano titanium dioxide photocatalysis field, particularly iron, the preparation of nitrogen co-doped nano titanium dioxide powder and low density polyethylene (LDPE) (LDPE) film load technology field thereof.The catalyst that this method is prepared is specially adapted to catalytic degradation diphenylamines under the radiation of visible light, reaches higher degradation rate.
Background technology
Nano titanium oxide has characteristics such as high-specific surface area, high density, lattice surface defective and high-ratio surface energy, have that chemical property is stable, nontoxic, catalytic activity is high, reaction speed is fast, low and can make it advantages such as thorough mineralising, non-secondary pollution to organic degraded selectivity, have a wide range of applications.When energy greater than TiO
2When semiconductor is penetrated in the illumination of energy gap, the optical excitation electron transition is to conduction band, form conduction band electron, simultaneously, stay the hole in valence band, because the discontinuity of semiconductor energy gap, the life-span in electronics and hole is longer, they can move under electric field action or by the mode of diffusion, with the material generation redox reaction that is adsorbed on the semiconductor catalyst particle surface, perhaps captured by the lattice surface defective, hole and electronics in catalyst particle inside or the surface also may be directly compound, the hole can be with being adsorbed on the OH of catalyst pellets sub-surface
-Or H
2The O generation high mars free radical of having an effect can not have the various organic matters of selectively oxidation and makes it mineralising.
Because nano-TiO
2(anatase) is the semi-conductor type catalysis material, its energy gap is 3.2eV, make and to have only wavelength to equal or the ultraviolet light of little 387.5nm just can make it to excite the demonstration catalytic activity, and sunshine medium ultraviolet light only accounts for about 4%, therefore very low to the utilization rate of sunshine, if it can be absorbed threshold value widens visible region, for nano-TiO
2To have crucial meaning in the photocatalysis degradation organic contaminant Application for Field.Therefore how to utilize natural daylight to carry out light-catalyzed reaction efficiently, exploitation can be caused people's interest just day by day by the high efficiency photochemical catalyst of excited by visible light, and will realize this goal, to TiO
2Carrying out doping vario-property is the method that generally adopts.According to the difference of dopant, mainly can be divided into metal-doped, nonmetal doping, metal and nonmetal codope.The doping of metal ion is a kind of realization nano-TiO
2One of visible photochemical effective means of photochemical catalyst.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,, transit to conduction band by impurity energy level by absorbing energy again, so just reduced and be excited required energy, thereby realized modification TiO
2The spectral response range of photochemical catalyst moves this target to visible region.According to band theory, semi-conductive conduction level depends primarily in the semiconductor metal ion (as Ti according to semiconductor
4+) energy level of empty d track, and semi-conductive valence-band level depends primarily on nonmetallic ion (as O
2-) energy level of the p track that is full of compares with the O2p track, nonmetallic ion (N, C, S, P) has the higher relatively p track of energy, and the doped with non-metals ion not only can be with TiO
2The photoresponse wavelength expand to visible region overseasly, can also remain on the photocatalytic activity of ultraviolet region.Discover recent years, to TiO
2Carry out two kinds of element codopes, the photochemical catalyst that obtains has than the higher photocatalysis performance of single-element doping.Bi-component codope catalyst its catalytic activity when optimum doping concentration and optimum doping condition are following is about the catalytic activity sum of corresponding one pack system doped samples, is referred to as cooperative effect.Metal current ion and nonmetalloid codope Preparation of catalysts method are the doping of elder generation's a kind of ion of doping or element substantially in the doping process, then in the doping of carrying out another kind of element.The metal ion that mixes plays expansion TiO
2The effect of photoresponse scope, and nonmetal inhibition photo-generated carrier is compound, the two synergy improves photocatalysis performance.
The use of photochemical catalyst mainly contains two kinds of forms in the photocatalysis technology, promptly directly uses TiO
2The suspension system of powder and with TiO
2Load on and carry out catalytic reaction on the carrier.At nano-TiO
2Actual use in, particularly in the application of water treatment, be to adopt TiO mostly
2Suspension system, with TiO
2Particle is suspended in the solution and reacts.The advantage of this method is: contact surface is bigger, can bring into play the suction-operated of catalyst, and mass transfer effect is good.But also have easily cohesion, reclaim and be not suitable for shortcoming such as current system difficult the separation, therefore, developing suitable solid-carrying type catalyst is the effective way that overcomes these shortcomings.At present, the catalyst immobilization technology that is adopted in photocatalysis research mainly contains sol-gel process, powder sintering, electrophoresis and dipping aeration drying etc.And the used carrier of load mainly contains category of glass, metal species, ceramic-like, adsorbent class, high molecular polymer class, zwitterion exchanger class etc.
Summary of the invention
The object of the present invention is to provide a kind of polyethylene film loading type titanium deoxide catalyst with visible light catalysis activity, its in titanium dioxide, mix a spot of iron ion and nitrogen element, the doping synergy of these two kinds of elements, thereby reduced the energy gap of semiconductor light-catalyst, made catalyst have absorbability visible light.
Enforcement the technical solution used in the present invention is as described below: adopt sol-gel process to prepare pulverous titanium deoxide catalyst, it is codoping modified when it is carried out iron, two kinds of elements of nitrogen, after mixing with the powder catalyst that makes again by dipper precipitation and heat treating process uniform load on low density polyethylene films, thereby obtain having the low density polyethylene films loaded photocatalyst of visible light activity.With the film support type Fe/N-TiO for preparing
2Being applied to the photocatalytic degradation experiment, is light source with the xenon long-arc lamp, and diphenylamines carries out the photocatalytic degradation experiment for the target degradation product, has obtained effect preferably.
Implement iron, nitrogen while codope TiO that the present invention adopts
2The preparation of fine catalyst comprises step as described below: (1) slowly is added drop-wise to butyl titanate, acetic acid in the absolute ethyl alcohol under intense agitation, obtains solution A; (2) respectively a small amount of ferric nitrate crystal, urea, acetic acid, water are joined in the absolute ethyl alcohol, obtain solution B; (3) under intense agitation B slowly is added drop-wise among the A, dropwises the back and continue to stir 3h, still aging 24h gets stable gel, and gel is obtained xerogel in 80 ℃ of oven dry; (4) 500 ℃ of roasting 3h obtain faint yellow Fe, N codope TiO in the tube type resistance furnace with being placed on behind the xerogel porphyrize powdered
2Powder.
Implement Fe, N codope TiO that the present invention adopts
2The LDPE film load of fine catalyst comprises step as described below: (1) is cut into rectangle with the LDPE film, with cleaning with clear water behind the isopropyl alcohol immersion certain hour, dries stand-by under the room temperature; (2) with the isopropyl alcohol be solvent, the suspension of preparation fine catalyst, the mass concentration of catalyst is 1g/L, fully stirs with magnetic stirring apparatus, leaves standstill 24h; (3) the LDPE film is immersed in 10h in this suspension, hangs on indoor drying, be put in the interior 105 ℃ of heat treatments of baking oven 10 hours then; (4) the LDPE film after the heat treatment is cleaned with ultrasonic washing instrument, distilled water washes down, and to remove the catalyst granules of surface for adhering to, at last the diaphragm hang airing can be obtained LDPE film supported titanium
2Catalyst.
The specific embodiment
Example 1 iron, nitrogen is codope TiO simultaneously
2The preparation of fine catalyst
(1) under intense agitation, 10mL butyl titanate, 10mL acetic acid slowly are added drop-wise in the 80mL absolute ethyl alcohol, obtain solution A;
(2) respectively a small amount of ferric nitrate crystal, urea, 5mL acetic acid, 6.25mL water are joined in the 25mL absolute ethyl alcohol, obtain solution B;
(3) under intense agitation B slowly is added drop-wise among the A, dropwises the back and continue to stir 3h, still aging 24h gets stable gel, and gel is obtained xerogel in 80 ℃ of oven dry;
(4) 500 ℃ of roasting 3h obtain faint yellow Fe, N codope TiO simultaneously in the tube type resistance furnace with being placed on behind the xerogel porphyrize powdered
2Powder.
The LDPE film load of example 2 fine catalysts
(1) the LDPE film is cut into the rectangle of 5 * 10cm, cleans with clear water after soaking certain hour with isopropyl alcohol, dry stand-by under the room temperature;
(2) with the isopropyl alcohol be solvent, preparation Fe, N be the TiO of codope simultaneously
2The suspension 100mL of fine catalyst, the mass concentration of catalyst is 1g/L, fully stirs with magnetic stirring apparatus, leaves standstill 24h;
(3) the LDPE film is immersed in 10h in this suspension, hangs on indoor drying, be put in the interior 105 ℃ of heat treatments of baking oven 10 hours then;
(4) the LDPE film after the heat treatment was cleaned 15 minutes with ultrasonic washing instrument, distilled water washes down, and to remove the catalyst granules of surface for adhering to, at last the diaphragm hang airing can be obtained LDPE film support type Fe, N codope TiO simultaneously
2Catalyst.
The application example of example 3 photocatalytic degradation diphenylamines (DPA)
With LDPE film support type Fe, the N while codope TiO that makes
2Catalyst carries out the experiment of photocatalytic degradation diphenylamines (DPA), and DPA concentration is 20mg/L, the initial pH=3 of solution.With the 500W xenon long-arc lamp is light source irradiation 90 minutes, and the degradation rate of DPA is 80.11%, and catalyst uses repeatedly still has higher degradation rate.Experimental result is as shown in table 1.
Table 1 catalyst is reused experimental result
Claims (7)
1. titanium dioxide optical catalyst of a film support type doping vario-property and preparation method thereof is characterized in that this catalyst is an active component with the titanium dioxide of iron, nitrogen co-doped modification, is carried on the low-density polyethylene film; It adopts sol-gel process to prepare pulverous titanium deoxide catalyst, it is codoping modified when it is carried out iron, two kinds of elements of nitrogen, after mixing with the powder catalyst that makes again by dipper precipitation and heat treating process uniform load on low density polyethylene films, thereby obtain having the low density polyethylene films loaded photocatalyst of visible light activity; With the film support type Fe/N-TiO for preparing
2Catalyst is applied to the photocatalytic degradation experiment, is light source with the xenon long-arc lamp, and diphenylamines is handled for the target degradation product carries out photocatalytic degradation, has obtained effect preferably.
2. the titanium dioxide optical catalyst of film support type doping vario-property according to claim 1 is characterized in that this catalyst is the titanium dioxide that source of iron and nitrogenous source are prepared into codope with ferric nitrate and urea respectively.
3. the preparation method of the titanium dioxide optical catalyst of film support type doping vario-property according to claim 1 is characterized in that it prepares iron, nitrogen co-doped titanium dioxide optical catalyst with sol-gel process.
4. the preparation method of the titanium dioxide optical catalyst of film support type doping vario-property according to claim 1 is characterized in that it is source of iron and nitrogenous source with ferric nitrate and urea respectively, mixes when carrying out iron and nitrogen, and does not have the branch of sequencing.
5. the preparation method of the titanium dioxide optical catalyst of film support type doping vario-property according to claim 4 is characterized in that iron, nitrogen codope TiO simultaneously
2The preparation of fine catalyst comprises step as described below: (1) slowly is added drop-wise to butyl titanate, acetic acid in the absolute ethyl alcohol under intense agitation, obtains solution A; (2) respectively a small amount of ferric nitrate crystal, urea, acetic acid, water are joined in the absolute ethyl alcohol, obtain solution B; (3) under intense agitation B slowly is added drop-wise among the A, dropwises the back and continue to stir 3h, still aging 24h gets stable gel, and gel is obtained xerogel in 80 ℃ of oven dry; (4) 500 ℃ of roasting 3h obtain faint yellow Fe, N codope TiO in the tube type resistance furnace with being placed on behind the xerogel porphyrize powdered
2Powder.
6. the preparation method of the titanium dioxide optical catalyst of film support type doping vario-property according to claim 1, it is characterized in that it with infusion process with the Fe, the N codope TiO that prepare
2Powder photocatalyst is carried on the low density polyethylene films.
7. the preparation method of the titanium dioxide optical catalyst of film support type doping vario-property according to claim 6 is characterized in that Fe, N codope TiO
2The LDPE film load of fine catalyst comprises step as described below: (1) is cut into rectangle with the LDPE film, with cleaning with clear water behind the isopropyl alcohol immersion certain hour, dries stand-by under the room temperature; (2) with the isopropyl alcohol be solvent, the suspension of preparation fine catalyst, the mass concentration of catalyst is 1g/L, fully stirs with magnetic stirring apparatus, leaves standstill 24h; (3) the LDPE film is immersed in 10h in this suspension, hangs on indoor drying, be put in the interior 105 ℃ of heat treatments of baking oven 10 hours then; (4) the LDPE film after the heat treatment is cleaned with ultrasonic washing instrument, distilled water washes down, and to remove the catalyst granules of surface for adhering to, at last the diaphragm hang airing can be obtained LDPE film supported titanium
2Catalyst.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905166A (en) * | 2010-07-27 | 2010-12-08 | 中国地质大学（武汉） | Magnetically separable nitrogen-doped TiO2 photocatalyst and preparation method thereof |
| CN101972662A (en) * | 2010-10-27 | 2011-02-16 | 华北电力大学（保定） | Preparation and use methods of nitrogen-vanadium co-doped modified titanium dioxide catalyst |
| CN102285686A (en) * | 2011-06-07 | 2011-12-21 | 西安交通大学 | Method for preparing iron-nitrogen codoped mesoporous nano titanium dioxide by fast sol-gel method |
| CN102945891A (en) * | 2012-11-01 | 2013-02-27 | 桂林师范高等专科学校 | Preparation method for FeS2/Ag2S/TiO2 composite film |
| CN106731881A (en) * | 2016-12-20 | 2017-05-31 | 济南大学 | Based on metal, nonmetallic codope nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method |
| CN106799166A (en) * | 2016-12-20 | 2017-06-06 | 济南大学 | Based on metal, nonmetallic codope nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method |
| CN108927215A (en) * | 2018-06-27 | 2018-12-04 | 上海大学 | Semiconductor/polymer composites visible-light photocatalyst, its application and preparation method |
| CN112058251A (en) * | 2020-07-27 | 2020-12-11 | 遵义师范学院 | Degradation of plastic microspheres in wastewater by ultrasonic iron-nitrogen doped titanium dioxide |
| CN114786805A (en) * | 2019-10-31 | 2022-07-22 | 卡罗比亚咨询有限责任公司 | Polymer support nano-functionalized with photocatalytic nanoparticles based on titanium dioxide and use thereof as a photocatalyst |
-
2009
- 2009-11-16 CN CN200910228598A patent/CN101716531A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905166B (en) * | 2010-07-27 | 2012-07-25 | 中国地质大学（武汉） | Magnetically separable nitrogen-doped TiO2 photocatalyst and preparation method thereof |
| CN101905166A (en) * | 2010-07-27 | 2010-12-08 | 中国地质大学（武汉） | Magnetically separable nitrogen-doped TiO2 photocatalyst and preparation method thereof |
| CN101972662A (en) * | 2010-10-27 | 2011-02-16 | 华北电力大学（保定） | Preparation and use methods of nitrogen-vanadium co-doped modified titanium dioxide catalyst |
| CN101972662B (en) * | 2010-10-27 | 2012-07-04 | 华北电力大学（保定） | Preparation and use methods of nitrogen-vanadium co-doped modified titanium dioxide catalyst |
| CN102285686B (en) * | 2011-06-07 | 2014-07-02 | 西安交通大学 | Method for preparing iron-nitrogen codoped mesoporous nano titanium dioxide by fast sol-gel method |
| CN102285686A (en) * | 2011-06-07 | 2011-12-21 | 西安交通大学 | Method for preparing iron-nitrogen codoped mesoporous nano titanium dioxide by fast sol-gel method |
| CN102945891A (en) * | 2012-11-01 | 2013-02-27 | 桂林师范高等专科学校 | Preparation method for FeS2/Ag2S/TiO2 composite film |
| CN102945891B (en) * | 2012-11-01 | 2015-07-01 | 桂林师范高等专科学校 | Preparation method for FeS2/Ag2S/TiO2 composite film |
| CN106731881A (en) * | 2016-12-20 | 2017-05-31 | 济南大学 | Based on metal, nonmetallic codope nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method |
| CN106799166A (en) * | 2016-12-20 | 2017-06-06 | 济南大学 | Based on metal, nonmetallic codope nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method |
| CN108927215A (en) * | 2018-06-27 | 2018-12-04 | 上海大学 | Semiconductor/polymer composites visible-light photocatalyst, its application and preparation method |
| CN108927215B (en) * | 2018-06-27 | 2021-05-07 | 上海大学 | Visible light photocatalyst of semiconductor/polymer composite material, application and preparation method thereof |
| CN114786805A (en) * | 2019-10-31 | 2022-07-22 | 卡罗比亚咨询有限责任公司 | Polymer support nano-functionalized with photocatalytic nanoparticles based on titanium dioxide and use thereof as a photocatalyst |
| CN112058251A (en) * | 2020-07-27 | 2020-12-11 | 遵义师范学院 | Degradation of plastic microspheres in wastewater by ultrasonic iron-nitrogen doped titanium dioxide |
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Application publication date: 20100602 |