CN114733534A - Bismuth oxybromide-lignin composite photocatalyst and preparation method and application thereof - Google Patents
Bismuth oxybromide-lignin composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 103
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 31
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims abstract description 74
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- 238000001035 drying Methods 0.000 claims abstract description 10
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- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
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- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 238000004043 dyeing Methods 0.000 claims abstract description 6
- 238000007639 printing Methods 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 19
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- 239000002351 wastewater Substances 0.000 claims description 12
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 14
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- 238000001228 spectrum Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
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- 238000007146 photocatalysis Methods 0.000 description 4
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- 230000007547 defect Effects 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
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- 244000166124 Eucalyptus globulus Species 0.000 description 1
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- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a bismuth oxybromide-lignin composite photocatalyst and a preparation method and application thereof, wherein the bismuth oxybromide-lignin composite photocatalyst comprises bismuth oxybromide and lignin, and the preparation method comprises the following steps: dispersing bromine salt and lignin in a dispersing agent to obtain a dispersion liquid, and dissolving bismuth salt in an alcohol reagent to obtain a bismuth salt solution; adding the bismuth salt solution into the dispersion liquid and uniformly mixing to obtain a reaction liquid; pouring the reaction liquid into a hydrothermal kettle, heating the hydrothermal kettle to perform hydrothermal reaction on the reaction liquid, cooling to room temperature after the reaction is completed, and separating, washing and drying the obtained product in sequence to obtain the bismuth oxybromide-lignin composite photocatalyst. The bismuth oxybromide-lignin composite photocatalyst prepared by the invention has the characteristics of high crystallinity, good reusability, high catalytic activity and the like. Can be used for treating rhodamine B (the degradation rate is as high as 99.2%) under visible light, and has wide application prospect in the fields of industrial wastewater of pulping, papermaking, printing and dyeing and the like.
Description
Technical Field
The invention relates to the field of environmental materials, in particular to a bismuth oxybromide-lignin composite photocatalyst and a preparation method and application thereof, aiming at industrial wastewater of printing, dyeing, pulping, papermaking and the like.
Background
With the development of industrialization process, environmental pollution becomes a serious problem, especially water pollution, wherein the discharge amount of the waste water of pulping and paper making industry and printing and dyeing industry is the front of the discharge amount of the waste water of China industry. Wastewater is characterized by high content of various organic substances and is therefore not easy to treat. Advanced Oxidation Processes (AOPs), such as ozone, Fenton and photo-Fenton processes, photolysis, photocatalysis, etc., have attracted considerable research interest due to the highly reactive intermediates (. O.) produced in the reaction2 -And. OH). Photocatalysis is considered to be an effective method for removing water pollutants because it has the excellent advantages of mild reaction conditions, simple operation process, high efficiency, low cost, etc. In the photocatalytic process, sunlight is converted into chemical energy or electric energy that can be continuously developed, and active substances having strong oxidizing power, including holes, superoxide radicals, and hydroxyl radicals, are generated. The oxidized substance can effectively convert harmful organic pollutants into small molecules with low toxicity without causing secondary pollution, so that the semiconductor photocatalysis technology is a very promising environmental remediation technology.
The bismuth oxybromide (BiOBr) has the forbidden band width of 2.7-2.9eV, is a narrow-forbidden-band semiconductor, has good visible light response and high photoproduction electron-hole separation efficiency. The excellent properties of BiOBr are mainly derived from its layered structure, which is composed of [ Bi ]2O2]The plate and the double-halogen atom plate are crossed. Bi and O in Bi2O2The layers are connected by strong covalent bonds. The special internal electric field between the bismuth oxide layer and the halogen atoms can effectively separate electrons and holes, so that the BiOBr material is widely used for degrading dyes, various phenols, water pollutants and a plurality of antibiotics. However, BiOBr has some disadvantages of poor adsorption performance, low quantum efficiency, rapid recombination of electron-hole pairs, and small specific surface area, which impair the performance of catalytic degradation. The composite material is an effective way for improving the separation efficiency of the photo-generated electron-hole pair of the photocatalyst. Lignin is one of the most abundant renewable aromatic polymers in nature, and the pulp and paper industry produces large quantities of lignin as a by-product every year. Lignin, which is inexpensive, easily degradable and low in toxicity, is considered as an effective substitute for petroleum fuels and has been widely used for the development of new materials. At present, no report related to the preparation of the BiOBr/Lignin composite photocatalyst by combining BiOBr and Lignin exists. The lignin forms biochar (biochar) by a hydrothermal method, and the photocatalysis effect of BiOBr can be effectively enhanced.
Disclosure of Invention
In order to solve the existing defects of bismuth oxybromide (BiOBr), the invention aims to provide a bismuth oxybromide-lignin composite photocatalyst, and a preparation method and application thereof, so as to enhance the visible light catalytic effect of the BiOBr, and further apply the bismuth oxybromide-lignin composite photocatalyst to actual wastewater treatment.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a bismuth oxybromide-lignin composite photocatalyst, which comprises bismuth oxybromide and lignin, wherein the mass of the lignin is 1 wt% -12 wt% of that of the bismuth oxybromide. The lignin is used as a byproduct of pulping and papermaking industry, the source is rich, the specific surface area of the lignin is large, the functional groups are rich, and biochar formed by a hydrothermal method has a plurality of pores, can effectively adsorb pollutants, and enhances the photocatalytic performance.
The second purpose of the invention is to provide a preparation method of the bismuth oxybromide-lignin composite photocatalyst. The commonly used synthesis methods of bismuth oxybromide include a hydrothermal method, a hydrolysis method, a precipitation method, a sol-gel method and a microwave method, wherein the hydrothermal method is simplest and convenient to operate, and the form of the synthesized bismuth oxybromide is easy to control and has good crystallinity. The steps of synthesizing the bismuth oxybromide-lignin composite photocatalyst by a hydrothermal method are as follows: dispersing bromine salt and lignin in a dispersing agent to obtain a dispersion liquid, and dissolving bismuth salt in an alcohol reagent to obtain a bismuth salt solution; adding the bismuth salt solution into the dispersion liquid and uniformly mixing to obtain a reaction liquid; pouring the reaction liquid into a hydrothermal kettle, heating the hydrothermal kettle to perform hydrothermal reaction on the reaction liquid, cooling to room temperature after the reaction is finished, sequentially separating, washing and drying the obtained product in vacuum at the temperature of 50-60 ℃ to obtain the bismuth oxybromide-Lignin composite photocatalyst (BiOBr/Lignin composite photocatalyst)
The main chemical reactions involved in the hydrothermal reaction process are as follows: bi and O in the reaction solution are linked by a covalent bond to form [ Bi2O2]And forming a BiOBr laminated structure with the double Br layer, wherein the Lignin is changed into biochar (biochar) through a hydrothermal reaction, and the BiOBr grows on the biochar to finally obtain the BiOBr/Lignin composite photocatalyst.
Preferably, the molar ratio of the bismuth salt to the bromine salt is 1: 1-1: 2.
Preferably, the temperature of the hydrothermal reaction is 140-200 ℃, and the time is 24-48 h.
Preferably, the dispersant is water, nitric acid or sulfuric acid; the alcohol reagent is absolute ethyl alcohol, ethylene glycol or isopropanol.
Preferably, the lignin is at least one of alkali lignin and lignosulfonate; the bismuth salt is any one of bismuth nitrate, bismuth sulfate, bismuth chloride or bismuth acetate; the bromine salt is any one of potassium bromide and sodium bromide.
The third object of the invention is to provide the application of the bismuth oxybromide-lignin composite photocatalyst as in the first object in treating wastewater under visible light. Further preferably, the wastewater is printing and dyeing wastewater or pulping and papermaking wastewater.
Compared with the prior art, the invention has the following advantages:
(1) the BiOBr/Lignin composite photocatalyst prepared by the invention effectively utilizes Lignin which is a byproduct in the pulping and papermaking industry, realizes sustainable utilization of resources, and can also treat wastewater in the pulping and papermaking industry.
(2) The BiOBr/Lignin composite photocatalyst prepared by the method overcomes the defects of poor adsorption performance, low quantum efficiency, rapid recombination of electron-hole pairs, small specific surface area and the like of BiOBr, improves the concentration of pollutants around the catalyst, and enhances the photocatalytic reaction performance of the catalyst.
Drawings
Fig. 1 is an XRD pattern of the products prepared in comparative example and examples 1 to 5;
FIG. 2 is a scanning electron microscope photograph of BiOBr (a), Biochar (b) and BiOBr/2 wt% Lignin (c-d);
FIG. 3 is an X-ray energy spectrum (EDS) of BiOBr/2 wt% Lignin;
FIG. 4 shows BiOBr4And XPS spectra (a) of BiOBr/2 wt% Lignin, high resolution XPS spectra (b-e) of Br, Bi, O and C elements.
Detailed Description
The present invention will be further described with reference to the following examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention. The starting materials or reagents used in the following examples are all commercially available products.
Example 1:
1g of alkali lignin is put into a beaker and dried in an oven at 40 ℃ for 30 minutes for later use. 4mmol of Bi (NO)3)3·5H2Dissolving O in 30mL of absolute ethyl alcohol, and uniformly stirring by ultrasonic waves to obtain Bi (NO)3)3·5H2O solution; respectively adding 4mmol KBr and 0.0244g lignin into 20ml distilled water, and stirring to obtain dispersion; then Bi (NO)3)3·5H2Adding the O solution into a dispersion liquid containing KBr and lignin, carrying out ultrasonic treatment for 30min, and then carrying out vigorous stirring for 30min to obtain a reaction liquid; pouring the reaction solution into a 100mL stainless steel water heating kettle with polytetrafluoroethylene lining, and heating in an oven at 160 ℃ for 24hTo carry out hydrothermal reaction; after the reaction is finished, the obtained product is sequentially separated, washed and dried to obtain the bismuth oxybromide-Lignin composite photocatalyst, namely a BiOBr/2 wt% Lignin photocatalyst (2 wt% represents the mass percentage of Lignin in the BiOBr catalyst), and the label is BL 2.
Comparative example 1
In comparison with example 1, in the comparative example, the amount of added lignin was 0g when preparing the dispersion, i.e., no lignin was added, and a BiOBr photocatalyst was obtained.
Examples 2 to 5
Compared with example 1, the difference between examples 2 to 5 is that the added amount of lignin is different, the other processes are the same as example 1, and the added amounts of lignin in examples 2 to 5 are respectively as follows: 0.0122g, 0.0488g, 0.0976g and 0.122 g; the products obtained in examples 2 to 5 were respectively identified as BiOBr/1 wt% Lignin (BL1), BiOBr/4 wt% Lignin (BL4), BiOBr/8 wt% Lignin (BL8), BiOBr/10 wt% Lignin (BL 10).
Photocatalytic Performance test
The photocatalysts prepared in examples 1 to 5 and the comparative example were respectively subjected to a photocatalytic performance test by the following methods: adding 50mg of photocatalyst into 250mL of 30mg/L rhodamine B solution, irradiating by using a 300wXe lamp (a cut-off filter with the wavelength of 420 nanometers is arranged at the outlet of a light source), and testing the degradation rate of the rhodamine B after 1 hour. The results are given in Table 1 below.
TABLE 1 degradation rate of rhodamine B by the photocatalysts prepared in examples 1-5 and comparative example
From table 1, it can be seen that the photocatalytic efficiency of the lignin-doped composite catalyst is higher than that of pure BiOBr, and the catalytic efficiency of the composite catalyst is increased and then decreased with the increase of the doping amount of lignin, wherein the effect of BL2 is the best.
The BiOBr/2 wt% Lignin which is subjected to the catalytic performance test for one time is centrifugally separated from the rhodamine B solution and taken out, after washing and drying, the BiOBr/2 wt% Lignin is repeatedly used for treating 250mL of 30mg/L rhodamine B solution for three times, a 300wXe lamp (a cut-off filter with the length of 420 nanometers is arranged at the outlet of a light source) is used for irradiation, and the degradation rate of the rhodamine B after 1 hour is shown in the following table 2:
table 2 degradation rate of rhodamine B after repeated use of BiOBr/2 wt% Lignin for three times
From table 2, it can be seen that the catalytic effect of the catalyst is only slightly reduced after three repeated experiments. The repeatability and stability of the catalyst are good.
Example 6
And (3) putting 1g of lignosulfonate into a beaker, and drying in a drying oven at 40 ℃ for 30 minutes to obtain lignin. 4mmol of BiCl3Dissolving the mixture in 30mL of absolute ethyl alcohol, and uniformly stirring the mixture by ultrasonic waves to obtain BiCl3A solution; adding 4mmol of KBr and 0.122g of lignin into 20ml of distilled water, and uniformly stirring to obtain a dispersion liquid; then adding BiCl3Adding the solution into a dispersion liquid containing NaBr and lignin, carrying out ultrasonic treatment for 30min, and then carrying out vigorous stirring for 30min to obtain a reaction liquid; pouring the reaction liquid into a 100mL stainless steel water heating kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven to be heated for 48 hours at 200 ℃ to carry out hydrothermal reaction; after the reaction is finished, separating, washing and drying the obtained product in sequence to obtain the BiOBr/10 wt% Lignin photocatalyst.
50mg of BiOBr/10 wt% of Lignin catalyst is added into 250mL of 30mg/L rhodamine B solution, a 300wXe lamp (a cut-off filter with the wavelength of 420 nanometers is arranged at the outlet of a light source) is used for irradiation, and the degradation rate of rhodamine B is 79.81% after 1 hour.
Example 7
The lignin was prepared as in example 6. 2mmol of Bi2(SO4)3Dissolving the Bi in 30mL of absolute ethyl alcohol and uniformly stirring by ultrasonic waves to obtain Bi2(SO4)3A solution; adding 4mmol NaBr and 0.0976g lignin into 20ml distilled water, and stirring uniformly to obtain a dispersion liquid; then Bi is added2(SO4)3Adding the solution into a dispersion liquid containing NaBr and lignin, carrying out ultrasonic treatment for 30min, and then carrying out vigorous stirring for 30min to obtain a reaction liquid; pouring the reaction liquid into a 100mL stainless steel hydrothermal kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven to be heated for 48 hours at 140 ℃ to carry out hydrothermal reaction; after the reaction is finished, separating, washing and drying the obtained product in sequence to obtain the BiOBr/8 wt% Lignin.
50mg of BiOBr/8 wt% of Lignin catalyst is added into 250mL of 30mg/L rhodamine B solution, a 300wXe lamp (a cut-off filter with the size of 420 nanometers is arranged at the outlet of a light source) irradiates, and the degradation rate of rhodamine B is 76.43% after 1 hour.
Example 8
The lignin was prepared as in example 1. 4mmol of Bi (NO)3)3·5H2Dissolving O in 30mL of absolute ethyl alcohol, and uniformly stirring by ultrasonic waves to obtain Bi (NO)3)3·5H2O solution; adding 4mmol of KBr and 0.122g of lignin into 20ml of nitric acid, and uniformly stirring to obtain a dispersion liquid; then Bi (NO)3)3·5H2Adding the O solution into a dispersion containing KBr and lignin, carrying out ultrasonic treatment for 30min, and then carrying out vigorous stirring for 30min to obtain a reaction solution; pouring the reaction liquid into a 100mL stainless steel water heating kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven to be heated for 12 hours at 160 ℃ to carry out hydrothermal reaction; after the reaction is finished, the obtained product is sequentially subjected to separation, washing and drying to obtain the BiOBr/10 wt% Lignin.
50mg of BiOBr/10 wt% of Lignin catalyst is added into 250mL of 30mg/L rhodamine B solution, a 300wXe lamp (a cut-off filter with the wavelength of 420 nanometers is arranged at the outlet of a light source) is used for irradiation, and the degradation rate of rhodamine B is 72.36% after 1 hour.
Example 9
The lignin was prepared as in example 1. 4mmol of Bi (CH)3COO)3Dissolving the mixture in 30mL of absolute ethyl alcohol, and uniformly stirring the mixture by ultrasonic waves to obtain Bi (CH)3COO)3A solution; adding 4mmol of KBr and 0.1464g of lignin into 20ml of distilled water, and uniformly stirring to obtain a dispersion liquid; then Bi (CH)3COO)3Adding the solution into a dispersion containing KBr and ligninPerforming ultrasonic treatment for 30min, and then stirring vigorously for 30min to obtain a reaction solution; pouring the reaction liquid into a 100mL stainless steel water heating kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven to be heated for 48 hours at 160 ℃ to carry out hydrothermal reaction; after the reaction is finished, the obtained product is sequentially subjected to separation, washing and drying to obtain the BiOBr/12 wt% Lignin.
50mg of BiOBr/12 wt% Lignin catalyst is added into 250mL of eucalyptus chemimechanical pulping effluent with COD of 273mg/L, and the effluent is irradiated by a 300wXe lamp (the outlet of a light source is provided with a 420-nanometer cut-off filter), and the removal rate of the COD after 1h is 52.65%.
Material characterization
In order to investigate the crystal phase and structure of the BiOBr prepared in the comparative example and the composite photocatalysts prepared in examples 1 to 5, we performed XRD characterization on them, and the results are shown in fig. 1. Fig. 1 shows that all samples showed similar diffraction peaks in the X-ray diffraction pattern, indicating that all samples were highly pure crystals without impurity peaks. All diffraction peaks of the BiOBr sample synthesized by the hydrothermal reaction are matched with the quadrilateral crystal JCPDF No.09-0393, and no impurity peak exists. No significant carbon structure diffraction peak was observed between 20 ° and 30 ° of the composite photocatalyst, probably because the main peak of the biochar at 20 ° to 30 ° and the (101) peak of the quadrilateral BiOBr at 25.16 ° overlap. The diffraction peak intensities of all the composite photocatalysts in the figure 1 are obviously reduced compared with that of pure BiOBr, which shows that the addition of lignin can cause the lattice defect of the BiOBr, and the change of the lattice constant also shows that after the synthesis by a hydrothermal method, a certain interaction exists between the BiOBr crystal and the lignin structure.
FIG. 2 is a scanning electron microscope photograph of BiOBr (a), Biochar (b) and BiOBr/2 wt% Lignin (c-d); as can be seen from the figure, BiOBr is a layered sheet structure and has a size distribution between 500nm and 1 μm. The product formed by the hydrothermal reaction of lignin is Biochar (Biochar), and the Biochar is a blocky structure with enough surface area and a plurality of scaly structures on the surface and is about 150 mu m in size. Fig. 2c and 2d are SEM images of the BiOBr/2 wt% Lignin composite photocatalyst at different magnifications, and it can be seen that in the BiOBr/2 wt% Lignin composite photocatalyst, BiOBr is uniformly dispersed on Biochar. This exposes the BiOBr more active sites, provides a transport channel for photo-generated electrons and increases more opportunities for contact between the BiOBr and the reactant molecules. EDS (electron-dispersive spectroscopy) energy spectrum analysis is carried out on the BiOBr/2 wt% Lignin, as shown in figure 3, it can be seen from figure 3 that the BiOBr/2 wt% Lignin catalyst contains Br, Bi, O and C elements, and further proves that the BiOBr successfully and uniformly disperses and grows on the surface of the Biochar.
In order to analyze the elemental composition and the valence state of each element in the BiOBr and BiOBr/2 wt% Lignin, an X-ray photoelectron energy spectrum is adopted to characterize the BiOBr and BiOBr/2 wt% Lignin and the XPS spectrogram of each element. FIG. 4b is a spectrum of Br 3d, and it can be found that there are two strong peaks of spin-orbit splitting energy at 68.46eV and 69.49eV, respectively, with Br 3d 5/2 and Br 3d3/2It is relevant. And the Bi 4f spectrum of 4c has two independent symmetrical peaks at 159.46 and 164.78eV, which belong to the Bi 4f7/2And Bi 4f5/2. The peak binding energy of Br 3d, Bi 4f and O1s of BL2 is 0.26-0.44eV less than that of BiOBr. This is because electron interactions occur, primarily due to strong interactions of some unpaired pi electrons of the conjugated carbon atoms with free electrons of the BiOBr surface, resulting in charge transfer switching. The O1s peak of BiOBr (fig. 4d) was split into two peaks at 530.21 and 531.61eV, associated with lattice O atoms (Bi-O bonds) and surface-OH, respectively. From the shift in the positions of the peaks of the O1s and Bi 4f spectra, we can guess that a Bi — C bond is formed between the conjugated carbon and the BiOBr. The binding energy of C1s of BL2 at 284.65, 286.11, 288.13eV is matched to the C-C, C-O, C ═ O bond, respectively. The peaks of C1s were very uneven due to the lower amount of lignin doping.
In conclusion, the BiOBr/Lignin photocatalyst prepared by the method can accelerate the separation of photoproduction electrons and cavities, improve the absorption of visible light and the concentration of pollutants around the catalyst, enhance the photocatalytic reaction performance, has stable property and high recycling efficiency, and has good effect on treatment of industrial wastewater of printing and dyeing, pulping, papermaking and the like.
It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A bismuth oxybromide-lignin composite photocatalyst is characterized in that: the bismuth oxybromide-lignin composite photocatalyst comprises bismuth oxybromide and lignin, wherein the mass of the lignin is 1 wt% -12 wt% of that of the bismuth oxybromide.
2. The method for preparing the bismuth oxybromide-lignin composite photocatalyst according to claim 1, wherein the bismuth oxybromide-lignin composite photocatalyst comprises the following components in percentage by weight: the method comprises the following steps: dispersing bromine salt and lignin in a dispersing agent to obtain a dispersion liquid, and dissolving bismuth salt in an alcohol reagent to obtain a bismuth salt solution; adding the bismuth salt solution into the dispersion liquid and uniformly mixing to obtain a reaction liquid; pouring the reaction liquid into a hydrothermal kettle, heating the hydrothermal kettle to perform hydrothermal reaction on the reaction liquid, cooling to room temperature after the reaction is completed, and separating, washing and drying the obtained product in sequence to obtain the bismuth oxybromide-lignin composite photocatalyst.
3. The method for preparing the bismuth oxybromide-lignin composite photocatalyst according to claim 2, wherein the bismuth oxybromide-lignin composite photocatalyst comprises the following components in percentage by weight: the molar ratio of the bismuth salt to the bromine salt is 1: 1-1: 2.
4. The method for preparing the bismuth oxybromide-lignin composite photocatalyst according to claim 2, wherein the bismuth oxybromide-lignin composite photocatalyst comprises the following components in percentage by weight: the dispersant is water, nitric acid or sulfuric acid; the alcohol reagent is absolute ethyl alcohol, ethylene glycol or isopropanol.
5. The method for preparing the bismuth oxybromide-lignin composite photocatalyst according to claim 2, wherein the bismuth oxybromide-lignin composite photocatalyst comprises the following components in percentage by weight: the temperature of the hydrothermal reaction is 140-200 ℃, and the time is 24-48 h.
6. The method for preparing the bismuth oxybromide-lignin composite photocatalyst according to any one of claims 2 to 5, wherein: the lignin is at least one of alkali lignin and lignosulfonate; the bismuth salt is any one of bismuth nitrate, bismuth sulfate, bismuth chloride or bismuth acetate; the bromine salt is any one of potassium bromide and sodium bromide.
7. The use of the bismuth oxybromide-lignin composite photocatalyst of claim 1 in the treatment of wastewater under visible light.
8. Use according to claim 7, characterized in that: the wastewater is printing and dyeing wastewater or pulping and papermaking wastewater.
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