CN101584985B - Ca-Bi-O series visible-light photocatalysis material and preparation method thereof - Google Patents
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- 238000007146 photocatalysis Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 35
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- 239000002243 precursor Substances 0.000 claims abstract description 18
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
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Abstract
The invention relates to a preparation method for a Ca-Bi-O series visible-light photocatalysis material, and belongs to the technical field of inorganic nano materials. The preparation method comprises the steps of preparing a precursor by using a chemical solution method and annealing for 10 to 15 hours at the temperature of between 450 and 800 DEG C. The method for preparing the Ca-Bi-O series visible-light photocatalysis material by using the chemical solution method through even reaction overcomes the defect of high reaction temperature in the prior art, and can obtain single-phase or heterogenous compound photocatalysis functional materials by controlling the annealing temperature respectively. The method has the advantages of simple operation, easy reaction control and good repeatability; and the obtained heterogenous compound photocatalysis functional material has remarkably-improved photocatalysis activity.
Description
Technical Field
The invention relates to a Ca-Bi-O series photocatalytic functional material and a preparation method thereof, belonging to the field of preparation of inorganic nano materials.
Background
The semiconductor photocatalytic oxidation technology is a novel water treatment technology for degrading pollutants by utilizing light energy, has the advantages of simple process, low cost, stable structure degradation of organic matters difficult to biodegrade under normal temperature and pressure, no pollution and the like, and is generally concerned by scholars at home and abroad. 1976 TiO used for Garey2The photocatalyst removes chlorine in polychlorinated biphenyl (Bull. environ. Contam. Toxical., 1976, 16, 697.), and Frank photocatalytic oxidation CN in 1977-Is OCN-(J.Phys.chem., 1977, 81, 1484.) pioneering the treatment of wastewater with photocatalysts. The core of the research of the photocatalysis technology is to find a photocatalysis material with excellent performance. Currently, the most extensively studied TiO2The absorption of light is limited to the ultraviolet region (Eg ═ 3.2eV), and the utilization of solar energy is limited, so that the search for a novel and efficient visible light photocatalytic functional material has become a new materialA new research hotspot.
Bi in bismuth-based oxide as a novel photocatalytic functional material3+The asymmetric coordination environment caused by the departure of the lone pair electrons with the stereo activity from the symmetric center of the ligand of the lone pair electrons can lead to Bi3+The oxides of (a) give rise to a range of interesting physical properties, especially photocatalytic properties. Research in recent years has found that a series of bismuth-containing multi-component composite oxides, due to the diversity of crystal structures and electronic structures thereof, may have both an energy band structure responding to visible light excitation and high photocarrier mobility, and have been widely researched as potential high-efficiency photocatalytic functional materials. In 2004, Chinese flowering quince reported a bismuth-based photocatalyst CaBi2O4The catalyst can efficiently degrade methylene blue and other organic pollutants under visible light (lambda is more than or equal to 420nm), but only a high-temperature stable phase compound can be obtained by adopting a high-temperature solid-phase synthesis method, and a low-temperature metastable phase bismuth oxide compound possibly having higher photocatalytic activity cannot be obtained. Another concern of the photocatalytic technology is the recombination of photogenerated carriers (holes and electrons), and the heterogeneous recombination can effectively improve the charge separation rate of the semiconductor photocatalyst, thereby improving or improving the photocatalytic activity of the semiconductor structure, and having a particularly important significance in the aspect of practical application.
Disclosure of Invention
Aiming at the current research situation, the invention provides a method for preparing a series of Ca-Bi-O series visible light photocatalytic materials by a chemical solution method through uniform reaction so as to overcome the defect of high reaction temperature in the prior art.
The Ca-Bi-O series visible light photocatalytic material is a series of compounds formed by Ca, Bi and O according to different proportions, and has the following general formula: caxBiyOzThe formula is 1-5, 2-14 and 4-26.
The preparation method of the Ca-Bi-O series visible light photocatalytic material comprises the following steps:
(1) preparation of the precursor
Weighing 0.24-0.48g Ca (NO)3)2And 0.97 to 1.94g Bi (NO)3)3Dissolving in 50mL of ethylene glycol, dropwise adding 0-1mL of polymaleic acid with the concentration of 12 wt%, stirring for 4-5 minutes at room temperature, adjusting the pH value to 8-10 by using concentrated ammonia water, and stirring for 20-24 hours at room temperature; washing the obtained product with 50-100mL of absolute ethyl alcohol at room temperature, then carrying out centrifugal separation, and drying the solid-phase product at 70 ℃ for 24 hours to obtain a precursor.
The preferred concentration of concentrated aqueous ammonia is 25-28% wt.
(2) Annealing
And (2) pretreating the precursor prepared in the step (1) at 300 ℃ for 1-10 hours, naturally cooling to room temperature, annealing at 450-800 ℃ for 10-15 hours, and naturally cooling to room temperature to obtain the product.
Preferably, the polishing is performed for 10-30 minutes before the annealing of the precursor in step (2) is started.
The reaction in the method is carried out in a reaction kettle with accurate temperature control so as to accurately control the reaction temperature.
In the step (2), the product is a single-phase product when the annealing temperature is 600 ℃ and 800 ℃, and the product is a heterogeneous composite-phase product when the annealing temperature is the rest.
The particle size diameter of the product prepared by the method is 10-90 nm.
The phase of the product prepared by the process of the invention was tested by X-ray diffraction spectroscopy (XRD) using a Bruker D8X-ray diffractometer using Cu-Ka radiation (wavelength)
) The product is subjected to X-ray diffraction analysis for a diffraction light source. The ultraviolet-visible diffuse reflectance (UV-Vis dispersion) spectrum of the product was measured with a U-1901 UV-Vis spectrophotometer. See in particular fig. 1-3.
The invention has the following characteristics and excellent effects:
1. firstly, a coordination method is combined with a coprecipitation method (belonging to a chemical solution method) to prepare a precursor so as to improve the uniformity of the material, and a multi-component dilute solution is a mixture of a molecular level and an atomic level, so that the synthesized material has high uniformity in composition and appearance. Polymaleic acid can be selected as a chelating agent during preparation of the precursor, so that uneven precipitation is prevented, and the calcination temperature is increased.
2. By controlling the annealing temperature, a single-phase or heterogeneous composite photocatalytic functional material can be obtained respectively, wherein the heterogeneous composite structure can effectively improve the charge separation rate and the photocatalytic activity of the semiconductor photocatalyst.
3. The method has the advantages of reasonable design, simple operation, easy control of reaction and good repeatability.
The invention makes metal ions achieve uniform reaction at molecular level and atomic level by a chemical solution method, can respectively obtain single-phase or heterogeneous composite photocatalytic functional materials by controlling annealing temperature, and the photocatalytic performance test result shows that heterogeneous composite can effectively improve the charge separation rate and photocatalytic activity of a semiconductor photocatalyst, so that the material is a novel high-efficiency visible light photocatalytic functional material.
Drawings
FIG. 1 shows X-ray diffraction spectra (XRD) of Ca-Bi-O-based visible light photocatalytic materials obtained by annealing at 450-800 ℃. The different phase compositions obtained at different annealing temperatures are shown in the molecular formula on each line in the XRD pattern.
FIG. 2 shows the ultraviolet-visible Diffuse Reflectance Spectra (DRS) of the obtained photocatalytic materials at different annealing temperatures. The curves in the graph are at 430nm, and the curves represent the temperature in sequence from top to bottom: 550. 800, 700, 750, 650, 600, 450, 500 ℃.
FIG. 3 shows the MB aqueous solution (15mg/L) of the photocatalytic material obtained at different annealing temperatures as a function of time t under irradiation with visible light: UV-Visible spectral changes of 0, 1, 2, 3, 4, 5, 6, 7 and 8 h. In the figure, (a) - (h) are annealing temperatures 450, 500, 550, 600, 650, 700, 750, 800 ℃ in sequence. Wherein,
(a) at 665nm, the curves from top to bottom represent the time: 0. 1, 2, 3, 4 and 5 h.
(b) At 665nm, the curves from top to bottom represent the time: 0. 1, 2, 3, 4, 5 and 6 h.
(c) At 665nm, the curves from top to bottom represent the time: 1. 2, 3, 4, 5, 0, 6, 7 and 8 h.
(d) At 620nm, the curves from top to bottom represent the time: 2. 0, 1, 3, 4 and 5 h.
(e) At 620nm, the curves from top to bottom represent the time: 2. 0, 1, 3, 4 and 5 h.
(f) At 665nm, the curves from top to bottom represent the time: 3. 4, 5, 2, 1, 6, 7, 0 and 8 h.
(g) At 665nm, the curves from top to bottom represent the time: 1. 2, 3, 4, 5, 0, 6, 7 and 8 h.
(h) At 665nm, the curves from top to bottom represent the time: 0. 1, 2, 3, 4, 5, 6, 7 and 8 h.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1: the preparation method of the Ca-Bi-O visible light photocatalysis nano material comprises the following steps:
(1) preparation of the precursor
0.24g Ca (NO) is weighed3)2And 0.97g Bi (NO)3)3Dissolving in 50mL of ethylene glycol, dropwise adding 1mL of polymaleic acid, stirring at room temperature for 5 minutes, adjusting the pH value to 9 with concentrated ammonia water, and stirring at room temperature for 24 hours; the resulting product was washed with 100mL of ethanol at room temperature, then centrifuged and dried at 70 ℃ for 24 hours to give a precursor.
(2) Annealing
Taking 0.4g of the precursor prepared in the step (1), pretreating at 300 ℃ for 8 hours, and naturally cooling to room temperature; grinding for 20 minutes, annealing for 10 hours at 450-800 ℃, and naturally cooling to room temperature to obtain the Ca-Bi-O series photocatalytic functional material.
The reaction in the steps (1) and (2) is to place the reaction kettle in an oven capable of accurately controlling the temperature.
The phase of the product was tested by X-ray diffraction spectroscopy (XRD) using a Bruker D8X-ray diffractometer with Cu-Ka radiation (wavelength)
) The product is subjected to X-ray diffraction analysis for a diffraction light source. The ultraviolet-visible diffuse reflectance (UV-Vis dispersion) spectrum of the product was measured with a U-1901 UV-Vis spectrophotometer. The results are as follows:
FIG. 1 shows X-ray diffraction spectra (XRD) of Ca-Bi-O photocatalytic functional materials prepared by annealing at 450, 500, 550, 600, 650, 700, 750, and 800 ℃. Wherein when the calcining temperature is 600 ℃ or 800 ℃, the product is respectively composed of single phase CaBi2O4(JCPDS card No.48-0216) and Ca3Bi8O15(JCPDS card No. 49-0021). The difference in calcination temperature was defined as 50 ℃ to clearly understand the phase transformation process. The product is CaBi at the calcining temperature of 450 ℃, 500 ℃ and 550 DEG C2O4And part of CaBi4O7(JCPDS card No.41-0309) and semi-quantitative analysis found that CaBi increases with temperature2O4The amount of the CaBi is gradually increased until the temperature reaches 600 DEG C4O7The phases disappeared completely. During the continuous increase of the calcination temperature, Ca is respectively present5Bi14O26(JCPDS card No.48-0215), Ca4Bi6O13(JCPDS card No.42-1439) and Ca3Bi8O15(JCPDS card No.49-0021) component generation, the final product is converted to Ca as the temperature is raised to 800 deg.C3Bi8O15A single phase.
FIG. 2 shows the ultraviolet-visible Diffuse Reflectance Spectra (DRS) of samples obtained at different annealing temperatures, and from the DRS spectra, it can be seen that the synthesized novel Ca-Bi-O series photocatalytic functional material has different degrees of absorption in the visible light region with lambda > 400 nm.
FIG. 3 shows the visible light photocatalytic degradation process of methylene blue wastewater solution by samples obtained at different annealing temperatures, the sequence of the photocatalytic activity of the obtained materials is S450 > S650 > S500 > S750 > S550 > S700 > S600 > S800, wherein the single phase CaBi obtained by annealing at 600 ℃ and 800 ℃ is2O4And Ca3Bi8O15The degradation efficiency is relatively low, and the heterogeneous combination can effectively improve the charge separation rate and the photocatalytic activity of the semiconductor photocatalyst.
Example 2:
the preparation procedure is the same as in example 1, except that: the calcium salt used in the step (1) is Ca (NO)3)2The bismuth salt is BiCl3。
Example 3:
the preparation procedure is the same as in example 1, except that: the calcium salt used in the step (1) is CaCl2The bismuth salt is: bi (NO)3)3。
Example 4:
the procedure is as in example 1, except that: step (1) 0.48g Ca (NO) is taken3)2And 0.97g Bi (NO)3)3Dissolve in 50mL of ethylene glycol.
Example 5:
the preparation steps are the same as in the example1, the difference is that: step (1) 0.24g Ca (NO) is taken3)2And 1.94g Bi (NO)3)3Dissolve in 50mL of ethylene glycol.
Example 6:
the preparation procedure is the same as in example 1, except that: during the process of preparing the precursor, polymaleic acid is not dripped.
Example 7:
the preparation procedure is the same as in example 1, except that: and (2) in the process of preparing the precursor in the step (1), adjusting the pH value to be 8 by using concentrated ammonia water.
Example 8:
the preparation procedure is the same as in example 1, except that: and (2) in the process of preparing the precursor in the step (1), adjusting the pH value to be 10 by using concentrated ammonia water.
Example 9:
the preparation procedure is the same as in example 1, except that: in the process of preparing the precursor in the step (1), the obtained product is washed by 50mL of water at room temperature.
Example 10:
the preparation procedure is the same as in example 1, except that: in the annealing procedure of the step (2), the pretreatment is carried out for 1 hour at 300 ℃.
Example 11:
the preparation procedure is the same as in example 1, except that: in the annealing procedure in the step (2), after pretreatment for 10 hours at 300 ℃, annealing is carried out at high temperature without grinding.
Example 12:
the preparation procedure is as in example 1, except that: in the annealing step in the step (2), after grinding for 30 minutes, annealing is carried out for 15 hours at 450-800 ℃.
Claims (2)
1. A preparation method of Ca-Bi-O series visible light photocatalytic material comprises the following steps:
(1) preparation of the precursor
Weighing 0.24-0.48g Ca (NO)3)2And 0.97 to 1.94g of Bi (NO)3)3Dissolving in 50mL of ethylene glycol, dropwise adding 0-1mL of polymaleic acid with the concentration of 12 wt%, stirring for 4-5 minutes at room temperature, adjusting the pH value to 8-10 by using concentrated ammonia water, and stirring for 20-24 hours at room temperature; washing the obtained product with 50-100mL of absolute ethyl alcohol at room temperature, then carrying out centrifugal separation, and drying the solid-phase product at 70 ℃ for 20-24 hoursThen obtaining a precursor;
the concentration of the strong ammonia water is 25-28 wt%;
(2) annealing
And (2) pretreating the precursor prepared in the step (1) at 300 ℃ for 1-10 hours, naturally cooling to room temperature, annealing at 450-800 ℃ for 10-15 hours, and naturally cooling to room temperature to obtain the product.
2. The method of claim 1, wherein the precursor is ground for 10-30 minutes before the annealing in step (2).
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| CN107866214A (en) * | 2017-11-17 | 2018-04-03 | 中国矿业大学 | A kind of chemical solution method prepares Ca3Bi8O15The method of film |
| CN111545189A (en) * | 2020-04-17 | 2020-08-18 | 中国地质大学（北京） | Visible light activity CaBi synthesized by hydrothermal technology2O4Photocatalyst and preparation method thereof |
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