CN103990474A - Preparation method of 3D-shaped silver/silver bromide/titanium dioxide catalyst - Google Patents
Preparation method of 3D-shaped silver/silver bromide/titanium dioxide catalyst Download PDFInfo
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- CN103990474A CN103990474A CN201410206753.8A CN201410206753A CN103990474A CN 103990474 A CN103990474 A CN 103990474A CN 201410206753 A CN201410206753 A CN 201410206753A CN 103990474 A CN103990474 A CN 103990474A
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Abstract
The invention relates to a preparation method of a 3D-shaped silver/silver bromide/titanium dioxide catalyst. The preparation method comprises the following steps: firstly mixing titanate with concentrated hydrochloric acid, and dropwise adding a water solution of cetyl trimethyl ammonium bromide into a titanate solution; respectively adding ethanol and urea into a mixed solution of the titanate and cetyl trimethyl ammonium bromide, uniformly mixing, and carrying out hydrothermal reaction at 150 DEG C; adding silver nitrate and ammonium hydroxide into turbid liquid obtained in the hydrothermal reaction, stirring for 24 hours, carrying out centrifugal washing and drying, and roasting for 2 hours at 400 DEG C; carrying out reduction on roasted samples for 3 hours under ultraviolet light, so as to obtain the 3D-shaped silver/silver bromide/titanium dioxide catalyst. The preparation method has the beneficial effects that the process is simple, requirements on equipment are low, and the prepared titanium dioxide photocatalyst has strong response under a visible light condition.
Description
Technical field
The present invention relates to the preparation method of the titanium dioxide optical catalyst of load silver under a kind of high temperature and high pressure environment.
Background technology
Titanium dioxide is as a kind of wide bandgap semiconductor, due to its stable chemical nature, photocatalytic activity efficiently, is widely used in the fields such as atmosphere, the degraded of water environment pollution thing, antibacterial, deodorizing and automatically cleaning.But the photoresponse scope of titanium dioxide is ultraviolet region, low to the utilization rate of sunshine; And excite the electronics of generation to be easy to hole-recombination, photo-quantum efficiency is low, seriously restricts its practical application at aspects such as photocatalysis.In recent years, people attempt the means such as and dye photoactivation compound by metal-doped, nonmetal doping, metal and nonmetal codope, semiconductor, expand the photoresponse scope of titanium dioxide, suppress the compound of electronics and hole, thereby improve the photocatalysis performance of titanium dioxide and compound thereof.Silver bromide is a kind of important inorganic light-sensitive material, has very high visible light-respondedly, and silver bromide can form heterogeneous semiconductor junction structure with titanium dioxide simultaneously, suppresses electronics and hole-recombination, improves the visible light catalysis activity of titanium dioxide.
But so far, for the bigger serface 3D pattern Ag/AgBr/TiO of photocatalytic degradation
2preparation method have not been reported.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of 3D pattern silver/silver bromide/titanium deoxide catalyst.
A preparation method for 3D pattern silver/silver bromide/titanium deoxide catalyst, is characterized in that, concrete steps are as follows:
First titanate esters is mixed with concentrated hydrochloric acid, then the aqueous solution of softex kw is added drop-wise in titanate esters solution; Ethylene glycol and urea are joined respectively in the mixed solution of above-mentioned titanate esters and softex kw, mix latter 150 DEG C and carry out hydro-thermal reaction; In the suspension obtaining in hydro-thermal reaction, add silver nitrate and ammoniacal liquor, stir after 24 hours centrifuge washing dry, roasting 2 hours at 400 DEG C; Sample after roasting reduces 3 hours under ultraviolet light, obtains 3D pattern silver/silver bromide/titanium deoxide catalyst.
The molar ratio of described titanate esters and hydrochloric acid is 1:50～200.
The molar ratio of described titanate esters and softex kw is 1:0.5～1, and the molar ratio of titanate esters and water is 1:1000～2000.
The molar ratio of described titanate esters and ethylene glycol is 1:1000～2000, and the molar ratio of titanate esters and urea is 1:20～40.
Described hydrothermal temperature is 150 DEG C, and the hydro-thermal time is 8～24 hours.
The molar ratio of described titanate esters and silver nitrate is 1:0.05～0.3.
3D Ag/AgBr/TiO
2performance evaluation in quartz glass tube, carry out, evaluate thing be 10mg/L reactive blue dye solution, photochemical catalyst consumption is 1mg/mL, suspension stir 1h.Suspension is exposed under xenon lamp, filters ultraviolet light and carry out after photocatalytic degradation 300min, suspension is taking 12000rpm as rotating speed, centrifugal 10min.Utilize reactive blue concentration in spectrophotometric determination supernatant, calculate reactive blue photocatalytic activity.
This preparation method can increase titanium dioxide optical catalyst specific area, widen the visible light-responded scope of titanium dioxide optical catalyst, technique is simpler.
Brief description of the drawings
Fig. 1 is 3D Ag/AgBr/TiO
2scanning electron microscope (SEM) photograph.
Fig. 2 is 3D Ag/AgBr/TiO
2ultraviolet-visible absorption spectroscopy figure.
Detailed description of the invention
Below embodiments of the invention is elaborated: the present embodiment is implemented under taking technical solution of the present invention as prerequisite, provided detailed embodiment and operating process, but protection scope of the present invention is not limited to following embodiment:
Embodiment 1:
First titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred, the molar ratio of titanate esters and hydrochloric acid is 1:50.In deionized water, add softex kw (CTAB), mix and stir.The CTAB aqueous solution is added drop-wise in titanate esters solution, stirs 1h.The molar ratio of titanate esters and CTAB is 1:0.5, and the molar ratio of titanate esters and water is 1:2000.A certain amount of ethylene glycol and urea are joined respectively in the mixed solution of above-mentioned titanate esters and CTAB, stir.The molar ratio of titanate esters and ethylene glycol is 1:1000, and the molar ratio of titanate esters and urea is 1:20.Above-mentioned mixed solution is joined in 100mL water heating kettle, and 150 DEG C of hydro-thermal reaction 24h generate the titanium dioxide of 3D pattern.Silver nitrate and 2mL ammoniacal liquor are joined to hydro-thermal reaction obtains containing in the suspension of 3D pattern titanium dioxide, stir 24h and bromizate silver and load on 3D pattern titanium dioxide, centrifugal, and wash respectively 3 times by ethanol and deionized water, at 80 DEG C more than dry 10h.The molar ratio of titanate esters and silver nitrate is 1:0.05.By above-mentioned dry sample roasting 2h at 400 DEG C, remove residual organic matter, the sample obtaining reduces under ultraviolet light processes 3h, makes catalyst surface generate Ag
0nano particle, obtains 3D Ag/AgBr/TiO
2.
By the 3D Ag/AgBr/TiO making
2photochemical catalyst carries out catalytic performance test by previous experiments condition, and the degradation rate of measuring reactive blue is 2.5%.
Embodiment 2:
First titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred, the molar ratio of titanate esters and hydrochloric acid is 1:100.In deionized water, add softex kw (CTAB), mix and stir.The CTAB aqueous solution is added drop-wise in titanate esters solution, stirs 1h.The molar ratio of titanate esters and CTAB is 1:1, and the molar ratio of titanate esters and water is 1:1000.A certain amount of ethylene glycol and urea are joined respectively in the mixed solution of above-mentioned titanate esters and CTAB, stir.The molar ratio of titanate esters and ethylene glycol is 1:2000, and the molar ratio of titanate esters and urea is 1:20.Above-mentioned mixed solution is joined in 100mL water heating kettle, and 150 DEG C of hydro-thermal reaction 24h generate the titanium dioxide of 3D pattern.Silver nitrate and 2mL ammoniacal liquor are joined to hydro-thermal reaction obtains containing in the suspension of 3D pattern titanium dioxide, stir 24h and bromizate silver and load on 3D pattern titanium dioxide, centrifugal, and wash respectively 3 times by ethanol and deionized water, at 80 DEG C more than dry 10h.The molar ratio of titanate esters and silver nitrate is 1:0.1.By above-mentioned dry sample roasting 2h at 400 DEG C, remove residual organic matter, the sample obtaining reduces under ultraviolet light processes 3h, makes catalyst surface generate Ag
0nano particle, obtains 3D Ag/AgBr/TiO
2.
By the 3D Ag/AgBr/TiO making
2photochemical catalyst carries out catalytic performance test by previous experiments condition, and the degradation rate of measuring reactive blue is 10.3%.
Embodiment 3:
First titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred, the molar ratio of titanate esters and hydrochloric acid is 1:200.In deionized water, add softex kw (CTAB), mix and stir.The CTAB aqueous solution is added drop-wise in titanate esters solution, stirs 1h.The molar ratio of titanate esters and CTAB is 1:1, and the molar ratio of titanate esters and water is 1:2000.A certain amount of ethylene glycol and urea are joined respectively in the mixed solution of above-mentioned titanate esters and CTAB, stir.The molar ratio of titanate esters and ethylene glycol is 1:2000, and the molar ratio of titanate esters and urea is 1:40.Above-mentioned mixed solution is joined in 100mL water heating kettle, and 150 DEG C of hydro-thermal reaction 12h generate the titanium dioxide of 3D pattern.Silver nitrate and 2mL ammoniacal liquor are joined to hydro-thermal reaction obtains containing in the suspension of 3D pattern titanium dioxide, stir 24h and bromizate silver and load on 3D pattern titanium dioxide, centrifugal, and wash respectively 3 times by ethanol and deionized water, at 80 DEG C more than dry 10h.The molar ratio of titanate esters and silver nitrate is 1:0.3.By above-mentioned dry sample roasting 2h at 400 DEG C, remove residual organic matter, the sample obtaining reduces under ultraviolet light processes 3h, makes catalyst surface generate Ag
0nano particle, obtains 3D Ag/AgBr/TiO
2.
By the 3D Ag/AgBr/TiO making
2photochemical catalyst carries out catalytic performance test by previous experiments condition, and the degradation rate of measuring reactive blue is 35.8%.
Embodiment 4:
First titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred, the molar ratio of titanate esters and hydrochloric acid is 1:200.In deionized water, add softex kw (CTAB), mix and stir.The CTAB aqueous solution is added drop-wise in titanate esters solution, stirs 1h.The molar ratio of titanate esters and CTAB is 1:1, and the molar ratio of titanate esters and water is 1:2000.A certain amount of ethylene glycol and urea are joined respectively in the mixed solution of above-mentioned titanate esters and CTAB, stir.The molar ratio of titanate esters and ethylene glycol is 1:2000, and the molar ratio of titanate esters and urea is 1:30.Above-mentioned mixed solution is joined in 100mL water heating kettle, and 150 DEG C of hydro-thermal reaction 8h generate the titanium dioxide of 3D pattern.Silver nitrate and 2mL ammoniacal liquor are joined to hydro-thermal reaction obtains containing in the suspension of 3D pattern titanium dioxide, stir 24h and bromizate silver and load on 3D pattern titanium dioxide, centrifugal, and wash respectively 3 times by ethanol and deionized water, at 80 DEG C more than dry 10h.The molar ratio of titanate esters and silver nitrate is 1:0.1.By above-mentioned dry sample roasting 2h at 400 DEG C, remove residual organic matter, the sample obtaining reduces under ultraviolet light processes 3h, makes catalyst surface generate Ag
0nano particle, obtains 3D Ag/AgBr/TiO
2.
By the 3D Ag/AgBr/TiO making
2photochemical catalyst carries out catalytic performance test by previous experiments condition, and the degradation rate of measuring reactive blue is 44.3%.
Claims (6)
1. a preparation method for 3D pattern silver/silver bromide/titanium deoxide catalyst, is characterized in that, concrete steps are as follows:
First titanate esters is mixed with concentrated hydrochloric acid, then the aqueous solution of softex kw is added drop-wise in titanate esters solution; Ethylene glycol and urea are joined respectively in the mixed solution of above-mentioned titanate esters and softex kw, mix latter 150 DEG C and carry out hydro-thermal reaction; In the suspension obtaining in hydro-thermal reaction, add silver nitrate and ammoniacal liquor, stir after 24 hours centrifuge washing dry, roasting 2 hours at 400 DEG C; Sample after roasting reduces 3 hours under ultraviolet light, obtains 3D pattern silver/silver bromide/titanium deoxide catalyst.
2. the preparation method of 3D pattern silver/silver bromide/titanium deoxide catalyst according to claim 1, is characterized in that, the molar ratio of described titanate esters and hydrochloric acid is 1:50～200.
3. the preparation method of 3D pattern silver/silver bromide/titanium deoxide catalyst according to claim 1, it is characterized in that, the molar ratio of described titanate esters and softex kw is 1:0.5～1, and the molar ratio of titanate esters and water is 1:1000～2000.
4. the preparation method of 3D pattern silver/silver bromide/titanium deoxide catalyst according to claim 1, is characterized in that, the molar ratio of described titanate esters and ethylene glycol is 1:1000～2000, and the molar ratio of titanate esters and urea is 1:20～40.
5. the preparation method of 3D pattern silver/silver bromide/titanium deoxide catalyst according to claim 1, is characterized in that, described hydrothermal temperature is 150 DEG C, and the hydro-thermal time is 8～24 hours.
6. the preparation method of 3D pattern silver/silver bromide/titanium deoxide catalyst according to claim 1, is characterized in that, the molar ratio of described titanate esters and silver nitrate is 1:0.05～0.3.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607214A (en) * | 2015-01-19 | 2015-05-13 | 上海交通大学 | Preparation method of AgBr/TiO2 catalyst responding to visible light |
| CN105013516A (en) * | 2015-07-01 | 2015-11-04 | 杭州臣工环保科技有限公司 | Supported multistage structure silver-silver halide-titanium dioxide composite light visible catalytic material and preparation method therefor |
| CN105289192A (en) * | 2015-10-13 | 2016-02-03 | 山东大学 | Room-temperature formaldehyde decomposing agent suitable for air purifier and preparation method thereof |
| CN105903347A (en) * | 2016-04-27 | 2016-08-31 | 吉首大学 | Photoelectric synergetic air purifier |
| CN107456983A (en) * | 2017-07-17 | 2017-12-12 | 山东大学 | A kind of Ag/AgCl/TiO2Composite photocatalyst material and its preparation method and application |
| CN107597092A (en) * | 2017-07-21 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | 3D patterns CeO2/TiO2Preparation method of catalyst |
| CN108666588A (en) * | 2018-05-10 | 2018-10-16 | 东北师范大学 | A kind of three-dimensional substrates material load Ag doping titanium dioxide optical catalyst and the preparation method and application thereof |
| CN108975383A (en) * | 2018-08-29 | 2018-12-11 | 淮阴师范学院 | The preparation method of porous Ag/AgBr nano material |
| CN109046401A (en) * | 2018-07-06 | 2018-12-21 | 上海纳米技术及应用国家工程研究中心有限公司 | 3D pattern silver/silver bromide/titanium dioxide optical catalyst preparation and products thereof and application |
| CN109046304A (en) * | 2018-09-04 | 2018-12-21 | 西北师范大学 | Hydrogenate the preparation method of the flower-shaped titanium dioxide of grey |
| CN111111708A (en) * | 2019-11-12 | 2020-05-08 | 常州良福朗清生物科技有限公司 | Preparation method and application of silver/silver halide loaded mesoporous titanium dioxide microspheres |
| CN111921545A (en) * | 2020-09-09 | 2020-11-13 | 上海腾灵冷暖设备工程有限公司 | Catalyst for degrading sulfapyridine under visible light and preparation method thereof |
| CN114405524A (en) * | 2022-01-29 | 2022-04-29 | 中国科学院东北地理与农业生态研究所 | P-n heterojunction type Pt/TiO2Preparation method of/AgBr/Ag composite photocatalyst |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607214A (en) * | 2015-01-19 | 2015-05-13 | 上海交通大学 | Preparation method of AgBr/TiO2 catalyst responding to visible light |
| CN105013516A (en) * | 2015-07-01 | 2015-11-04 | 杭州臣工环保科技有限公司 | Supported multistage structure silver-silver halide-titanium dioxide composite light visible catalytic material and preparation method therefor |
| CN105289192A (en) * | 2015-10-13 | 2016-02-03 | 山东大学 | Room-temperature formaldehyde decomposing agent suitable for air purifier and preparation method thereof |
| CN105903347A (en) * | 2016-04-27 | 2016-08-31 | 吉首大学 | Photoelectric synergetic air purifier |
| CN107456983B (en) * | 2017-07-17 | 2020-03-17 | 山东大学 | Ag/AgCl/TiO2Composite photocatalytic material and preparation method and application thereof |
| CN107456983A (en) * | 2017-07-17 | 2017-12-12 | 山东大学 | A kind of Ag/AgCl/TiO2Composite photocatalyst material and its preparation method and application |
| CN107597092A (en) * | 2017-07-21 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | 3D patterns CeO2/TiO2Preparation method of catalyst |
| CN108666588A (en) * | 2018-05-10 | 2018-10-16 | 东北师范大学 | A kind of three-dimensional substrates material load Ag doping titanium dioxide optical catalyst and the preparation method and application thereof |
| CN109046401A (en) * | 2018-07-06 | 2018-12-21 | 上海纳米技术及应用国家工程研究中心有限公司 | 3D pattern silver/silver bromide/titanium dioxide optical catalyst preparation and products thereof and application |
| CN108975383A (en) * | 2018-08-29 | 2018-12-11 | 淮阴师范学院 | The preparation method of porous Ag/AgBr nano material |
| CN109046304A (en) * | 2018-09-04 | 2018-12-21 | 西北师范大学 | Hydrogenate the preparation method of the flower-shaped titanium dioxide of grey |
| CN111111708A (en) * | 2019-11-12 | 2020-05-08 | 常州良福朗清生物科技有限公司 | Preparation method and application of silver/silver halide loaded mesoporous titanium dioxide microspheres |
| CN111921545A (en) * | 2020-09-09 | 2020-11-13 | 上海腾灵冷暖设备工程有限公司 | Catalyst for degrading sulfapyridine under visible light and preparation method thereof |
| CN114405524A (en) * | 2022-01-29 | 2022-04-29 | 中国科学院东北地理与农业生态研究所 | P-n heterojunction type Pt/TiO2Preparation method of/AgBr/Ag composite photocatalyst |
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Application publication date: 20140820 |