CN108236967B - CdS-U composite visible light catalyst - Google Patents
CdS-U composite visible light catalyst Download PDFInfo
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- CN108236967B CN108236967B CN201611220853.1A CN201611220853A CN108236967B CN 108236967 B CN108236967 B CN 108236967B CN 201611220853 A CN201611220853 A CN 201611220853A CN 108236967 B CN108236967 B CN 108236967B
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- light catalyst
- composite visible
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000013877 carbamide Nutrition 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 15
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 5
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001782 photodegradation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 150000003672 ureas Chemical group 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract 1
- 239000002738 chelating agent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000010146 3D printing Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical class [H]N([H])C(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/39—
Abstract
The invention discloses a preparation method and application of a surface functionalized cadmium sulfide/carbamide CdS-U composite visible-light-induced photocatalyst. The preparation method of the catalyst is to use CdS So as to serve as a matrix, use carbamide U as a chelating agent and carry out self-assembly by utilizing ionic bonds. The catalyst has good plasticity, and the morphology of the catalyst can be regulated and controlled in the preparation process. The recyclable writing paper made of the CdS-U material can be subjected to in-situ photocatalytic degradation of dye under the irradiation of visible light, and still maintains stable performance after being recycled for ten times. The mass ratio of CdS So to U in CdS-U is 1: 10-1: 20. The invention has important significance for the practical application of visible light catalysis, and has good application prospect in the preparation of recyclable carbon paper.
Description
Technical Field
The invention belongs to the field of visible light catalysis, and particularly relates to a CdS-U composite visible light catalyst prepared by a chemical hydrothermal-in-situ assembly method, a preparation method and application thereof.
Background
The photocatalysis technology as a novel environmental pollution treatment method has a plurality of unique advantages, such as mild reaction conditions, simple and convenient operation, capability of mineralizing most organic matters, less secondary pollution, capability of utilizing sunlight and the like. Most of the reported photocatalysts have wide band gaps and show high catalytic activity only in an ultraviolet region. But the ultraviolet light only accounts for 5% of the total energy of the sunlight, and the visible light at 400-700 nm accounts for 43% of the total energy of the sunlight. Therefore, in order to make better use of solar energy, the development of a catalyst having visible light activity is a necessary trend for further industrialization of photocatalysis. Meanwhile, the development of the high-efficiency visible light catalyst has profound significance for solving the current environmental problems and energy crisis.
CdS is an important type II-VI semiconductor, has a forbidden band width of 2.42eV, and is widely used as a visible light catalyst. However, the CdS catalyst is unstable in the process of photocatalytic reaction and is easily oxidized by photo-induced holes to generate a photo-corrosion phenomenon. The occurrence of the photo-corrosion phenomenon can lead the stability of the CdS catalyst to be poor and the photo-catalytic activity to be reduced, so that the cyclic utilization can not be realized and the application of the CdS catalyst in practice is limited. In order to improve the stability and photocatalytic activity of CdS in the photocatalytic reaction process, the use of element doping or composite photocatalysts and surface modification has become a focus of research in recent years.
Based on the analysis, the sodium oleate and the carbamide modified CdS are utilized, so that the separation efficiency of electrons and holes in the catalyst can be improved, the photo-corrosion effect is inhibited, and the stability and the catalytic efficiency of the catalyst are effectively improved. The development of the novel efficient composite catalyst has important significance for the practical application of the visible-light-driven photocatalyst and has good application prospect in the writing paper and 3D printing directions.
Disclosure of Invention
The invention aims to provide a CdS-U composite photocatalyst with high visible light response, a preparation method and application thereof in writing paper and 3D printing.
The technical scheme for realizing the purpose of the invention is to prepare the CdS-U composite visible-light-driven photocatalyst and apply the CdS-U composite visible-light-driven photocatalyst to writing paper and 3D printing.
The CdS-U composite visible light catalyst is characterized by being prepared by the following steps:
(1) preparing CdS So powder;
(2) adding the CdS So obtained in the step (1) into a carbamide aqueous solution, performing ultrasonic treatment to form uniformly dispersed suspension, and stirring at room temperature;
(3) and (3) evaporating the product obtained in the step (2) to remove redundant water, thus obtaining the CdS-U composite visible light catalyst.
Wherein the molar ratio of cadmium nitrate to thioacetamide to sodium oleate (So) in the step (1) is 1:1: 1-1: 1:3, the reaction temperature in the reaction kettle is 100-200 ℃, and the pressure is 1-3 Mpa; the mass ratio of the carboxamide in the step (2) to the CdSo in the step (1) is 10: 1-20: 1, and the stirring time is 24-72 hours; in the step (3), the stirring temperature in the oil bath is 60-200 ℃ and the stirring time is 1-5 h.
The CdS-U composite visible-light-driven photocatalyst prepared by the preparation method is used for writing paper and 3D printing, and CdS-U is recycled.
Compared with the prior art, the invention has the following remarkable advantages: (1) the CdS-U composite photocatalyst has response to visible light, can better utilize solar energy and has better prospect in the aspect of energy utilization; (2) the CdS-U composite photocatalyst can adsorb cationic dyes such as methylene blue and the like through electrostatic action, inhibit the recombination of electrons and holes on the surface of the catalyst and improve the photocatalytic efficiency; (3) the film prepared from the CdS-U composite photocatalyst can be used for manufacturing writing paper and can be repeatedly utilized; (4) the CdS-U composite photocatalyst has good plasticity, can be used for 3D printing, and can be repeatedly utilized. Therefore, the invention has certain practical significance for solving the environmental problems and energy crisis.
The present invention is described in further detail below with reference to the attached drawing figures.
Description of the drawings:
FIG. 1: a structural diagram of the CdS-U composite visible light catalyst;
FIG. 2: XRD pattern of CdS-U composite visible light catalyst;
FIG. 3: an infrared diagram of the CdS-U composite visible light catalyst;
FIG. 4: a writing film diagram made of CdS-U composite visible light catalyst;
FIG. 5: an entity model diagram made of the CdS-U composite visible-light-driven photocatalyst;
FIG. 6: the in-situ photocatalytic degradation dye of the writing film prepared by the CdS-U composite visible light catalyst and a regeneration process diagram thereof.
Detailed Description
The CdS-U composite visible light catalyst is characterized by being prepared by the following steps:
(1) cadmium nitrate, thioacetamide and sodium oleate (So) react in a reaction kettle, and CdS So is obtained by cooling and grinding;
(2) adding the CdS So obtained in the step (1) into a carbamide aqueous solution, performing ultrasonic treatment to form uniformly dispersed suspension, and stirring at normal temperature;
(3) and (3) stirring the product obtained in the step (2) in an oil bath pan, and removing redundant water to obtain the CdS-U composite visible light catalyst.
Wherein in the step (1), the molar ratio of cadmium nitrate to thioacetamide to sodium oleate (So) is 1:1: 1-1: 1:3, and the reaction temperature in the reaction kettle is 100-200 ℃; the mass ratio of the carboxamide in the step (2) to the CdSo in the step (1) is 10: 1-20: 1, and the stirring time is 24-72 hours; in the step (3), the stirring temperature in the oil bath is 60-200 ℃, and the stirring time is 1-5 h.
Example 1: CdS So/U is 1:20 (mass ratio), the stirring temperature in an oil bath is 80 ℃, and the preparation and application of the composite visible-light-driven photocatalyst
(1) Cadmium nitrate, sodium oleate and thioacetamide according to a molar ratio of 1:1: 2, reacting for 20 hours in a reaction kettle at the temperature of 100 ℃, and cooling and grinding to obtain CdS So;
(2) adding 1g of CdS So into 20g of carbamide aqueous solution, performing ultrasonic treatment to form uniformly dispersed suspension, and stirring at normal temperature;
(3) stirring the product obtained in the step (2) in an oil bath kettle at the temperature of 80 ℃, and removing redundant water to obtain the CdS So-Ca composite visible light catalyst;
fig. 1 shows the structure of CdS-U composite visible light catalyst, which can be seen by combining the XRD characterization of fig. 2 and the infrared characterization of fig. 3, indicating the presence of CdS, So and Ca in the composite material at the same time.
Writing film made of CdS-U composite visible light catalyst
2g of CdS-U composite visible light catalyst is dissolved in 4mL of aqueous solution, hydrothermal reaction is carried out for 30min at 80 ℃, the solution is spread on a glass sheet, and the glass sheet is spread by a glass rod, so that the carbon paper with the photocatalytic performance is obtained. See FIG. 4
Solid model made of CdS-U composite visible light catalyst
2g of CdS-U composite visible light catalyst is dissolved in 4mL of aqueous solution, hydrothermal reaction is carried out for 30min at 80 ℃, and the solution is poured into a template, so that the entity model with the photocatalytic performance is obtained. See FIG. 5
Recycled writing film made of CdS-U composite visible light catalyst, in-situ photocatalytic degradation dye and regeneration process thereof
Writing some characters on the prepared CdS-U composite visible light catalyst writing film by using dyes such as methylene blue, then dissolving the characters in water, illuminating, and recrystallizing to obtain the film again. See fig. 6.
Claims (8)
1. The CdS-U composite visible light catalyst is characterized by being prepared by the following steps
(1) Preparing CdS So powder;
(2) adding the CdS So obtained in the step (1) into a carbamide aqueous solution, performing ultrasonic treatment to form uniformly dispersed suspension, and stirring at room temperature;
(3) evaporating and dehydrating the product obtained in the step (2) to obtain a CdS-U composite visible light catalyst; the So is sodium oleate, and the U is carbamide.
2. The CdS-U composite visible light catalyst as defined in claim 1, wherein in step (2), the mass ratio of carbamide to CdSo is 10: 1-20: 1.
3. The CdS-U composite visible light catalyst as defined in claim 1, wherein in step (2), the stirring time is 24-72 h.
4. The CdS-U composite visible light catalyst as defined in claim 1, wherein in step (3), water is removed by stirring in an oil bath at 60-200 deg.C for 1-5 h.
5. The CdS-U composite visible light catalyst according to claim 1, wherein the step of preparing the CdSSo powder in the step (1) is: cadmium nitrate, thioacetamide and sodium oleate are reacted at the molar ratio of 1:1: 1-1: 1:3 at the temperature of 100-200 ℃ and under the pressure of 1-3 MP a, and the CdS So powder is prepared by cooling and grinding.
6. A method of preparing a CdS-U composite visible light catalyst as defined in any one of claims 1-5.
7. Use of a CdS-U composite visible light catalyst, characterized in that the catalyst according to claims 1-5 is used for writing paper and 3D printed raw materials that can photodegrade dyes in situ.
8. The use of the CdS-U composite visible light catalyst as defined in claim 7, wherein the writing paper capable of in-situ photodegradation of dye is prepared by the following steps: after the CdS-U writing paper is written by dye, the CdS-U writing paper is dissolved in water, and the dye is degraded in situ under the irradiation of visible light; and after the CdS-U is recovered, the CdS-U can be reused.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792445A (en) * | 2005-11-28 | 2006-06-28 | 浙江大学 | Nanometer, composite semiconductor photocatalyst, and its prepn. method |
| CN102861562A (en) * | 2012-09-28 | 2013-01-09 | 东北大学秦皇岛分校 | Nitrogen organic modified titanium-containing blast furnace slag catalyst with visible light catalytic activity and preparation method thereof |
| CN104190442A (en) * | 2014-09-03 | 2014-12-10 | 上海电力学院 | Cadmium sulfide visible light photocatalyst and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20060005703A (en) * | 2004-07-14 | 2006-01-18 | 강영수 | A preparation of semiconducting nanoparticle by -irradiation |
| CN101045552A (en) * | 2007-04-02 | 2007-10-03 | 沈阳工业大学 | Surface chemical preparation method of cadmium sulfide semiconductor nanoparticle |
| EP2660268B1 (en) * | 2010-12-28 | 2019-08-07 | Shanghai Genius Advanced Material (Group) Co. Ltd | Nano particle/polyamide composite material, preparation method therefor, and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792445A (en) * | 2005-11-28 | 2006-06-28 | 浙江大学 | Nanometer, composite semiconductor photocatalyst, and its prepn. method |
| CN102861562A (en) * | 2012-09-28 | 2013-01-09 | 东北大学秦皇岛分校 | Nitrogen organic modified titanium-containing blast furnace slag catalyst with visible light catalytic activity and preparation method thereof |
| CN104190442A (en) * | 2014-09-03 | 2014-12-10 | 上海电力学院 | Cadmium sulfide visible light photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 纳米CdS新型合成方法研究;何艳娥;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131215;第7-13页 * |
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