CN114014360B - Sillin-Aurivillius layered structure material Bi 4 SbO 8 Cl and synthesis method - Google Patents
Sillin-Aurivillius layered structure material Bi 4 SbO 8 Cl and synthesis method Download PDFInfo
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Abstract
The invention discloses a Sillin-Aurivillius layered structure material Bi 4 SbO 8 Cl and a synthesis method thereof. The microstructure is as follows: -Cl-Bi 2 O 2 —SbO 4 —Bi 2 O 2 -Cl-. The synthesis steps are as follows: sb is made of 2 O 4 Mixing with Bi and Cl-containing compounds according to a certain proportion and fully grinding; further obtaining the Sillin-Aurivillius layered structure material Bi through high-temperature solid-phase reaction 4 SbO 8 Cl can absorb visible light and ultraviolet light with the wavelength less than 500 and nm, and the conduction band position satisfies H 2 /H + Potential requirements. The material can be applied to the fields of dye, carbon dioxide reduction, hydrogen production by decomposing water, nitrogen fixation and the like.
Description
Technical Field
The invention relates to a layered structure narrow band gap semiconductor material, belonging to the field of nano material preparation.
Background
The Sillin-Aurivillius layered structure material is a kind of composite bismuth oxide layered material, and consists of-Bi 2 O 2 Layer and MO x The perovskite-like layer is formed by laminating (M is other metal elements), has excellent photoelectric performance, is wide in application field, and has remarkable economic and social benefits. The Sillin-Aurivillius layered structure material which is successfully synthesized at present comprises Bi 4 NbO 8 Cl、Bi 4 TaO 8 Cl, etc., wherein-MO x M element in the perovskite-like layer comprises Nb, ta, V, W, pb and the like, but the materials mainly have wider forbidden band width, high electron-hole recombination rate and unsatisfied conduction band position meeting H 2 /H + The problems of reduction potential requirement, or expensive M element, etc. need to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the technical problems and provides a Sillin-Aurivillius layered structure material Bi 4 SbO 8 Cl and a synthesis method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
Sillin-Aurivillius layered structure material Bi 4 SbO 8 Cl, its microstructure is-Cl-Bi 2 O 2 —SbO 4 —Bi 2 O 2 Cl-, capable of absorbing visible and ultraviolet light having a wavelength of less than 500 nm and having a conduction band position satisfying H 2 /H + Potential requirements.
The invention also provides a Sillin-Aurivillius layered structure material Bi 4 SbO 8 The synthesis method of Cl comprises the following steps:
(1) Sb is made of 2 O 4 Grinding the oxide containing Bi and Cl or the salt thereof, and carrying out high-temperature solid-phase reaction on the obtained mixture;
(2) Grinding the reactant obtained in the step (1) for a period of time, and carrying out high-temperature solid-phase reaction again.
Preferably, in step (1), sb 2 O 4 The preparation method adopts a high-temperature solid phase method, and comprises the following steps: sb is made of 2 O 5 Grinding for a period of time, and then carrying out high-temperature solid-phase reaction to obtain Sb 2 O 4 。
Specifically, grinding is carried out for 5-30 min.
Specifically, the conditions of the high-temperature solid phase reaction are as follows: the calcination temperature is 700-1000 ℃, the reaction time is 1-6 h, and the temperature rising rate is 3-7 ℃ per minute.
Preferably, in step (1), sb 2 O 4 The preparation method adopts a hydrothermal method, and comprises the following steps: will SbCl 3 Dissolving urea in water, regulating pH to 10, and performing hydrothermal reaction for a period of time to obtain Sb 2 O 4 。
Specifically, sbCl 3 And urea in a molar ratio of 1:1.
Specifically, the hydrothermal reaction temperature is 150 ℃, and the hydrothermal reaction time is 18 hours.
Preferably, in the step (1), the grinding is performed for 5 to 30 minutes.
Preferably, in step (1), the oxide of Bi and Cl or salts thereof, comprises Bi 2 O 3 ，NH 4 Cl, biOCl and BiCl 3 。
Preferably, in the step (1), the high-temperature solid phase reaction conditions are as follows: the calcination temperature is 700-900 ℃, the reaction time is 1-20 h, and the temperature rising rate is 3-7 ℃ per minute.
Preferably, in the step (2), grinding is performed for 5-30 min.
Preferably, in the step (2), the high-temperature solid phase reaction conditions are as follows: the calcination temperature is 800-1000 ℃, the reaction time is 1-20 h, and the temperature rising rate is 3-7 ℃ per minute.
Preferably, in the step (2), the high-temperature solid phase reaction is performed again for 1 to 3 times.
Compared with the prior art, the invention has the following beneficial effects:
the Sillin-Aurivillius layered structure material Bi provided by the invention 4 SbO 8 The microstructure of Cl is-Cl-Bi 2 O 2 —SbO 4 —Bi 2 O 2 Cl-, can absorb visible light and ultraviolet light with a wavelength less than 500 nm, and the conduction band position satisfies H 2 /H + Potential requirements. The material can be applied to the fields of dye, carbon dioxide reduction, hydrogen production by decomposing water, nitrogen fixation and the like.
Drawings
FIG. 1 shows Bi according to the present invention 4 SbO 8 Cl microstructure.
FIG. 2 shows Sb prepared by the present invention 2 O 4 Is an X-ray diffraction pattern of (2).
FIG. 3 shows Bi prepared by the present invention 4 SbO 8 X-ray diffraction pattern of Cl.
FIG. 4 shows Bi prepared by the present invention 4 SbO 8 Ultraviolet visible light absorption spectrum of Cl.
FIG. 5 shows Bi prepared by the present invention 4 SbO 8 And (3) a hydrogen production performance graph by decomposing water of Cl.
Detailed Description
The invention is further elucidated below with reference to the drawings and the examples.
The innovation point of the invention is that: 1) In the energy band structure, sb is used for replacing Nb, bi 4 SbO 8 Cl conduction band position satisfies H 2 /H + Reduction potential requirements. 2) In terms of synthesis, the Sb source must be Sb 2 O 4 Such as Sb 2 O 5 Through 950 ℃ and 4h high temperature solid phase reaction or SbCl reaction 3 Hydrothermal reaction at 150 ℃ under alkaline condition for 18h to convert into Sb 2 O 4 Then, the mixture can be further mixed with a compound containing Bi and Cl to react to prepare the Sillin-Aurivillius layered structure material Bi 4 SbO 8 Cl。
Example 1
High temperature solid phase synthesis of Sb 2 O 4 Further preparing a photocatalyst Bi 4 SbO 8 The Cl process is as follows:
(1) Weigh Sb of 2 g 2 O 5 Grinding for 10 min, and then carrying out high-temperature solid-phase reaction at 950 ℃ for 4h to obtain Sb 2 O 4 The X-ray diffraction pattern is shown in FIG. 2.
(2) Sb is made of 2 O 4 (0.312, g) and Bi 2 O 3 （0.932 g）、NH 4 Cl (0.108, g) is measured and ground for 10 min, and the mixture is subjected to solid phase reaction at a high temperature of 6h at 800 ℃ in a muffle furnace.
(3) Grinding the obtained mixture for 10 min again, and then carrying out high-temperature solid-phase reaction for 6h at 850 ℃ in a muffle furnace to obtain a final product Bi 4 SbO 8 Cl, the microstructure of which is shown in FIG. 1, and the X-ray diffraction pattern of which is shown in FIG. 3. Bi obtained 4 SbO 8 The ultraviolet and visible light absorption spectrum of Cl is shown in figure 4, and the hydrogen production performance by photocatalytic decomposition of water is shown in figure 5.
Example 2
Synthesis of Sb by hydrothermal method 2 O 4 Further preparing a photocatalyst Bi 4 SbO 8 The Cl process is as follows:
(1) 0.005 mol of SbCl is weighed 3 And 0.005 mol of urea in 50 mL water, and adjusting with ammonia waterRegulating pH to 10, transferring the mixed solution into a reaction kettle, reacting at 150 ℃ for 18h, washing with deionized water, centrifuging and drying to obtain Sb after the reaction is finished 2 O 4 The X-ray diffraction pattern is shown in FIG. 2.
(2) Sb is made of 2 O 4 (0.312, g) and Bi 2 O 3 （1.864 g）、NH 4 Cl (0.108, g) is measured and ground for 10 min, and the mixture is subjected to solid phase reaction at a high temperature of 6h at 800 ℃ in a muffle furnace.
(3) Grinding the obtained mixture for 10 min again, and then carrying out high-temperature solid-phase reaction for 6h at 850 ℃ in a muffle furnace to obtain a final product Bi 4 SbO 8 Cl, the X-ray diffraction diagram of which is shown in figure 3, and the hydrogen production performance by photocatalytic decomposition of water is shown in figure 5. As can be seen from FIG. 5, bi prepared in example 1 4 SbO 8 The hydrogen production performance of Cl photocatalytic water splitting is ten times higher than that of the embodiment 2, and the performance is probably Sb synthesized by two methods 2 O 4 The microscopic properties (particle size, surface defects, etc.) differ, leading to the final synthesized Bi 4 SbO 8 The microscopic nature of Cl varies.
Comparative example 1
Sb 2 O 5 Directly mixing and reacting with Bi and Cl-containing compounds without high-temperature calcination.
(1) Sb is made of 2 O 5 (0.167. 0.167 g) and Bi 2 O 3 （0.932 g）、NH 4 Cl (0.054) g) is measured and ground for 10 min, and the mixture is subjected to solid phase reaction at a high temperature of 6h at 800 ℃ in a muffle furnace.
(2) Grinding the obtained mixture for 10 min again, and performing high-temperature solid-phase reaction at 850 deg.C in a muffle furnace for 6 hr to obtain a product containing BiSbO as main ingredient 4 The X-ray diffraction pattern is shown in FIG. 3, and compared with examples 1 and 2, sb 2 O 5 Directly mixing the material with a compound containing Bi and Cl without high-temperature calcination to react to obtain the Sillen-Aurivillius layered structure material Bi 4 SbO 8 Cl. Under the same photocatalytic water splitting hydrogen production test conditions as in examples 1 and 2, no hydrogen generation was detected.
Claims (10)
1. Sillin-Aurivillius layered structure material Bi 4 SbO 8 Cl is characterized in that the microstructure is-Cl-Bi 2 O 2 —SbO 4 —Bi 2 O 2 Cl-, capable of absorbing visible and ultraviolet light having a wavelength of less than 500 nm and having a conduction band position satisfying H 2 /H + Potential requirements.
2. A material Bi of laminated structure of bellen-Aurivillius as claimed in claim 1 4 SbO 8 The synthesis method of Cl is characterized by comprising the following steps:
(1) Sb is made of 2 O 4 Grinding the oxide containing Bi and Cl or the salt thereof, and carrying out high-temperature solid-phase reaction on the obtained mixture;
(2) Grinding the reactant obtained in the step (1) for a period of time, and carrying out high-temperature solid-phase reaction again.
3. The method of claim 2, wherein Sb 2 O 4 The preparation method adopts a high-temperature solid phase method, and comprises the following steps: sb is made of 2 O 5 Grinding for a period of time, and then carrying out high-temperature solid-phase reaction to obtain Sb 2 O 4 。
4. A method according to claim 3, wherein the high temperature solid phase reaction conditions are: the calcination temperature is 700-1000 ℃, the reaction time is 1-6 h, and the temperature rising rate is 3-7 ℃ per minute.
5. The method of claim 2, wherein Sb 2 O 4 The preparation method adopts a hydrothermal method, and comprises the following steps: will SbCl 3 Dissolving urea in water, regulating pH to 10, and performing hydrothermal reaction for a period of time to obtain Sb 2 O 4 。
6. The method of claim 5, wherein the hydrothermal reaction temperature is 150 ℃ and the hydrothermal reaction time is 18 hours.
7. The method of claim 2, wherein in step (1), the high temperature solid phase reaction conditions are: the calcination temperature is 700-900 ℃, the reaction time is 1-20 h, and the temperature rising rate is 3-7 ℃ per minute.
8. The method of claim 2, wherein in step (2), the high temperature solid phase reaction conditions are: the calcination temperature is 800-1000 ℃, the reaction time is 1-20 h, and the temperature rising rate is 3-7 ℃ per minute.
9. The method according to claim 2, wherein in the step (2), the high temperature solid phase reaction is performed again 1 to 3 times.
10. The Sillin-Aurivillius layered structure material Bi as defined in claim 1 4 SbO 8 Use of Cl in the production of hydrogen by decomposition of water.
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| CN105366720A (en) * | 2015-12-04 | 2016-03-02 | 新疆大学 | Method for synthesizing carbonate bismuth oxide nanosheets through solid-phase chemical reaction at room temperature |
| JP2017124365A (en) * | 2016-01-13 | 2017-07-20 | 国立大学法人京都大学 | Water decomposition method under visible light irradiation using silene-aurivillius laminar acid halide as photocatalyst |
| CN109603864A (en) * | 2019-01-14 | 2019-04-12 | 青岛科技大学 | It is a kind of to prepare Sill é n-Aurivillius phase Bi4NbO8The method of Br nanometer sheet |
| CN110694650A (en) * | 2019-11-13 | 2020-01-17 | 青岛科技大学 | Bi loaded Bi4NbO8Preparation method of Cl composite visible light catalyst |
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| EP2640666B1 (en) * | 2010-11-16 | 2017-11-01 | Yissum Research Development Company of the Hebrew University of Jerusalem, Ltd. | Bismuth oxyhalide compounds useful as photocatalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366720A (en) * | 2015-12-04 | 2016-03-02 | 新疆大学 | Method for synthesizing carbonate bismuth oxide nanosheets through solid-phase chemical reaction at room temperature |
| JP2017124365A (en) * | 2016-01-13 | 2017-07-20 | 国立大学法人京都大学 | Water decomposition method under visible light irradiation using silene-aurivillius laminar acid halide as photocatalyst |
| CN109603864A (en) * | 2019-01-14 | 2019-04-12 | 青岛科技大学 | It is a kind of to prepare Sill é n-Aurivillius phase Bi4NbO8The method of Br nanometer sheet |
| CN110694650A (en) * | 2019-11-13 | 2020-01-17 | 青岛科技大学 | Bi loaded Bi4NbO8Preparation method of Cl composite visible light catalyst |
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