CN102989498A - Method for preparing carbon, nitrogen and sulfur codoped modified titanium dioxide visible-light-induced photocatalyst - Google Patents
Method for preparing carbon, nitrogen and sulfur codoped modified titanium dioxide visible-light-induced photocatalyst Download PDFInfo
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- CN102989498A CN102989498A CN2012105605726A CN201210560572A CN102989498A CN 102989498 A CN102989498 A CN 102989498A CN 2012105605726 A CN2012105605726 A CN 2012105605726A CN 201210560572 A CN201210560572 A CN 201210560572A CN 102989498 A CN102989498 A CN 102989498A
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Abstract
The invention relates to a method for preparing a carbon, nitrogen and sulfur codoped modified titanium dioxide visible-light-induced photocatalyst, comprising the following steps of mixing titanate with an organic solvent, preparing a thiourea aqueous solution in acid deionized water, slowly dropwise adding the prepared titanate solution in the prepared thiourea solution under the magnetic stirring, stirring till the solution is changed into transparent gel, standing, obtaining the transparent gel, drying the transparent gel at the low temperature, putting the dried transparent gel in a muffle furnace, roasting at the low temperature and obtaining the target product. The method is simple in process and has the advantage that the visible light absorption range of the titanium dioxide photocatalyst can be effectively expanded to 550nm.
Description
Technical field
The present invention relates to that doping carbon nitrogen sulphur carries out the titanium dioxide visible light catalyzer modification under a kind of normal temperature and pressure environment.Relate to that doping carbon nitrogen sulphur carries out the titanium dioxide visible light catalyzer modification under a kind of normal temperature and pressure environment.
Background technology
Titanium dioxide is as a kind of wide bandgap semiconductor, because its stable chemical nature, efficient photocatalytic activity, is widely used in the fields such as atmosphere, the degraded of water environment pollution thing, antibiotic, deodorizing and automatically cleaning.But the energy gap of titanium dioxide (Detitanium-ore-type) is 3.2eV, and absorbing wavelength is less than 388nm, and absorption bands is ultraviolet region, seriously restricts it in the practical application of the aspects such as photocatalysis.The multiple nonmetalloids such as titania additive carbon, fluorine, nitrogen, sulphur can improve its photocatalytic activity, expand its visible light-responded scope.
The researcher has done large quantity research around the nonmetal doping of titanium dioxide.Bibliographical information a kind of preparation method who prepares at a lower temperature nitrogen doping type titanium dioxide visible light catalyzer, use up the method that helps synthetic sol-gel, prepare the titanium dioxide optical catalyst of nitrogen doping type as raw material take titanate esters, ammonium salt.Bibliographical information set up a kind of nonmetal doping titanium base film electrode, preparation method and application thereof, nonmetal doping titanium dioxide granule, pore creating material be mixed with into latex with titanium dioxide nanocrystalline emulsion and film after heat-treat, be prepared into titanium base film electrode.Bibliographical information the titania-doped composite manufacture method of a kind of carbon, take titanium trichloride as the titanium source, take sucrose as carbon source, prepare the composite of indefiniteness titanium dioxide and carbon.But said method complex steps or calcining heat are higher, are unfavorable for operation.
Summary of the invention
In order to overcome the defective of prior art, the invention provides the preparation method of the codoping modified titanium dioxide visible light catalyzer of a kind of carbon nitrogen sulphur.
The preparation method of the codoping modified titanium dioxide visible light catalyzer of a kind of carbon nitrogen sulphur is characterized in that, comprises the steps:
(1) titanate esters is mixed with organic solvent;
(2) in acid deionized water, dispose thiourea solution;
(3) under magnetic agitation, the titanate esters solution of step (1) preparation is slowly dropwise joined and be stirred to solution in the thiourea solution of step (2) preparation and become clear gel; Gel leaves standstill, and obtains clear gel;
(4) clear gel low temperature drying is put into the Muffle furnace low-temperature bake with the gel of drying and is obtained target product.
The volume ratio of described titanate esters and organic solvent is 1:2～1:10.
The compound method of described acid deionized water in deionized water, add citric acid to pH be 3～5.
The volume ratio of described titanate esters solution and thiourea solution is 1:1～3:1.
The mol ratio 1:100 of described thiocarbamide and titanium～1:20.
Described gel bake out temperature is 50～80 ℃, and sintering temperature is 250～350 ℃, and roasting time is 3～12 hours.
Described titanate esters is a kind of or its combination in isopropyl titanate, tetrabutyl titanate, the tetraethyl titanate.
Described organic solvent is a kind of or its combination in ethanol, methyl alcohol, propyl alcohol, the isopropyl alcohol.
Doping carbon nitrogen sulphur of the present invention carries out the titanium dioxide visible light catalyzer modification can expand the absorption spectrum of titanic oxide material to 550nm.
Description of drawings
Fig. 1 is according to embodiment 1～embodiment 5, when the doping mol ratio of thiocarbamide and titanate esters is respectively 1:100,1:50,1:40,1:30,1:20, and the ultraviolet-visible absorption spectroscopy of the titanium dioxide visible light catalyzer of the doping carbon nitrogen sulphur that obtains.
The specific embodiment
The below elaborates to embodiments of the invention: present embodiment is implemented under take technical solution of the present invention as prerequisite, has provided detailed embodiment and operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
At first titanate esters is mixed with organic solvent, the volume ratio of titanate esters and organic solvent is 1:5.In deionized water, add citric acid, to pH be 3～5.The certain density thiourea solution of configuration in acid deionized water.Then under magnetic agitation titanate esters solution slowly dropwise joined and be stirred to solution in the thiourea solution and become clear gel, the volume ratio of titanate esters solution and thiourea solution is 1:1, and the mol ratio of thiocarbamide and titanate esters is 1:100.The static 12h of gel obtains clear gel.Clear gel is at 50～80 ℃ of lower low temperature dryings, the gel of drying put into Muffle furnace be warming up to 250 ℃ of roasting 6h with the speed of 5 ℃/min and obtain target product.The absorption spectrum of the titanium dioxide optical catalyst that the method doping vario-property obtains is extended to 550nm.
Embodiment 2:
At first titanate esters is mixed with organic solvent, the volume ratio of titanate esters and organic solvent is 1:2.In deionized water, add citric acid, to pH be 3～5.The certain density thiourea solution of configuration in acid deionized water.Then under magnetic agitation titanate esters solution slowly dropwise joined and be stirred to solution in the thiourea solution and become clear gel, the volume ratio of titanate esters solution and thiourea solution is 3:1, and the mol ratio of thiocarbamide and titanate esters is 1:50.The static 24h of gel obtains clear gel.Clear gel is at 50～80 ℃ of lower low temperature dryings, the gel of drying put into Muffle furnace be warming up to 350 ℃ of roasting 6h with the speed of 5 ℃/min and obtain target product.The absorption spectrum of the titanium dioxide optical catalyst that the method doping vario-property obtains is extended to 570nm.
Embodiment 3:
At first titanate esters is mixed with organic solvent, the volume ratio of titanate esters and organic solvent is 1:10.In deionized water, add citric acid, to pH be 3～5.The certain density thiourea solution of configuration in acid deionized water.Then under magnetic agitation titanate esters solution slowly dropwise joined and be stirred to solution in the thiourea solution and become clear gel, the volume ratio of titanate esters solution and thiourea solution is 2:1, and the mol ratio of thiocarbamide and titanate esters is 1:40.The static 24h of gel obtains clear gel.Clear gel is at 50～80 ℃ of lower low temperature dryings, the gel of drying put into Muffle furnace be warming up to 300 ℃ of roasting 6h with the speed of 5 ℃/min and obtain target product.The absorption spectrum of the titanium dioxide optical catalyst that the method doping vario-property obtains is extended to 570nm.
Embodiment 4:
At first titanate esters is mixed with organic solvent, the volume ratio of titanate esters and organic solvent is 1:4.In deionized water, add citric acid, to pH be 3～5.The certain density thiourea solution of configuration in acid deionized water.Then under magnetic agitation titanate esters solution slowly dropwise joined and be stirred to solution in the thiourea solution and become clear gel, the volume ratio of titanate esters solution and thiourea solution is 2:1, and the mol ratio of thiocarbamide and titanate esters is 1:30.The static 24h of gel obtains clear gel.Clear gel is at 50～80 ℃ of lower low temperature dryings, the gel of drying put into Muffle furnace be warming up to 300 ℃ of roasting 3h with the speed of 5 ℃/min and obtain target product.The absorption spectrum of the titanium dioxide optical catalyst that the method doping vario-property obtains is extended to 580nm.
Embodiment 5:
At first titanate esters is mixed with organic solvent, the volume ratio of titanate esters and organic solvent is 1:5.In deionized water, add citric acid, to pH be 3～5.The certain density thiourea solution of configuration in acid deionized water.Then under magnetic agitation titanate esters solution slowly dropwise joined and be stirred to solution in the thiourea solution and become clear gel, the volume ratio of titanate esters solution and thiourea solution is 3:1, and the mol ratio of thiocarbamide and titanate esters is 1:20.The static 24h of gel obtains clear gel.Clear gel is at 50～80 ℃ of lower low temperature dryings, the gel of drying put into Muffle furnace be warming up to 350 ℃ of roasting 12h with the speed of 5 ℃/min and obtain target product.The absorption spectrum of the titanium dioxide optical catalyst that the method doping vario-property obtains is extended to 570nm.
Claims (8)
1. the preparation method of the codoping modified titanium dioxide visible light catalyzer of carbon nitrogen sulphur is characterized in that, comprises the steps:
(1) titanate esters is mixed with organic solvent;
(2) in acid deionized water, dispose thiourea solution;
(3) under magnetic agitation, the titanate esters solution of step (1) preparation is slowly dropwise joined and be stirred to solution in the thiourea solution of step (2) preparation and become clear gel; Gel leaves standstill, and obtains clear gel;
(4) clear gel low temperature drying is put into the Muffle furnace low-temperature bake with the gel of drying and is obtained target product.
2. the preparation method of the codoping modified titanium dioxide visible light catalyzer of described a kind of carbon nitrogen sulphur according to claim 1 is characterized in that the volume ratio of described titanate esters and organic solvent is 1:2～1:10.
3. the preparation method of the codoping modified titanium dioxide visible light catalyzer of described a kind of carbon nitrogen sulphur according to claim 1 is characterized in that, the compound method of described acid deionized water in deionized water, add citric acid to pH be 3～5.
4. the preparation method of the codoping modified titanium dioxide visible light catalyzer of described a kind of carbon nitrogen sulphur according to claim 1 is characterized in that the volume ratio of described titanate esters solution and thiourea solution is 1:1～3:1.
5. the preparation method of the codoping modified titanium dioxide visible light catalyzer of described a kind of carbon nitrogen sulphur according to claim 1 is characterized in that the mol ratio 1:100 of described thiocarbamide and titanium～1:20.
6. the preparation method of the codoping modified titanium dioxide visible light catalyzer of described a kind of carbon nitrogen sulphur according to claim 1 is characterized in that described gel bake out temperature is 50～80 ℃, and sintering temperature is 250～350 ℃, and roasting time is 3～12 hours.
7. the preparation method of the codoping modified titanium dioxide visible light catalyzer of described a kind of carbon nitrogen sulphur according to claim 1 is characterized in that described titanate esters is a kind of or its combination in isopropyl titanate, tetrabutyl titanate, the tetraethyl titanate.
8. the preparation method of the codoping modified titanium dioxide visible light catalyzer of described a kind of carbon nitrogen sulphur according to claim 1 is characterized in that described organic solvent is a kind of or its combination in ethanol, methyl alcohol, propyl alcohol, the isopropyl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657685B (en) * | 2013-11-27 | 2015-08-26 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of titanium dioxide optical catalyst of sulphur vanadium codope |
| CN108906107A (en) * | 2018-07-06 | 2018-11-30 | 广东海洋大学 | A kind of preparation method of sulfur and nitrogen co-doped titanium dioxide |
| CN112076775A (en) * | 2020-09-15 | 2020-12-15 | 湖南中医药大学 | Composite material for industrial wastewater treatment and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108354A (en) * | 2007-08-16 | 2008-01-23 | 华东师范大学 | Titanium dioxide visible light catalyzer and method of manufacturing the same |
| EP2123605A1 (en) * | 2008-05-15 | 2009-11-25 | Kyungpook National University Industry-Academic Cooperation Foundation | Production method of titanium dioxide (TIO2) photocatalyst and TIO2 photocatalyst produced by the same |
| CN101721985A (en) * | 2008-10-10 | 2010-06-09 | 北京化工大学 | Method for preparing sulfur and nitrogen co-doped titanium dioxide with visible light catalytic activity |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108354A (en) * | 2007-08-16 | 2008-01-23 | 华东师范大学 | Titanium dioxide visible light catalyzer and method of manufacturing the same |
| EP2123605A1 (en) * | 2008-05-15 | 2009-11-25 | Kyungpook National University Industry-Academic Cooperation Foundation | Production method of titanium dioxide (TIO2) photocatalyst and TIO2 photocatalyst produced by the same |
| CN101721985A (en) * | 2008-10-10 | 2010-06-09 | 北京化工大学 | Method for preparing sulfur and nitrogen co-doped titanium dioxide with visible light catalytic activity |
Non-Patent Citations (2)
| Title |
|---|
| QUANJUN XIANG等: "Nitrogen and sulfur co-doped TiO2 nanosheets with exposed {001} facets:synthesis,characterization and visible-light photocatalytic activity", 《PHYS.CHEM.CHEM.PHYS.》 * |
| 周武艺等: "硫掺杂对纳米TiO2的结构相变及可见光催化活性的影响", 《中国有色金属学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657685B (en) * | 2013-11-27 | 2015-08-26 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of titanium dioxide optical catalyst of sulphur vanadium codope |
| CN108906107A (en) * | 2018-07-06 | 2018-11-30 | 广东海洋大学 | A kind of preparation method of sulfur and nitrogen co-doped titanium dioxide |
| CN112076775A (en) * | 2020-09-15 | 2020-12-15 | 湖南中医药大学 | Composite material for industrial wastewater treatment and preparation method thereof |
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