CN102614877B - Preparation method of transition metallic element and non-metallic element doped nano titanium dioxide modified photocatalyst - Google Patents
Preparation method of transition metallic element and non-metallic element doped nano titanium dioxide modified photocatalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a transition metallic element and non-metallic element doped nano titanium dioxide modified photocatalyst. The preparation method comprises the following steps of: forming a titanium dioxide thin film on a metal substrate by using an anode oxidation method; drying eluting solvent and then mixing transition metallic solution and non-metallic element solution; modifying the formed titanium dioxide thin film by using an electrolysis method under a neutral condition; and heating the modified titanium dioxide thin film to 400-500 DEG C to prepare the modified photocatalyst. The method is simple; expensive equipment is not required; the prepared modified titanium dioxide photocatalyst is greatly improved in visible light compared with unmodified titanium dioxide photocatalyst; sunlight and an indoor fluorescent lamp can be utilized as a light source; and the photocatalyst is applied to industrial wastewater treatment and degradation of organic matters, so that the problem of difficulty in recovery after use of the powdery photocatalyst can be avoided.
Description
Technical field
The present invention relates to photocatalysis technology field, be specifically related to the preparation method of transition metal and the nano-titanium dioxide modified photochemical catalyst of nonmetal doping.
Background technology
Titanium dioxide is due to its unique photocatalysis characteristic, has a wide range of applications and becomes the focus of research as the environmental type catalyst that has most exploitation future of a new generation in water environment purified treatment, air contaminant treatment, anti-biotic material.But due to the wider Eg=3.2eV of titanium dioxide band gap degree of Detitanium-ore-type, can only respond the ultraviolet light wave band that optical wavelength is less than 400nm, very weak to the photoresponse of visible region, but ultraviolet light accounts for 4% of sunshine, and visible ray accounts for 43% of sunshine; Moreover electronics and hole that optical excitation produces are very easily compound, cause light-catalysed Efficiency Decreasing, and quantization efficiency are low; More the powder of titanium dioxide reclaims the problems such as difficulty.These have all seriously restricted TiO
2light-catalysed practical application.Therefore, doping vario-property TiO
2become with the photocatalysis performance and the rate of recovery that to its immobilization are all raising titanium dioxide the two large keys whether this technology can be applied.
One, the immobilization of titanium dioxide
In order to overcome powder TiO
2the difficult separation and recycling that catalyst exists, easily cohesion, free settling, the problems such as poor stability, the emphasis of research is turned to stationary state TiO by people
2catalyst.The effective way of catalyst recovery recycling is not only in catalyst immobilization, is also the various functions of application of active component and carrier, the ideal form of design optimum catalyst.In recent years, both at home and abroad to fixing phase TiO
2film catalyst has done many explorations, has carried out a series of about TiO
2powder immobilization (Li Xuandong etc., the journal .2004 of Harbin Institute of Technology, 36 (1): 79 ~ 83; X. Z. Li, et al. Environ. Sci. Technol. 2000,34:4401 ~ 4406) and preparation TiO
2research work (C. J. Tavares, J. Vieira, et al. Materials Science and Engineering B. 2007,138:139 ~ 143 of film; B. Z. Maria, J. S. Jeosadaque, et al. Environ. Sci. Technol. 2004,38:3203 ~ 3208; N. M. Mahmoodi, M. Arami, N. Y. Limaee. Materials Research Bulletin. 2007,42:797 ~ 806) have made some progress.Research shows: the technical problem underlying that photocatalytic method is applied to actual needs solution is carrier and the TiO of selecting catalyst
2the immobilization of catalyst on carrier.
The immobilized method of titanium dioxide is a lot of at present, and current stationary state catalyst is prepared used raw material and mainly contained two sources: one, and the direct current stationary state catalyst of commodity in use is prepared used raw material and is mainly contained two sources: one, directly
Commodity in use TiO
2powder, is dispersed in the water that is added with additive and is made TiO
2slurries, then loaded on carrier; Its two, take titanium-containing compound as raw material, generate TiO by chemical reaction
2powder, then select appropriate loading method.The loading method of report mainly contains at present: sol-gel process, electrophoretic deposition, powder sintering, chemical vapour deposition technique and anodizing etc.Sol-gel process is conventional TiO
2catalyst fixing means, the method technique is simple, cost is low, can be used for large area and irregularly shaped base coated film, but has the shortcomings such as insecure and catalytic amount load of plated film is very few.
Two, improve the photocatalysis efficiency of titanium dioxide
The approach that improves optically catalytic TiO 2 activity has following several respects.(1) improvement to catalyst itself, at preparation TiO
2the specific sensitization material that adulterates when catalyst, improves the conevying efficiency of light induced electron, suppresses the compound of electronics and hole.At present, research means both domestic and external is mainly the means modification TiO such as and semiconductor surface photoactivate compound by semiconductor surface noble metal loading, doped transition metal ions, nonmetal doping, semiconductor
2, widen its wavelength response range, improve photocatalysis efficiency.
(2) improve the device of photochemical catalyst reaction or add cocatalyst, improving utilization rate and the reaction efficiency of sunshine.
Summary of the invention
The preparation method who the object of this invention is to provide transition metal and the nano-titanium dioxide modified photochemical catalyst of nonmetal doping, has overcome TiO
2the weak points such as the not high and titanium dioxide recycling difficulty of photoresponse narrow range, photocatalysis efficiency.Titanium dioxide after codoping modified both can be used as the photochemical catalyst of degradable organic pollutant, can be used as again the anode material of photoelectrocatalysis reaction.Under light source and applied voltage effect, carry out photoelectrocatalysis reaction, improve the speed of degraded organic contamination.
The present invention will be by TiO
2/ Ti catalyst carries out doping vario-property research, is intended to reduce the recombination probability in electronics and hole, expands excitation wavelength range, further improves its utilization rate to luminous energy, thereby increases TiO
2the economy of photoelectrocatalysioxidization oxidization technology and practicality.For achieving the above object, the invention provides following technical scheme.
The preparation method of transition metal and the nano-titanium dioxide modified photochemical catalyst of nitrogen-doping, first adopt anodizing on metal substrate, to form titanium deoxid film, after eluting solvent is dried, again transition metal solution and nonmetalloid solution are mixed, under neutrallty condition, adopt electrolysis that established titanium deoxid film is carried out to modification, the titanium deoxid film after modification is heated to 400 ℃-500 ℃ and makes described modified light catalyst.
In above-mentioned preparation method, described anodizing comprises the steps: a), clean metal substrate surface: described metallic substrate surfaces is wiped surface oxide layer with fine sandpaper, after cleaning, use alcohol immersion, then put into baking oven after cleaning with distilled water, dry stand-by; B), anodic oxidation: in acid medium, take graphite as negative electrode, metal substrate is anode, at room temperature, adopts 40 mA/cm
2-66mA/cm
2current density be oxidized 10-60 minute; C), hydrolysis process: the metal substrate after oxidation is left standstill in distilled water to aquation 1-2 hour, dry stand-by.Described in step b), acid medium adopts salpeter solution and hydrofluoric acid solution, and interim nitric acid and hydrofluoric acid mol ratio are 2:1.
In above-mentioned preparation method, described electrolysis comprises the steps: a), transition metal solution and nonmetalloid solution is mixed by the mol ratio 1:3 of transition metal and nonmetalloid ~ 3:1, stirs; B), electrolysis: will be after anodizing be processed metal substrate immerse described in step a) in mixed solution, take graphite as anode, metal substrate is negative electrode, at room temperature, adopts 20 mA/cm
2-40 mA/cm
2current density by transition metal and nonmetalloid codope in the titanium deoxid film on metal substrate, electrolysis 1-2 hour, dry after cleaning; After dry, put into Muffle furnace, be warmed up to 400 ℃-500 ℃, 1 ~ 4 hour (preferably 3 hours) of calcination insulation.
In above-mentioned preparation method, described transition metal solution and nonmetalloid solution are respectively copper nitrate solution and ammonium chloride solution, and described metal substrate is titanium-base.
The method of described transition metal and the nano-titanium dioxide modified photochemical catalyst of nitrogen-doping, described metal is titanium sheet.
The present invention proposes the preparation method of a kind of transition metal ions and non-metallic ion co-doped modified titanium dioxide photocatalyst, successively by metallic substrate surfaces processing, metallic substrate surfaces is carried out to anodic oxidation, aquation under acid condition, then under neutrallty condition, take copper nitrate solution and ammonium chloride solution as electrolyte, adopt electrodeposition process to carry out doping vario-property to titanium dioxide optical catalyst, and then the step such as calcination is carried out under proper temperature.Be characterized in: method is easy, do not need expensive equipment, both can be used for laboratory operation, can be used for again industrial production, titanium deoxid film stationarity is good, there is stronger photocatalysis, can be used for the degraded of organic pollution, the photochemical catalyst of preparation has good electric conductivity and machining property, can be used for anode material and photoelectrocatalysis reaction unit material etc. in photoelectrocatalysis reaction.
The present invention compared with prior art has following outstanding advantages:
1, preparation technology is simple, and raw material is easy to get, and cost is lower, and cost performance is high.
2, adopt environmental protection raw material, non-environmental-pollution in preparation process and in using.
3, controlled change operating condition, reaches best photocatalysis efficiency.Can recently control the thickness that titanium deoxid film forms by changing current density, temperature, electrolytical mole; Control the cambial quality of titanium deoxid film by the mol ratio of alloy and the difference of calcination temperature.
4, the codoping modified titanium dioxide film photocatalyst that prepared by the method has good stability.Immersion and flushing by the aqueous solution and flowing water experiment showed, that this photochemical catalyst has good stability.Therefore, can in photocatalysis apparatus, use and as the anode in photoelectrocatalysis reaction, strengthen the efficiency of catalyzing oxidizing degrading organic pollution.
Accompanying drawing explanation
Fig. 1 is gained photochemical catalyst and the UV-Vis of doped titanium dioxide photocatalyst and the titanium-base spectrogram that diffuses not after embodiment 1 and embodiment 2 adopt the copper nitrate of different mol ratio and ammonium chloride to titania additive modification.
Fig. 2 is gained photochemical catalyst and the XRD figure of doped titanium dioxide photocatalyst and titanium-base not after embodiment 1 and embodiment 2 adopt the copper nitrate of different mol ratio and ammonium chloride to titania additive modification.
Fig. 3 is gained photochemical catalyst and the FE-SEM figure of doped titanium dioxide photocatalyst and titanium-base not after embodiment 1 and embodiment 2 adopt the copper nitrate of different mol ratio and ammonium chloride to titania additive modification.
Fig. 4 is gained photochemical catalyst and the EDX figure of doped titanium dioxide photocatalyst and titanium-base not after embodiment 1 and embodiment 2 adopt the copper nitrate of different mol ratio and ammonium chloride to titania additive modification.
Fig. 5 is that after embodiment 1 and embodiment 2 adopt the copper nitrate of different mol ratio and ammonium chloride to titania additive modification, speed is removed in the degraded of gained photochemical catalyst and not doped titanium dioxide photocatalyst and titanium-base light-catalyzed reaction within the differential responses time to humic acid.
The specific embodiment
Below in conjunction with example, enforcement of the present invention is described further, but for a person skilled in the art, enforcement of the present invention and protection are not limited to this.
(1) by No. 600 fine sandpaper sanding and polishing metal titanium sheet, totally put into distilled water flushing the ethanolic solution configuring and soak
Bubble is removed the organic matter of metal surface, then uses distilled water cleaned standby seam.
(2) salpeter solution and the 0.05mol/L hydrofluoric acid solution of preparation 0.1mol/L, mix by 1:1 volume ratio, and take graphite as negative electrode, titanium sheet is anode, at room temperature, is connected on D.C. regulated power supply, according to titanium sheet area, at 40 mA/cm
2in scope, regulate current density, carry out anodized, the time was at 10 minutes.
(3) take out metal titanium sheet, water rinses, and puts into distilled water and leaves standstill aquation 1 hour, puts into baking oven stand-by with 100 ℃ of oven dry.
(4) copper nitrate solution and ammonium chloride solution are mixed in molar ratio in the scope of 1:1, stir, then carry out electrolysis, established titanium dioxide optical catalyst is immersed in mixed solution, and take graphite as anode, photochemical catalyst is negative electrode, at room temperature, adopt 20 mA/cm
2in scope by its copper and nitrogen element codope in optically catalytic TiO 2, electrolysis 1 hour, after cleaning in 100 ℃ of oven dry.
(5) dried processing plating piece is put into Muffle furnace, be warmed up to gradually 500 ℃, calcination insulation 3 hours, naturally cooling with furnace temperature.
Embodiment 2
(1), by No. 600 fine sandpaper sanding and polishing metal titanium sheet, totally put into distilled water flushing the ethanolic solution configuring and soak the organic matter of removing metal surface, then use distilled water cleaned standby seam.
(2) salpeter solution and the 0.05mol/L hydrofluoric acid solution of preparation 0.1mol/L, mix by 1:1 volume ratio, and take graphite as negative electrode, titanium sheet is anode, at room temperature, is connected on D.C. regulated power supply, according to titanium sheet area, at 66mA/cm
2
In scope, regulate current density, carry out anodized, the time was at 60 minutes.
(3) take out metal titanium sheet, water rinses, and puts into distilled water and leaves standstill aquation 1.5 hours, puts into baking oven stand-by with 100 ℃ of oven dry.
(4) copper nitrate solution and ammonium chloride solution are mixed in molar ratio in the scope of 1:3, stir, then carry out electrolysis, established titanium dioxide optical catalyst is immersed in mixed solution, and take graphite as anode, photochemical catalyst is negative electrode, at room temperature, adopt 40 mA/cm
2in scope by its copper and nitrogen element codope in titanium dioxide optical catalyst, electrolysis 2 hours, after cleaning in 100 ℃ of oven dry.
(5) dried processing plating piece is put into Muffle furnace, be warmed up to gradually 500 ℃, calcination insulation 3.5 hours, naturally cooling with furnace temperature.
The performance characterization of prepared titanium dioxide optical catalyst comprises: adopt ultraviolet-visible spectrophotometer to measure the ultraviolet-visible light diffuse reflection spectrum of codoping modified titanium deoxid film.Adopt the photocatalysis performance under light source irradiates to the codoping modified titanium dioxide film photocatalyst of the rate of photocatalytic oxidation quantitative assay of humic acid.
As shown in Figure 1, the titanium dioxide optical catalyst after the copper doped element that in figure, curve a and curve b corresponding instance 1 and example 2 make and nitrogen are element modified, the corresponding unadulterated titanium dioxide optical catalyst of curve d, the corresponding titanium-base of curve c.Transverse axis is incident wavelength, and the longitudinal axis is absorbance.In figure, show that the titanium dioxide optical catalyst after doping vario-property has a distinct increment to photoresponse efficiency at visible light wave range.
As shown in Figure 2, the titanium dioxide optical catalyst after the copper doped element that in figure, curve c and curve d corresponding instance 1 and example 2 make and nitrogen are element modified, the corresponding unadulterated titanium dioxide optical catalyst of curve b, the corresponding titanium-base of curve a.Transverse axis is angle of diffraction, and the longitudinal axis is diffracted intensity.In figure, show that unadulterated titanium dioxide optical catalyst and copper doped element and the nitrogen titanium dioxide optical catalyst after element modified all has response more by force in the specific 2 θ angles of the Detitanium-ore-type of titanium dioxide crystal form, illustrates by described method and can successfully prepare described photochemical catalyst.
As shown in Figure 3 a and Figure 3 b shows, not doped titanium dioxide photocatalyst of Fig. 3 a correspondence, the surface topography of the titanium dioxide optical catalyst after the corresponding copper doped element of Fig. 3 b and nitrogen are element modified, the photocatalyst film surface alignment out-of-flatness before doping of explanation in figure, and by the photochemical catalyst energy refinement surface microstructure after doping vario-property and make its crystal grain aligned growth.
As shown in Figure 4, the percentage composition that in figure, the characterization method explanation copper doped element of explanation by EDX and the nitrogen titanium dioxide optical catalyst after element modified contains described element.Concrete element percentage composition is as shown in table 1.
Table 1
| Element | Percentage by weight | Atomicity percentage composition |
| Carbon | 1.33 | 3.45 |
| Oxygen | 25.51 | 49.55 |
| Titanium | 70.02 | 45.46 |
| Copper | 3.14 | 1.54 |
| Matrix element | Correction value | Atomic number absorbs fluorescence corrigendum |
As shown in Figure 5, transverse axis is the time, the degradation efficiency (%) that the longitudinal axis is humic acid.Titanium dioxide optical catalyst after the copper doped element that in figure, curve 3 and curve 4 corresponding instances 1 and example 2 make and nitrogen are element modified, the corresponding unadulterated titanium dioxide optical catalyst of curve 2, the corresponding titanium-base of curve 1.In figure, show curve 1 under dark condition or having under the condition of light source do not possess photocatalysis efficiency, curve 2,3 and 4 is under the condition that has light source, all high than the photocatalysis efficiency under dark condition, the photochemical catalyst after doping vario-property has a distinct increment compared to the photochemical catalyst photocatalysis efficiency of doping vario-property not.
Claims (1)
1. the preparation method of transition metal and the nano-titanium dioxide modified photochemical catalyst of nonmetal doping, it is characterized in that: first adopt anodizing on metal substrate, to form titanium deoxid film, after eluting solvent is dried, again transition metal solution and nonmetalloid solution are mixed, under neutrallty condition, adopt electrolysis that established titanium deoxid film is carried out to modification, the titanium deoxid film after modification is heated to 400 ℃-500 ℃ and makes described modified light catalyst; Described anodizing comprises the steps: a), clean metal substrate surface: described metallic substrate surfaces is wiped surface oxide layer with fine sandpaper, after cleaning, uses alcohol immersion, then puts into baking oven after cleaning with distilled water, dries stand-by; B), anodic oxidation: in acid medium, take graphite as negative electrode, metal substrate is anode, at room temperature, adopts 40 mA/cm
2-66mA/cm
2current density be oxidized 10-60 minute; Described acid medium adopts salpeter solution and hydrofluoric acid solution, and wherein nitric acid and hydrofluoric acid mol ratio are 2:1; C), hydrolysis process: the metal substrate after oxidation is left standstill in distilled water to aquation 1-2 hour, dry stand-by; Described electrolysis comprises the steps: a), transition metal solution and nonmetalloid solution is mixed by the mol ratio 1:3 of transition metal and nonmetalloid ~ 3:1, stirs; B), electrolysis: will be after anodizing be processed metal substrate immerse described in step a) in mixed solution, take graphite as anode, metal substrate is negative electrode, at room temperature, adopts 20 mA/cm
2-40 mA/cm
2current density by transition metal and nonmetalloid codope in the titanium deoxid film on metal substrate, electrolysis 1-2 hour,
Dry after cleaning; After dry, put into Muffle furnace, be warmed up to 400 ℃-500 ℃, calcination insulation 1 ~ 4 hour; Described transition metal solution and nonmetalloid solution are respectively copper nitrate solution and ammonium chloride solution, and described metal substrate is titanium-base.
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| CN108654662A (en) * | 2017-07-12 | 2018-10-16 | 中国地质大学（北京） | A kind of molten-salt growth method prepares the nitrogen co-doped single-crystal meso-pore TiO of fluorine2The method of catalysis material |
| CN111041523B (en) * | 2020-01-02 | 2021-09-07 | 东莞理工学院 | Copper-doped titanium dioxide photoelectrode, preparation method thereof and application thereof in photoelectrocatalysis decomposition of water |
| CN111632619A (en) * | 2020-06-17 | 2020-09-08 | 湖北民族大学 | Copper-nitrogen co-doped titanium dioxide photocatalytic material, preparation method and application |
| CN115744974B (en) * | 2022-11-22 | 2024-03-15 | 北京师范大学 | TiO with cation vacancy doped by nonmetallic element 2 Preparation method of nanorods, product obtained by preparation method and application of nanorods |
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| CN1515351A (en) * | 2003-08-29 | 2004-07-28 | 哈尔滨工业大学 | Modified titanium dioxide immobilization method for degrading organic pollutant in water |
| CN101219373A (en) * | 2008-01-16 | 2008-07-16 | 中南大学 | Process for producing codope titanium dioxide thin film of nitrogen and bismuth |
| CN101684566A (en) * | 2008-09-27 | 2010-03-31 | 比亚迪股份有限公司 | Titanium dioxide nanometer membrane and preparation method thereof |
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| CN1515351A (en) * | 2003-08-29 | 2004-07-28 | 哈尔滨工业大学 | Modified titanium dioxide immobilization method for degrading organic pollutant in water |
| CN101219373A (en) * | 2008-01-16 | 2008-07-16 | 中南大学 | Process for producing codope titanium dioxide thin film of nitrogen and bismuth |
| CN101684566A (en) * | 2008-09-27 | 2010-03-31 | 比亚迪股份有限公司 | Titanium dioxide nanometer membrane and preparation method thereof |
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