CN103816932A - Preparation method of heterogeneous distribution metal and nonmetal co-doped TiO2 nanotube - Google Patents
Preparation method of heterogeneous distribution metal and nonmetal co-doped TiO2 nanotube Download PDFInfo
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- CN103816932A CN103816932A CN201410086614.6A CN201410086614A CN103816932A CN 103816932 A CN103816932 A CN 103816932A CN 201410086614 A CN201410086614 A CN 201410086614A CN 103816932 A CN103816932 A CN 103816932A
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Abstract
The invention discloses a preparation method of a heterogeneous distribution metal and nonmetal co-doped TiO2 nanotube. The method mainly comprises the processes as follows: firstly, TiCl4 is taken as a precursor, N-doped TiO2 photocatalysis powder is prepared, then the well prepared N-doped TiO2 photocatalysis powder is mixed with a NaOH solution in a polytetrafluoroethylene hydrothermal kettle, a N-doped TiO2 nanotube is prepared under certain reaction conditions, finally, heterogeneous distribution of metal elements on the surface of the nanotube is realized through impregnation step by step, that is, a rich metal element concentration area exists on the surface, a poor concentration area exists in a body phase, and concentration difference exists from the outside to the inside. The provided method can prepare the novel metal and nonmetal co-doped TiO2 nanotube, the sensitivity range of the nanotube is expanded to the visible light area, at the same time, balance of electric charges in a doping material system is kept, and the photocatalytic performance of a catalyst is improved.
Description
Technical field
The present invention relates to a kind of metal and nonmetal codope TiO of heterogeneous distribution
2the preparation method of nano-tube material, belongs to field of photocatalytic material.
Background technology
Catalysis material can utilize himself special semiconductor energy band structure that light energy conversion is become to electric energy or chemical energy, or utilizes it to drive the catalysis characteristics of oxidation-reduction reaction, carries out oxidation Decomposition organic pollution.In numerous catalysis materials, the feature that titanium dioxide is inexpensive because having, stable, nontoxic and catalytic activity is high becomes the catalysis material of tool actual application prospect.But its greater band gap, can only can not be made full use of the visible light part that accounts for solar energy 42% left and right by ultraviolet excitation.Develop at present several different methods and expanded TiO
2response wave length, as compound in semiconductor, noble metal loading, dye sensitization and ion doping etc.Wherein ion doping is a kind of TiO that effectively expands
2the method of response wave length, can be divided into metal ion mixing, nonmetallic ion-doped and metal and non-metallic ion co-doped.
Metal ion mixing can improve TiO on the one hand
2ultraviolet light activity, also can expand on the other hand its photoresponse scope to visible region.But metal ion mixing TiO
2aspect also exists some problems not yet to solve, as poor in the material heat endurance of metal ion mixing, and the doping oxidized rear metal conduction band of ion position will change, and energy level will reduce; The ion of doping itself also can become electron-hole complex centre, has reduced photocatalysis efficiency etc.Metal and nonmetalloid codope have overcome above-mentioned shortcoming to a certain extent, become gradually the important directions of research.
Different doping way has caused dopant at TiO
2form on particle and the difference of distribution mode, thus doping ion pair TiO affected
2the effect of photocatalytic process.Because the reaction of photo-generated carrier and surface hydroxyl, water, oxygen and adsorb organic compound all occurs in the surface of doped samples, and directly or be connected to doping ion and participate in.Therefore, to doping ion at TiO
2distribution mode on particle has proposed higher requirement.For making TiO
2particle interface reaction is effectively carried out, therefore surface doping ion concentration can not be too low; On the other hand, for reduce body mutually in the recombination probability in light induced electron and hole, sample body mutually in the concentration of doping ion can not be too high.
Titanium dioxide (TiO
2) nanotube is because of its unique structure and good physicochemical properties, have broad application prospects in photocatalysis, solar cell, sensor and Chu Qing field.As compound other less particles in nanotube, construct new nanostructured pattern, prepare Novel composite nano material, be expected to improve its photoelectricity, electromagnetism and catalytic performance.Therefore, on nano-tube material basis, realize the heterogeneous distribution of metal ion on metal and nonmetal codope particle, meet the requirement of photocatalytic process to doping ion distribution form and mode, become the focus and emphasis problem of this area research.
Summary of the invention
For effectively solving above-mentioned metal-doped TiO
2the shortcoming that material exists, the object of this invention is to provide a kind of metal and nonmetal codope TiO of heterogeneous distribution
2the preparation method of nanotube, with nonmetal doping TiO
2nano-tube material is matrix, and metal ion, in the heterogeneous distribution of nanotube surface, is existed to the rich concentration of metal district on surface, there is poor concentration district in mutually in body, on dispersal direction, there is concentration difference, with reduce body mutually in the recombination probability in light induced electron and hole, improve photocatalysis performance.
The technical solution used in the present invention is:
The metal of heterogeneous distribution and nonmetal codope TiO
2the preparation method of nanotube, comprises the steps:
(1) under the condition of vigorous stirring, by TiCl
4slowly be added drop-wise in a certain amount of deionized water, agitating solution 10-30min, the temperature of controlling deionized water is-5 to-2 ℃;
(2) by concentrated ammonia liquor regulator solution pH value to 4-7, stir after 1-5h and leave standstill, obtain solid after ageing and filtration, and by deionized water, it is cleaned repeatedly, eliminate Cl-in solid;
(3) after solid step (2) being obtained is dried, grinds under 60-100 ℃ of vacuum condition, in Muffle furnace, 300-500 ℃ of roasting obtains nitrogen doped Ti O
2photochemical catalyst;
(4) by a certain amount of nitrogen doped Ti O
2the concentration of photochemical catalyst and 50-100mL is 5-10molL
-1naOH solution mix, stir 5-30min, then move in water heating kettle with teflon lined 100-150 ℃ of hydro-thermal reaction 12-24h;
(5) outwell supernatant, be precipitated and wash by deionized water after centrifugation, controlling pH value is 8-10; After filtration, obtain solid;
(6) the HCl washing step that is 0.05-0.2mol/L by concentration (5) is obtained solid 10-30min, after filtration, is washed till neutrality by deionized water, and controlling pH value is 6-7; Centrifugation goes out solid;
(7) by the solid after step (6) centrifugation at 60-80 ℃ of vacuum drying 4-6 hour, grind; 300-500 ℃ of roasting temperature 2-4h in Muffle furnace, obtains nitrogen doped Ti O
2nanotube;
(8) under agitating heating evaporation conditions, by nitrogen doped Ti O
2it is in 0.1-1wt% metal compound solution that nanotube is mixed in mass fraction, and after solution evaporate to dryness, the solid obtaining is dry under 60-100 ℃ of vacuum condition, and after grinding, at 300-500 ℃, roasting obtains powder I;
(9) the powder I obtaining being mixed in to mass fraction is in 1.0-1.5wt% metal compound solution, and after solution evaporate to dryness, the solid obtaining is dry under 60-100 ℃ of vacuum condition, and after grinding, at 300-500 ℃, roasting obtains powder II;
(10) the powder II obtaining being mixed in to mass fraction is in 1.5-2.0wt% metal compound solution, after solution evaporate to dryness, the solid obtaining is dry under 60-100 ℃ of vacuum condition, and after grinding, at 300-500 ℃, roasting obtains metal and nitrogen co-doped TiO
2nanotube.
Described metal and nitrogen co-doped TiO
2metallic element in nanotube is the one in Cr, Mn, Fe, Co, Ni, Cu, Zn.
Method provided by the invention can be prepared metal and nonmetal nitrogen co-doped TiO
2nanotube, realizes the heterogeneous distribution of metal ion on nanotube, has the rich concentration of metal district in nanotube surface, and body exists poor concentration district in mutually, has concentration difference on dispersal direction, has maintained TiO
2the balance of electric charge in catalysis material system, expands to visible region the sensitive volume of catalyst, possesses visible light-responded ability, has improved catalyst photocatalysis performance.
Accompanying drawing explanation
Fig. 1 is the nitrogen co-doped TiO of nickel
2nanotube UV-Vis DRS collection of illustrative plates, abscissa is wavelength, ordinate is absorption intensity.
Fig. 2 is the nitrogen co-doped TiO of nickel
2xPS collection of illustrative plates before and after nanotube sputter, abscissa is that ordinate is Relative Peak intensity in conjunction with energy.
The nitrogen co-doped TiO of Fig. 3 nickel
2nanotube TEM figure.
Fig. 4 is under UV-irradiation condition, the nitrogen co-doped TiO of nickel
2nanotube and the active correlation curve of powder degraded 4-chlorophenol ultraviolet catalytic.
Fig. 5 is under radiation of visible light condition, the nitrogen co-doped TiO of nickel
2nanotube and powder Visible Light Induced Photocatalytic 4-chlorophenol catalytic activity are to its curve.
Fig. 6 is that metal ion is at nanotube surface distribution schematic diagram.
The specific embodiment
The TiO preparing in order to investigate the present invention
2the photocatalytic activity of nano tube catalyst, under ultraviolet light and radiation of visible light, take 4-chlorophenol as degradation product, carries out photocatalytic degradation experiment respectively, and experimental data is as follows:
Experiment condition: catalyst activity evaluation experimental condition is that catalyst amount is 0.8
gl
-1, the initial concentration of 4-chlorophenol is 1.2 × 10
-4m
olL
-1, 250W xenon lamp is as visible light source, and by 400nm optical filter filtering ultraviolet light part, controlling water-bath temperature is 30 ℃.
TiO
2the preparation method of nano tube catalyst comprises the steps:
(1) under the condition of vigorous stirring, by TiCl
4slowly be added drop-wise in a certain amount of deionized water, agitating solution 10min, the temperature of controlling deionized water is-5 to-2 ℃;
(2), by concentrated ammonia liquor regulator solution pH value to 6, stir after 120min and leave standstill, obtain solid after ageing and filtration, and it is cleaned repeatedly by deionized water to Cl-in elimination solid;
(3) after solid step (2) being obtained is dried, grinds under 80 ℃ of vacuum conditions, in Muffle furnace, 350 ℃ of roastings obtain nitrogen doped Ti O
2photochemical catalyst;
(4) by a certain amount of nitrogen doped Ti O
2the concentration of photochemical catalyst and 50mL is 10molL
-1naOH solution mix, stir 10min, then move in water heating kettle with teflon lined 100 ℃ of hydro-thermal reaction 12h;
(5) outwell supernatant, be precipitated and wash by deionized water after centrifugation, controlling pH value is 8; After filtration, obtain solid;
(6) the HCl washing step that is 0.05mol/L by concentration (5) is obtained solid 20min, after filtration, is washed till neutrality by deionized water, and controlling pH value is 7; Centrifugation goes out solid;
(7) by the solid after step (6) centrifugation at 80 ℃ of vacuum drying 4h, grind; 350 ℃ of roasting temperature 4h in Muffle furnace, obtain nitrogen doped Ti O
2nanotube;
(8) under agitating heating evaporation conditions, by nitrogen doped Ti O
2nanotube is mixed in 0.052g Ni (NO
3)
2in, after solution evaporate to dryness, the solid obtaining is dry under 80 ℃ of vacuum conditions, and after grinding, at 300-500 ℃, roasting obtains powder I;
(9) the powder I obtaining being mixed in to mass fraction is 0.14g Ni (NO
3)
2in solution, after solution evaporate to dryness, the solid obtaining is dry under 80 ℃ of vacuum conditions, and after grinding, at 450 ℃, roasting obtains powder II;
(10) the powder II obtaining being mixed in to mass fraction is 0.156g Ni (NO
3)
2in, after solution evaporate to dryness, the solid obtaining is dry under 80 ℃ of vacuum conditions, and after grinding, at 500 ℃, roasting obtains metal and nitrogen co-doped TiO
2nanotube.
Fig. 1 is the nitrogen co-doped TiO of nickel
2nanotube UV-Vis DRS collection of illustrative plates.As can be seen from Figure 1, the nitrogen co-doped TiO of prepared nickel
2nanotube photosensitive region is expanded to visible region.
Fig. 2 is the nitrogen co-doped TiO of nickel
2xPS collection of illustrative plates before and after nanotube sputter.As seen from Figure 2, the concentration of the concentration of Ni before sputter after higher than sputter, has verified metal ion heterogeneous distribution on nanotube, and surface exists rich concentration district, and body exists poor concentration district in mutually, has concentration difference.
Fig. 3 is the nitrogen co-doped TiO of nickel
2nanotube TEM figure.From Fig. 3, can find out, prepared material has nano tube structure.
Fig. 4 has investigated under UV-irradiation condition, the nitrogen co-doped TiO of nickel
2nanotube and the active correlation curve of powder degraded 4-chlorophenol ultraviolet catalytic.Can find out the nitrogen co-doped TiO of nickel
2nanotube degradation rate is 88.96%, the nitrogen co-doped TiO of nickel
2powder degradation rate is 53.48%, and ultraviolet degradation efficiency has improved 66.34%.
Fig. 5 has investigated under radiation of visible light condition, the nitrogen co-doped TiO of nickel
2nanotube and powder Visible Light Induced Photocatalytic 4-chlorophenol catalytic activity correlation curve.The nitrogen co-doped TiO of nickel
2nanotube Visible Light Induced Photocatalytic efficiency is 80.73%, the nitrogen co-doped TiO of nickel
2powder Visible Light Induced Photocatalytic efficiency is 45.77%, and Visible Light Induced Photocatalytic efficiency has improved 76.38 percentage points.
In Fig. 4-5, C is the concentration after degraded, C
0for the concentration before degraded.
Fig. 6 has shown that metallic element of the present invention is heterogeneous distribution in nanotube surface,, by showing and the interior rich concentration district of metal and the poor concentration district of existing, has concentration difference.
Claims (2)
1. the metal of heterogeneous distribution and nonmetal codope TiO
2the preparation method of nanotube, is characterized in that, comprises the steps:
(1) under the condition of vigorous stirring, by TiCl
4slowly be added drop-wise in a certain amount of deionized water, agitating solution 10-30min, the temperature of controlling deionized water is-5 to-2 ℃;
(2) by concentrated ammonia liquor regulator solution pH value to 4-7, stir after 1-5h and leave standstill, obtain solid after ageing and filtration, and by deionized water, it is cleaned repeatedly, eliminate Cl-in solid;
(3) after solid step (2) being obtained is dried, grinds under 60-100 ℃ of vacuum condition, in Muffle furnace, 300-500 ℃ of roasting obtains nitrogen doped Ti O
2photochemical catalyst;
(4) by a certain amount of nitrogen doped Ti O
2the concentration of photochemical catalyst and 50-100mL is 5-10molL
-1naOH solution mix, stir 5-30min, then move in water heating kettle with teflon lined 100-150 ℃ of hydro-thermal reaction 12-24h;
(5) outwell supernatant, be precipitated and wash by deionized water after centrifugation, controlling pH value is 8-10; After filtration, obtain solid;
(6) the HCl washing step that is 0.05-0.2mol/L by concentration (5) is obtained solid 10-30min, after filtration, is washed till neutrality by deionized water, and controlling pH value is 6-7; Centrifugation goes out solid;
(7) by the solid after step (6) centrifugation at 60-80 ℃ of vacuum drying 4-6 hour, grind; 300-500 ℃ of roasting temperature 2-4h in Muffle furnace, obtains nitrogen doped Ti O
2nanotube;
(8) under agitating heating evaporation conditions, by nitrogen doped Ti O
2it is in 0.1-1wt% metal compound solution that nanotube is mixed in mass fraction, and after solution evaporate to dryness, the solid obtaining is dry under 60-100 ℃ of vacuum condition, and after grinding, at 300-500 ℃, roasting obtains powder I;
(9) the powder I obtaining being mixed in to mass fraction is in 1.0-1.5wt% metal compound solution, and after solution evaporate to dryness, the solid obtaining is dry under 60-100 ℃ of vacuum condition, and after grinding, at 300-500 ℃, roasting obtains powder II;
(10) the powder II obtaining being mixed in to mass fraction is in 1.5-2.0wt% metal compound solution, after solution evaporate to dryness, the solid obtaining is dry under 60-100 ℃ of vacuum condition, and after grinding, at 300-500 ℃, roasting obtains metal and nitrogen co-doped TiO
2nanotube.
2. the metal of heterogeneous distribution according to claim 1 and nonmetal codope TiO
2the preparation method of nanotube, is characterized in that, described metal and nitrogen co-doped TiO
2metallic element in nanotube is the one in Cr, Mn, Fe, Co, Ni, Cu, Zn.
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Cited By (3)
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CN105107494A (en) * | 2015-07-30 | 2015-12-02 | 苏州弗莱希智能科技有限公司 | Activated carbon based nano TiO2 composite MnO2 catalytic material and preparation method therefor |
CN111632618A (en) * | 2020-07-08 | 2020-09-08 | 青岛哈工程正和环保科技有限公司 | Preparation method and application of supported double-doped modified titanium dioxide photocatalyst |
CN114797918A (en) * | 2022-05-30 | 2022-07-29 | 安徽工业大学 | Titanium dioxide-based hydrogenation catalyst material and preparation method and application thereof |
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CN102500405A (en) * | 2011-10-26 | 2012-06-20 | 辽宁大学 | Cerium, nitrogen and fluoride co-doped titanium dioxide photocatalyst and application thereof in degrading organic pollutants in visible light |
CN102764667A (en) * | 2012-07-30 | 2012-11-07 | 江苏高淳陶瓷股份有限公司 | Samarium/nitrogen-co-doped titanium dioxide catalyst capable of responding to visible light and preparation method thereof |
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Patent Citations (4)
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CN101462068A (en) * | 2009-01-14 | 2009-06-24 | 南开大学 | Iron and nitrogen co-doped mesoporous titanium oxide photochemical catalyst material and preparation method thereof |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105107494A (en) * | 2015-07-30 | 2015-12-02 | 苏州弗莱希智能科技有限公司 | Activated carbon based nano TiO2 composite MnO2 catalytic material and preparation method therefor |
CN111632618A (en) * | 2020-07-08 | 2020-09-08 | 青岛哈工程正和环保科技有限公司 | Preparation method and application of supported double-doped modified titanium dioxide photocatalyst |
CN114797918A (en) * | 2022-05-30 | 2022-07-29 | 安徽工业大学 | Titanium dioxide-based hydrogenation catalyst material and preparation method and application thereof |
CN114797918B (en) * | 2022-05-30 | 2024-02-27 | 安徽工业大学 | Titanium dioxide-based hydrogenation catalyst material, and preparation method and application thereof |
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Application publication date: 20140528 |