CN109759122B - Bismuth oxybromide ternary heterostructure photocatalyst and preparation method and application thereof - Google Patents
Bismuth oxybromide ternary heterostructure photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a bismuth oxybromide ternary heterostructure photocatalyst. Bismuth nitrate pentahydrate, potassium bromide, graphite-phase carbon nitride and silver nitrate are used as raw materials, the prepared graphite-phase carbon nitride and silver bromide are compounded with bismuth oxybromide to realize modification, and the bismuth oxybromide ternary heterostructure photocatalyst is prepared by a one-step solvothermal method. Compared with pure bismuth oxybromide, the modified bismuth oxybromide prepared by the invention has smaller forbidden band width and higher visible light absorption effect. The smaller forbidden band width reduces the transmission distance of the photoproduction electron holes, improves the separation efficiency of the photoproduction electron holes, reduces the recombination rate, has higher light absorption effect, improves the photon utilization rate, improves the electron hole pair generation rate, and greatly improves the photocatalytic activity under visible light. The method has the advantages of low cost and convenient operation. The organic pollutant can be degraded by using the organic pollutant-degrading agent under visible light, and the organic pollutant-degrading agent has important practical value in environmental purification.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a bismuth oxybromide ternary heterostructure photocatalyst as well as a preparation method and application thereof.
Background
The photocatalytic technology can effectively solve the problems of energy and environment, and is receiving increasingly wide attention. The photocatalytic material can be hydrolyzed by sunlight to produce hydrogen, and can decompose harmful substances and wastes generated in production and living, thereby solving the problems of energy and environment for human survival. At present, the electron-hole pair recombination rate generated after the photocatalyst is irradiated by light is high, the photon utilization efficiency is low, and the photocatalytic activity is not high. Therefore, it is necessary to research modification of semiconductor photocatalysts, and the purpose and effect of the modification include inhibiting electron-hole pair recombination to improve quantum efficiency and increase the specific surface area of the photocatalyst.
The bismuth oxybromide photocatalyst (BiOBr) is a non-metal P-type semiconductor, consists of Bi, O and Br elements, is widely concerned by people due to good chemical stability, thermal stability and optical characteristics, has a forbidden band width of 2.7eV, can absorb visible light with the wavelength less than 600nm, and shows great potential of the non-metal photocatalyst in degrading pollutants. BiOBr is an important ternary bismuth semiconductor compound, is of a chlorofluoro-lead ore type and belongs to a tetragonal system. Has unique electronic structure, excellent visible light absorbing capacity, high stability, low preparation cost and excellent organic pollutant degrading capacity. The pure BiOBr photocatalyst has limited photocatalytic capability due to weak visible light absorption response, high charge recombination, small specific surface area and easy recombination of photo-generated electrons and holes, and therefore needs to be modified.
Disclosure of Invention
The invention aims to provide a preparation method of a ternary heterostructure bismuth oxybromide photocatalyst, which has the advantages of simplicity, convenience in operation, low cost, mild condition and high catalytic efficiency. The technical scheme adopted by the invention is as follows: a preparation method of a bismuth oxybromide ternary heterostructure photocatalyst comprises the following steps:
1) dissolving potassium bromide in ethylene glycol under stirring, adding g-C3N4 powder, and stirring uniformly to obtain solution A;
2) heating, stirring and dissolving bismuth nitrate pentahydrate in ethylene glycol, cooling the solution to room temperature, adding silver nitrate, and ultrasonically dissolving to obtain a solution B;
3) dropwise adding the solution A into the solution B, stirring for 1-2h, placing the solution A into a high-pressure hydrothermal kettle, placing the high-pressure hydrothermal kettle into an oven, heating for reaction, cooling the high-pressure hydrothermal kettle to room temperature after the reaction is finished, centrifugally washing, and drying in the oven to obtain the target product.
In the step 2), the heating temperature is 70-100 ℃.
The bismuth oxybromide ternary heterostructure photocatalyst is prepared from the following components in molar ratio: bismuth nitrate pentahydrate: silver nitrate: graphite-phase carbon nitride 1:0.8:0.08: 0.04.
In the step 3), the heating temperature is 100-120 ℃, and the heating time is 10-16 h.
The bismuth oxybromide ternary heterostructure photocatalyst is applied to degradation of organic pollutants under visible light.
In the application, the bismuth oxybromide ternary heterostructure photocatalyst is added into the wastewater containing organic pollutants, and the wastewater is degraded for 1-2 hours under visible light.
In the above application, the organic pollutant is rambutan B.
The invention has the beneficial effects that:
the invention prepares BiOBr and g-C by one-step solvothermal modification3N4The BiOBr obtained by the ternary heterostructure photocatalyst compounded with AgBr has lower forbidden bandwidth and higher visible light absorption response. The lower forbidden band width reduces the transmission distance of photoproduction electron holes, improves the separation efficiency of the photoproduction electron holes, reduces the recombination rate, improves the photon utilization rate due to higher visible light absorption response, improves the electron hole pair generation rate, and greatly improves the visible light absorption responsePhotocatalytic activity under light. The catalyst prepared by the method has good stability and stable chemical property, and can be repeatedly used. The rate of degrading rhodamine B under visible light is higher than that of pure g-C3N4The height is 3.5 times higher.
Drawings
Figure 1 is an XRD pattern of the pure BiOBr catalyst prepared in example 1.
Figure 2 is an SEM image of the pure BiOBr catalyst prepared in example 1.
Figure 3 is an XRD pattern of the ternary heterostructure BiOBr catalyst prepared in example 2.
Figure 4 is an SEM image of the ternary heterostructure BiOBr catalyst prepared in example 2.
Figure 5 is a comparison of the uv-vis absorption spectra of a pure BiOBr catalyst and a ternary heterostructure BiOBr catalyst.
Figure 6 is a graph comparing the band gap of a pure BiOBr catalyst and a ternary heterostructure BiOBr catalyst.
FIG. 7 is a graph comparing the degradation rates of pure BiOBr and ternary heterostructure BiOBr catalysts in photocatalytic degradation of rhodamine B.
Detailed Description
Example 1 pure BiOBr photocatalyst
(I) preparation method
1.94g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 20ml of ethylene glycol, and cooled to room temperature. 0.595g of potassium bromide are weighed out and dissolved in 20ml of ethylene glycol with stirring. And (3) dropwise adding ethylene glycol dissolved with potassium bromide into the bismuth nitrate solution, stirring for 1h, and then keeping in a high-pressure hydrothermal kettle at the temperature of 120 ℃ for 12 h. And after the high-pressure hydrothermal kettle is cooled to room temperature, centrifugally washing and drying by using deionized water and ethanol to obtain the pure BiOBr photocatalyst.
(II) detection
Figure 1 is an XRD examination of a sample of pure BiOBr photocatalyst. As can be seen from fig. 1, no other peaks were present, indicating that no other impurity phases were present in the product, resulting in a single phase. It can be seen from the figure that the sample has better crystallinity. Figure 2 is an SEM examination of a pure BiOBr photocatalyst sample. As can be seen from fig. 2, pure BiOBr shows a typical spherical structure with individual spheres having a diameter of 2-3 μm.
Example 2 ternary heterostructure BiOBr photocatalyst
1) 0.595g of potassium bromide is dissolved in 20mL of ethylene glycol with stirring, and then 0.0184g g-C3N4 is added and stirred for 30min to obtain solution A.
2) 1.94g of pentahydrate bismuth nitrate is heated and dissolved in 20mL of ethylene glycol, then cooled to room temperature, and then 0.068g of silver nitrate is added and stirred for dissolution, thus obtaining a solution B.
3) Dropwise adding the solution A into the solution B, stirring for 1-2h, placing into a high-pressure hydrothermal kettle, placing the high-pressure hydrothermal kettle into a 120 ℃ drying oven, keeping for 12h, centrifugally washing with deionized water and ethanol after the reaction is finished, and drying to obtain the ternary heterostructure BiOBr.
(II) detection
Figure 3 is an XRD examination of a ternary heterostructure BiOBr catalyst sample. It can be seen from fig. 3 that the sample has good crystallinity, and as shown the sample exhibits two diffraction peaks at 31.1 degrees and 44.5 degrees, corresponding to the (200) and (220) crystal planes of AgBr, respectively. As XRD characteristic peaks of pure BiOBr and the ternary heterostructure BiOBr are similar, the formation of BiOBr microspheres is not influenced in the process of preparing the BiOBr by using the composite g-C3N4 and AgBr.
Figure 4 is an SEM examination of a ternary heterostructure BiOBr catalyst sample. As can be seen from FIG. 4, the microsphere structure of the sample is densely packed with a large number of nanosheets having irregular edges and a width of about 50-100 nm.
Figure 5 is a comparison of the uv-vis absorption spectra of pure BiOBr and ternary heterostructure BiOBr samples. As can be seen from FIG. 5, the absorption effect of the ternary heterostructure BiOBr photocatalyst in the 450-nm visible light band is obviously higher than that of the pure BiOBr photocatalyst, and the light energy utilization rate is greatly improved.
Fig. 6 shows the band gap spectrum detection of pure BiOBr and ternary heterostructure BiOBr samples. It can be seen from fig. 6 that the band gap of the ternary heterostructure BiOBr photocatalyst is significantly lower than that of a pure BiOBr catalyst, the small forbidden band width reduces the transmission distance of the photo-generated electron holes, improves the separation efficiency of the photo-generated electron holes, and reduces the recombination rate.
Example 3 application of ternary heterostructure BiOBr photocatalyst
The ternary heterostructure BiOBr photocatalyst prepared in the embodiment 1 and the embodiment 2 is subjected to a photocatalyst material performance test. The method comprises the following steps: respectively putting 0.01g of pure BiOBr and 0.01g of ternary heterostructure BiOBr in 100ml glass beakers, respectively adding 50ml of 2g/ml rhodamine b solution, and stirring for 1 hour in a dark room. Taking a 300W xenon lamp as a light source, adjusting the photocurrent to a position of 20mA, placing a glass beaker under the xenon lamp light source, starting the xenon lamp for illumination immediately after extracting a first sample, extracting a second sample after 10min, extracting the samples once every 10min, performing visible light absorption test on each sample, and comparing the absorption peak areas. The result is shown in figure 7, after 1h of illumination, rhodamine b is degraded by the pure BiOBr catalyst by 30%, and rhodamine b is degraded by the ternary heterostructure BiOBr by about 95%, so that the ternary heterostructure BiOBr has higher catalytic capability.
Claims (4)
1. The bismuth oxybromide ternary heterostructure photocatalyst is characterized in that the preparation method comprises the following steps:
step 1) adding g-C after potassium bromide is stirred and dissolved in ethylene glycol3N4Uniformly stirring the powder to obtain a solution A;
step 2) heating, stirring and dissolving bismuth nitrate pentahydrate in ethylene glycol, adding silver nitrate for ultrasonic dissolution after the solution is cooled to room temperature, and obtaining a solution B;
step 3) dropwise adding the solution A into the solution B, stirring for 1-2h, placing the solution A into a high-pressure hydrothermal kettle, placing the high-pressure hydrothermal kettle into an oven, heating for reaction, cooling the high-pressure hydrothermal kettle to room temperature after the reaction is finished, centrifugally washing a product in the kettle, and drying the product in the oven to obtain a target product;
in the step 2), the heating temperature is 70-100 ℃;
in terms of molar ratio, potassium bromide: bismuth nitrate pentahydrate: silver nitrate: graphite phase carbon nitride =1:0.8:0.08: 0.04;
in the step 3), the heating temperature is 100-120 ℃, and the heating time is 10-16 h.
2. The use of the bismuth oxybromide ternary heterostructure photocatalyst of claim 1 to degrade organic contaminants under visible light.
3. The use of claim 2, wherein the bismuth oxybromide ternary heterostructure photocatalyst of claim 1 is added into wastewater containing organic pollutants, and is degraded for 1 to 3 hours under visible light.
4. The use according to claim 2, wherein the organic contaminant is rambutan B.
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| CN111036243B (en) * | 2019-12-31 | 2021-08-31 | 福州大学 | Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof |
| CN112850649B (en) * | 2020-12-29 | 2022-03-25 | 杭州电子科技大学 | Preparation method of bismuth oxybromide nanosheet |
| CN114405531B (en) * | 2022-03-07 | 2022-12-13 | 广西民族大学 | Z-type heterojunction photocatalytic nano material with crystal face synergistic effect and preparation method and application thereof |
| CN115957787A (en) * | 2022-11-23 | 2023-04-14 | 浙江大学 | Preparation method of layered ternary composite photocatalytic material |
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| CN108080008A (en) * | 2017-12-05 | 2018-05-29 | 重庆大学 | A kind of preparation method of BiOBr/AgBr/GO Three-element composite photocatalysts |
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