CN109201088B - Eu (Eu)3+Se co-doping of TiO2/GO material and its application in photocatalysis - Google Patents
Eu (Eu)3+Se co-doping of TiO2/GO material and its application in photocatalysis Download PDFInfo
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- CN109201088B CN109201088B CN201811304956.5A CN201811304956A CN109201088B CN 109201088 B CN109201088 B CN 109201088B CN 201811304956 A CN201811304956 A CN 201811304956A CN 109201088 B CN109201088 B CN 109201088B
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- butyl titanate
- graphene oxide
- ethyl alcohol
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 9
- 238000007146 photocatalysis Methods 0.000 title abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 23
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 22
- 239000011669 selenium Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to Eu3+Se co-doping of TiO2(ii) GO materials and their use in photocatalysis by Eu3+Se co-doping to make TiO2the/GO material catalyzes isopropanol to be oxidized into acetone under visible light, and the acetone has high selectivity.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to Eu3+Se co-doping of TiO2a/GO material and its use in photocatalysis.
Background
The traditional titanium dioxide has poor response to visible light, so that the application of the traditional titanium dioxide is greatly limited, and the Eu is used for the invention3+Se co-doping to obtain novel Eu capable of catalyzing isopropanol to be oxidized into acetone under visible light3+Se co-doping of TiO2a/GO material.
Disclosure of Invention
The invention provides a Eu3+Se co-doping of TiO2a/GO material, characterized in that said Eu3+Se co-doping of TiO2The preparation method of the/GO material comprises the following steps:
(1) dispersing selenium powder and graphene oxide in an acetic acid solution, adding a europium nitrate solution, and uniformly stirring to obtain a component A for later use;
(2) at room temperature, dropwise adding the component A obtained in the step (1) into an absolute ethyl alcohol solution of n-butyl titanate, stirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, sequentially washing the precipitate with ethanol and water, and vacuum-drying at 60 ℃ for 24h to obtain the Eu3+Se co-doping of TiO2a/GO material.
In the step (1), the mass ratio of the selenium powder to the graphene oxide is 1:20, the concentration of an acetic acid solution is 1mol/L, the concentration of a europium nitrate solution is 0.1mol/L, 25mL of acetic acid solution is used for every gram of graphene oxide, and 10mL of europium nitrate solution is used; in the step (2), the absolute ethyl alcohol solution of the n-butyl titanate is prepared from the n-butyl titanate and absolute ethyl alcohol according to the mass ratio of 1:5, and the using amount of the n-butyl titanate is 2 times of the mass of the graphene oxide used for preparing the component A.
Another embodiment of the present invention provides the above Eu3+Se co-doping of TiO2The preparation method of the/GO material is characterized by comprising the following steps:
(1) dispersing selenium powder and graphene oxide in an acetic acid solution, adding a europium nitrate solution, and uniformly stirring to obtain a component A for later use;
(2) at room temperature, dropwise adding the component A obtained in the step (1) into an absolute ethyl alcohol solution of n-butyl titanate, stirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, sequentially washing the precipitate with ethanol and water, and vacuum-drying at 60 ℃ for 24h to obtain the Eu3+Se co-doping of TiO2a/GO material.
In the step (1), the mass ratio of the selenium powder to the graphene oxide is 1:20, the concentration of an acetic acid solution is 1mol/L, the concentration of a europium nitrate solution is 0.1mol/L, 25mL of acetic acid solution is used for every gram of graphene oxide, and 10mL of europium nitrate solution is used; in the step (2), the absolute ethyl alcohol solution of the n-butyl titanate is prepared from the n-butyl titanate and absolute ethyl alcohol according to the mass ratio of 1:5, and the using amount of the n-butyl titanate is 2 times of the mass of the graphene oxide used for preparing the component A.
Another embodiment of the present invention provides the above Eu3+Se co-doping of TiO2Use of a/GO material as a photocatalyst. The use of visible light photocatalytic oxidation of isopropanol to acetone is preferred.
Drawings
SEM image of product A in FIG. 1;
FIG. 2 SEM image of product C;
FIG. 3 is a graph of the change in acetone concentration in a product A-E catalyzed isopropanol oxidation system;
FIG. 4 is a graph of the change in isopropanol concentration in the product A-E catalyzed isopropanol oxidation system.
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
(1) Dispersing selenium powder (10mg) and graphene oxide (200mg) in an acetic acid solution (5mL, 1mol/L), adding a europium nitrate solution (2mL, 0.1mol/L), and uniformly stirring to obtain a component A for later use;
(2) at room temperature, the stepsDropwise adding the component A obtained in the step (1) into an absolute ethyl alcohol solution (prepared from 400mg of n-butyl titanate and 2g of absolute ethyl alcohol) of n-butyl titanate, stirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, washing the precipitate with ethanol and water in sequence, and vacuum-drying at 60 ℃ for 24h to obtain the Eu3+Se co-doping of TiO2the/GO material (hereinafter referred to as product A).
Example 2
(1) Dispersing selenium powder (10mg) and graphene oxide (200mg) in an acetic acid solution (5mL, 1mol/L), and uniformly stirring to obtain a component A1 for later use;
(2) at room temperature, dropwise adding the component A1 obtained in the step (1) into an absolute ethyl alcohol solution of n-butyl titanate (prepared from 400mg of n-butyl titanate and 2g of absolute ethyl alcohol), stirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, washing the precipitate with ethanol and water in sequence, and vacuum-drying at 60 ℃ for 24h to obtain the Se-doped TiO2the/GO material (hereinafter referred to as product B).
Example 3
(1) Dispersing graphene oxide (200mg) in an acetic acid solution (5mL, 1mol/L), adding a europium nitrate solution (2mL, 0.1mol/L), and uniformly stirring to obtain a component A2 for later use;
(2) at room temperature, dropwise adding the component A2 obtained in the step (1) into an absolute ethyl alcohol solution of n-butyl titanate (prepared from 400mg of n-butyl titanate and 2g of absolute ethyl alcohol), stirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, washing the precipitate with ethanol and water in sequence, and vacuum-drying at 60 ℃ for 24h to obtain Eu3+Doped TiO 22the/GO material (hereinafter referred to as product C).
Example 4
(1) Dispersing graphene oxide (200mg) in an acetic acid solution (5mL, 1mol/L), and uniformly stirring to obtain a component A3 for later use;
(2) at room temperature, dropwise adding the component A3 obtained in the step (1) into an absolute ethyl alcohol solution of n-butyl titanate (prepared from 400mg of n-butyl titanate and 2g of absolute ethyl alcohol), stirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, washing the precipitate with ethanol and water in sequence, and vacuum-drying at 60 ℃ for 24h to obtain the compoundTiO2the/GO material (hereinafter referred to as product D).
Example 5
(1) Dispersing selenium powder (2mg) and graphene oxide (200mg) in an acetic acid solution (5mL, 1mol/L), adding a europium nitrate solution (2mL, 0.1mol/L), and uniformly stirring to obtain a component A4 for later use;
(2) at room temperature, dropwise adding the component A4 obtained in the step (1) into an absolute ethyl alcohol solution of n-butyl titanate (prepared from 400mg of n-butyl titanate and 2g of absolute ethyl alcohol), stirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, washing the precipitate with ethanol and water in sequence, and vacuum-drying at 60 ℃ for 24h to obtain Eu3+Se co-doping of TiO2the/GO material (hereinafter referred to as product E).
Example 6 photocatalytic oxidation experiment of isopropanol
Isopropanol photocatalytic oxidation experiment: weighing 100mg of products A-E respectively, irradiating with ultraviolet lamp, uniformly spreading and dispersing at the bottom of glass surface dish
The glass petri dish and 125mL of 500ppm isopropyl alcohol/pure air mixed gas were injected into a Tedlar transparency bag, placed in a dark room for 2 hours to establish an adsorption-desorption equilibrium between the products A-E and isopropyl alcohol, and then 3mW/cm was used2The products A-E were illuminated by LED lamps of light intensity (centre wavelength 435nm) and monitored in real time for changes in isopropanol consumption and acetone concentration produced by on-line gas chromatography (3000A Micro-GC, Agilent, TCD detector) with OV1 and PLOT-Q columns (FIGS. 3-4).
Claims (5)
1. Eu (Eu)3+Se co-doping of TiO2a/GO material, characterized in that said Eu3+Se co-doping of TiO2The preparation method of the/GO material comprises the following steps:
(1) dispersing selenium powder and graphene oxide in an acetic acid solution, adding a europium nitrate solution, and uniformly stirring to obtain a component A for later use;
(2) dripping the component A obtained in the step (1) into absolute ethyl alcohol solution of n-butyl titanate at room temperatureStirring for 0.5h, heating to 70 ℃, continuing stirring for 2h, filtering to obtain a precipitate, washing the precipitate with ethanol and water in sequence, and vacuum-drying at 60 ℃ for 24h to obtain the Eu3+Se co-doping of TiO2a/GO material.
2. Eu according to claim 13+Se co-doping of TiO2the/GO material is characterized in that the mass ratio of the selenium powder to the graphene oxide in the step (1) is 1:20, the concentration of an acetic acid solution is 1mol/L, the concentration of a europium nitrate solution is 0.1mol/L, 25mL of acetic acid solution is used for every gram of graphene oxide, and 10mL of europium nitrate solution is used.
3. Eu according to any one of claims 1 to 23+Se co-doping of TiO2the/GO material is characterized in that in the step (2), the absolute ethyl alcohol solution of the n-butyl titanate is prepared by the mass ratio of the n-butyl titanate to the absolute ethyl alcohol of 1:5, and the using amount of the n-butyl titanate is 2 times of the mass of the graphene oxide used in the preparation component A.
4. Eu according to any one of claims 1 to 33+Se co-doping of TiO2Use of a/GO material as a photocatalyst.
5. Use according to claim 4, characterized in that in the visible light photocatalytic oxidation of isopropanol to acetone.
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|---|---|---|---|---|
| CN102212365A (en) * | 2011-04-12 | 2011-10-12 | 东华大学 | Preparation method for europium-doping calcium titanate fluorescent powder |
| CN103872293A (en) * | 2014-03-18 | 2014-06-18 | 中国科学院化学研究所 | Novel lithium ion battery electrode material and application of lithium ion battery electrode material |
| CN104474791A (en) * | 2014-11-07 | 2015-04-01 | 桂林新竹大自然生物材料有限公司 | Microcrystalline bamboo-charcoal cellular pottery-texture air filter panel with catalytic function and preparation method thereof |
| CN108212138A (en) * | 2016-12-09 | 2018-06-29 | 北京有色金属研究总院 | A kind of preparation process of lanthanum and graphene oxide codope lightweight catalysis material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212365A (en) * | 2011-04-12 | 2011-10-12 | 东华大学 | Preparation method for europium-doping calcium titanate fluorescent powder |
| CN103872293A (en) * | 2014-03-18 | 2014-06-18 | 中国科学院化学研究所 | Novel lithium ion battery electrode material and application of lithium ion battery electrode material |
| CN104474791A (en) * | 2014-11-07 | 2015-04-01 | 桂林新竹大自然生物材料有限公司 | Microcrystalline bamboo-charcoal cellular pottery-texture air filter panel with catalytic function and preparation method thereof |
| CN108212138A (en) * | 2016-12-09 | 2018-06-29 | 北京有色金属研究总院 | A kind of preparation process of lanthanum and graphene oxide codope lightweight catalysis material |
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