CN114425371B - Method for inducing self-assembly of bismuth-based photocatalytic material by using biosurfactant and application - Google Patents
Method for inducing self-assembly of bismuth-based photocatalytic material by using biosurfactant and application Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 164
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 161
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000000463 material Substances 0.000 title claims abstract description 158
- 238000000034 method Methods 0.000 title claims abstract description 70
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- 229960004150 aciclovir Drugs 0.000 claims description 2
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 2
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 claims description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- B01J35/39—Photocatalytic properties
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Abstract
The invention discloses a self-assembly method of a biosurfactant-induced bismuth-based photocatalytic material and application thereof, wherein the method comprises the following steps: dispersing the Chinese honeylocust fruit powder in bismuth-based precursor solution by ultrasonic, and carrying out hydrothermal reaction after fully stirring; the solute of the bismuth-based precursor solution is A salt and bismuth salt; the A salt comprises one of halogen salt, tungstate, molybdate and metavanadate. According to the invention, the gleditsia sinensis powder is used as a biosurfactant to induce the self-assembly of the bismuth-based photocatalytic material for the first time, wherein active groups in the gleditsia sinensis powder are attached to the surface of the bismuth-based photocatalytic material, so that the self-assembly of the bismuth-based photocatalytic material into a unique flower ball structure can be induced, the interfacial force between the bismuth-based photocatalytic material and water can be reduced as an activator, the surface adsorption site of the bismuth-based photocatalytic material can be further increased, and the photocatalytic activity of the bismuth-based photocatalytic material can be synergistically enhanced.
Description
Technical Field
The invention relates to the technical field of functional nano materials. More particularly, relates to a method for inducing self-assembly of bismuth-based photocatalytic materials by using a biosurfactant and application thereof.
Background
Hydrogen peroxide (H) 2 O 2 ) Is always considered as a clean energy source which has great prospect and can replace hydrogen energy, and can be used in various fields such as single-chamber battery power generation and the like. In particular, H 2 O 2 As a carrier of energy, its own energy density and compressed H 2 Equivalent, but H 2 O 2 Having a ratio of H 2 Safer storage means and more convenient transportation means. At the same time H 2 O 2 Also a multifunctional cleaning oxidizer which is applied in various chemical industry and environmental treatment fields including pulp manufacture and bleaching, electronic industry, disinfection industry, water treatment industry and the like. Currently, H is produced 2 O 2 The most common commercial process is the anthraquinone process. Anthraquinone process is to catalyze H with noble metal 2 And O 2 Direct conversion to H 2 O 2 However, the anthraquinone process is not only complicated but also generates a large amount of toxic byproducts due to its high production cost, thus limiting its wide application. In addition, catalyzing H with noble metal catalytic materials 2 And O 2 There are also potential explosion hazards and high energy consumption problems with the process of (a). Thus, an efficient and inexpensive H is sought 2 O 2 The production method is of paramount importance.
Photocatalytic production of H by semiconductor catalytic material 2 O 2 Is considered to be a very promising route. Theoretically, the rich water and oxygen on earth can generate H through semiconductor photocatalysis 2 O 2 The process is as follows: first photo-generating valence band holes (VB h) + ) Oxidizing water to produce O 2 Conduction band electron (CB e - ) Promote O 2 To generate H 2 O 2 . Thus, the photocatalytic production of H 2 O 2 Is a new candidate for artificial photosynthesis. However, these redox reactions all have positive gibbs free energy changes and are thermodynamically unfavorable for H 2 O 2 Is generated. And O is 2 Single electron reduction of (2) generally occurs as the dominant reaction, forming superoxide radicals, thereby inhibiting O 2 Is reduced to H by two electrons 2 O 2 . In addition, the catalytic material may be generating H 2 O 2 After that, by disproportionation or VBh + Oxidation to decompose H on semiconductor surface 2 O 2 Resulting in reduced yields. Therefore, the method has the advantages of low searching and developing cost, good photocatalytic performance and capability of recycling the photocatalytic material to produce H 2 O 2 Still is one of the important directions in the field of photocatalytic research. For this purpose, the photocatalytic material chosen is: (1) it must have a strong photocatalytic ability; (2) for O 2 High selectivity and promote O 2 Reduction, hinder H 2 O 2 Decomposing; (3) the stability is good; (4) the usage amount is low, the efficiency is high, and the environment is protected without toxicity.
The bismuth-based catalyst material has [ Bi ] 2 O 2 ] 2+ The layered structure is favored in the field of photocatalysis as a separation channel. As a typical bismuth-based catalytic material, bismuth-based composite oxides have been intensively studied in the field of photocatalysis, such as water splitting, N 2 And the fixation of organic pollutants. Meanwhile, the interlayer region of the bismuth-based composite oxide is used as an active center of a photocatalytic reaction, so that excellent activity/stability of the material is provided. In addition, the orbitals of Bi 6s and Bi 6p contribute to bismuth-based complexes, respectively
The Valence (VB) and Conduction (CB) bands of the oxide result in a reduction of the band gap of the catalytic material, extending the light harvesting range into the visible region. In fact, hybridization can also occur between Bi 6s and O2 p, resulting in an increase in the dispersion of VB, improving the transfer efficiency of VB photogenerated holes, and inhibiting recombination with photogenerated electrons. In addition, the bismuth-based composite oxide photocatalytic material can be prepared by a simple and low-energy-consumption strategy, such as a rapid and simple wet chemical method. More interestingly, the CB and VB positions of the bismuth-based composite oxide photocatalytic material can be effectively adjusted to accommodate a variety of photocatalytic redox reactions. To improve the photocatalytic H production 2 O 2 Several strategies have been adopted by researchers. For example, su et al directly transferred holes from the valence band of BiOCl to HCOO by adding HCOOH to the reaction solution as a hole shuttle - HCOO. Was generated. HCOO further with OH - React to form OH. (see: internal Electric Field Assisted Photocatalytic Generationof Hydrogen Peroxide over BiOCl with HCOOH, ACS Sustainable Chemistry&Engineering,2018,6,8704-8710). Sn introduced by Wei et al regulates the growth of BiOCl to form ultrathin nanoplatelets with surface oxygen vacancies. The separation of photogenerated charges is accelerated by inducing an electric field within the interface by surface modification at the BiOCl and redistributing charges at the interface. Sn modification reduces the work function of Sn-BiOCl, and improves the conduction band and valence band of Sn-BiOCl, thereby improving the photocatalytic reducibility and the O 2- Provides a new strategy for modification of BiOCl materials (see: interfacial internal electricfield and oxygen vacancies synergisticallyenhance photocatalytic performance of bismuth oxychloride, journ)l of Hazardous Materials,2021,402,123470)。
In summary, the improvement of photocatalytic efficiency of modified bismuth-based composite oxide photocatalytic materials has been widely studied. However, there is still a lack of research on the induction of self-assembly of bismuth-based composite oxides using biosurfactants.
Disclosure of Invention
The first object of the invention is to provide a method for inducing self-assembly of bismuth-based photocatalytic material by using biosurfactant.
A second object of the present invention is to provide a bismuth-based photocatalytic material.
A third object of the present invention is to provide the use of a bismuth-based photocatalytic material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, a method for inducing self-assembly of bismuth-based photocatalytic material by a biosurfactant comprises the steps of:
and dispersing the Chinese honeylocust fruit powder in the bismuth-based precursor solution by ultrasonic, and fully stirring to perform hydrothermal reaction.
The solute of the bismuth-based precursor solution is A salt and bismuth salt; the A salt comprises one of halogen salt, tungstate, molybdate and metavanadate.
The preparation method of the invention is to add the Chinese honeylocust fruit powder as the biosurfactant into the precursor solution of the bismuth-based photocatalytic material, and then induce the bismuth-based photocatalytic material to grow and age along different crystal planes in the hydrothermal process, thereby obtaining the bismuth-based photocatalytic material with lower surface energy. The invention provides a method for inducing the growth of bismuth-based photocatalytic materials by using the honey locust powder as a biosurfactant for the first time. Wherein, the Chinese honeylocust fruit powder and the catalytic material can form non-covalent interactions such as hydrogen bond and Van der Waals force interactions, so as to induce the catalytic material to self-assemble into a unique structure. Meanwhile, active groups in the Chinese honeylocust fruit powder are attached to the surface of the bismuth-based photocatalytic material, so that the interfacial force between the bismuth-based photocatalytic material and water can be reduced, the surface energy of the bismuth-based photocatalytic material is further reduced, the surface adsorption sites of the bismuth-based photocatalytic material are increased, and the photocatalytic activity of the bismuth-based photocatalytic material is synergistically enhanced.
Further, in the above method, the mass ratio of the total mass of the a salt and the bismuth salt (solute of bismuth-based precursor solution) to the powder of the gleditsia sinensis is 1:0.05-0.5.
The molar ratio of the A salt to the bismuth salt is 1:1-2.
The solvent of the bismuth-based precursor solution is water and alcohol; preferably, the alcohol is ethanol or ethylene glycol. The amount of the solvent and the solute in the bismuth-based precursor solution can be adjusted according to the requirement, for example, the mass-volume ratio of the solute to the solvent is 1-5g:80-200mL.
The volume ratio of the alcohol to the water is 1:5-10.
According to a specific embodiment of the present invention, the solvent is an aqueous ethanol solution.
The halogen salt is one of sodium chloride, potassium bromide and potassium iodide.
The bismuth salt is bismuth nitrate pentahydrate.
The tungstate is sodium tungstate.
The molybdate is sodium molybdate.
The metavanadate is ammonium metavanadate.
The dispersion mode of dispersing the Chinese honeylocust fruit powder in the bismuth-based precursor solution is preferably ultrasonic dispersion, more preferably ultrasonic treatment time is 0.5-1h, wherein the ultrasonic dispersion can better uniformly disperse the Chinese honeylocust fruit powder in the bismuth-based precursor solution, and further better regulate and control the structure of the bismuth-based photocatalytic material.
The stirring time is 0.5-1 hour. The soap powder can be uniformly dispersed in the bismuth-based precursor solution more optimally in the time range.
The hydrothermal reaction is carried out for 16-24 hours at 160-200 ℃. For example, the hydrothermal reaction is carried out at 160 to 180℃for 18 to 20 hours, the hydrothermal reaction is carried out at 180 to 200℃for 18 to 20 hours, and the like.
The method further comprises washing and drying after the hydrothermal reaction.
Preferably, the drying is under vacuum. Wherein, the vacuum drying is used for preventing the bismuth-based photocatalytic material from agglomerating in the drying process.
More preferably, the drying is performed in a vacuum environment at a temperature of 70-105 ℃ for 6-8 hours.
The Chinese honeylocust fruit powder is nano-scale and/or micro-scale Chinese honeylocust fruit powder. For example, the particle size of the honey locust powder is 1 nm to 1000 microns, 10 nm to 100 microns, 50nm to 100 microns, 100nm to 50 microns, etc. Wherein, the nano-scale and/or micro-scale Chinese honeylocust fruit powder can be more uniformly attached on the surface of the bismuth-based photocatalytic material, thereby better regulating and controlling the structure of the bismuth-based photocatalytic material.
In a second aspect, the present invention provides a bismuth-based photocatalytic material produced by the above-described production method.
In a third aspect, the invention provides a bismuth-based photocatalytic material for producing H in photocatalysis 2 O 2 Or in the photocatalytic degradation of antibiotics.
Preferably, the antibiotic comprises one or more of sulfanilamide, diclofenac sodium, tetracycline, acyclovir.
Further, the bismuth-based photocatalytic material is used for producing H by photocatalysis 2 O 2 The application comprises the following steps:
and ultrasonically dispersing the bismuth-based photocatalytic material into deionized water, and carrying out illumination.
Further, the light source of illumination is visible light with the wavelength of more than or equal to 420 nm.
According to the specific embodiment of the invention, the mass volume ratio of the bismuth-based photocatalytic material to the deionized water is 10-50mg:50-200mL.
According to the specific embodiment of the invention, the mass volume ratio of the bismuth-based photocatalytic material to deionized water is 10 mg/50 mL.
According to the specific embodiment of the invention, the mass volume ratio of the bismuth-based photocatalytic material to deionized water is 20 mg/50 mL.
According to the specific embodiment of the invention, the mass volume ratio of the bismuth-based photocatalytic material to deionized water is 50 mg/50 mL.
Further, the bismuth-based photocatalytic material is used for photocatalytic degradation of antibiotics, the application comprising the steps of:
and (3) ultrasonically dispersing the bismuth-based photocatalytic material into an aqueous solution of antibiotics, and carrying out illumination.
Further, the light source of illumination is visible light with the wavelength of more than or equal to 420 nm.
According to a specific embodiment of the invention, the concentration of the aqueous solution of the antibiotic is 1-10ppm; the mass volume ratio of the bismuth-based photocatalytic material to the aqueous solution of the antibiotic is 10-50mg:50-200mL.
According to a specific embodiment of the invention, the concentration of the aqueous solution of the antibiotic is 3ppm.
According to a specific embodiment of the invention, the concentration of the aqueous solution of the antibiotic is 10ppm.
The beneficial effects of the invention are as follows:
1. the preparation method of the bismuth-based photocatalytic material mainly uses the Chinese honeylocust fruit powder as a biosurfactant to induce the bismuth-based precursor to self-assemble into the bismuth-based photocatalytic material with a flower-sphere structure. The active groups in the Chinese honeylocust fruit powder are attached to the surface of the photocatalytic material, so that the self-assembly of the bismuth-based photocatalytic material can be induced, the surface energy of the bismuth-based photocatalytic material can be reduced as an active ingredient, the migration efficiency of carriers of the bismuth-based photocatalytic material can be synergistically improved, and the photocatalytic activity of the bismuth-based photocatalytic material can be enhanced.
2. The bismuth-based photocatalytic material provided by the invention has stable structure and is respectively used for producing H by photocatalysis 2 O 2 And photocatalytic degradation of antibiotics, H 2 O 2 The yield can reach 100.3 mu mol/L, and the degradation rate of the sulfanilamide is about 1.2 to 12.8 times of that of the bismuth-based photocatalytic material prepared by the ordinary method.
3. The preparation method of the bismuth-based photocatalytic material provided by the invention has the advantages of simple process and convenience in operation, and is suitable for large-scale production and application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a scanning electron microscope image of the bismuth-based photocatalytic material SA-BiOCl prepared in example 1;
FIG. 2 shows a transmission electron microscope image of the bismuth-based photocatalytic material SA-BiOCl prepared in example 1;
FIG. 3 shows a scanning electron microscope image of the bismuth-based photocatalytic material SA-BiOBr prepared in example 9;
FIG. 4 shows a transmission electron microscope image of the bismuth-based photocatalytic material SA-BiOBr prepared in example 9;
FIG. 5 shows a scanning electron microscope image of the bismuth-based photocatalytic material SA-BiOI prepared in example 17;
FIG. 6 shows a transmission electron microscope image of the bismuth-based photocatalytic material SA-BiOI prepared in example 17;
FIG. 7 is a chart showing the Fourier transform infrared spectra of the bismuth-based photocatalytic material and the powder of Gleditsia sinensis obtained in example 1 and comparative example 1;
FIG. 8 is a chart showing the Fourier transform infrared spectra of the bismuth-based photocatalytic materials prepared in example 9 and comparative example 2;
FIG. 9 is a chart showing the Fourier transform infrared spectra of the bismuth-based photocatalytic materials produced in example 17 and comparative example 3;
FIG. 10 is a graph showing the comparison of fluorescence spectra of the bismuth-based photocatalytic materials produced in example 1 and comparative example 1;
FIG. 11 shows XRD contrast patterns of bismuth-based photocatalytic materials prepared in example 1, example 9, example 17 and comparative examples 1 to 3;
FIG. 12 shows a degradation comparison graph of photocatalytic degradation of sulfonamides by the bismuth-based photocatalytic material prepared in example 1 and comparative example 1;
FIG. 13 shows a degradation comparison graph of photocatalytic degradation of sulfonamides by the bismuth-based photocatalytic material prepared in example 9 and comparative example 2;
FIG. 14 shows a degradation comparison graph of photocatalytic degradation of sulfonamides by the bismuth-based photocatalytic material prepared in example 17 and comparative example 3;
FIG. 15 shows the photocatalytic H production by the bismuth-based photocatalytic material produced in example 1 and comparative example 1 2 O 2 Yield vs.
Detailed Description
The present invention will be described in detail with reference to specific examples for further understanding of technical features of the present invention. The examples are given solely for the purpose of illustration and are not intended to be limiting, as any insubstantial modifications made by a person skilled in the art based on the description herein shall fall within the scope of the invention.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The reactants bismuth (III) nitrate pentahydrate, sodium chloride, potassium bromide, potassium iodide, absolute ethanol, powdered honey locust, methanol, formic acid, hydrogen peroxide used in the examples below were all commercially available analytical grade, and deionized water was self-made.
The following examples were SEM tested using SU-8000 scanning electron microscope from Hitachi, japan, with an acceleration voltage of 100kV;
the following examples were TEM tested using an HT7700 transmission electron microscope from Hitachi, japan, with an acceleration voltage of 100kV;
the following examples employ an IR spectrometer of the Bruker VERTEX 700 type, germany, for analysis of the functional group structure, scanning wavenumbers in the range 4000-500cm -1 ；
The following test examples were subjected to photocatalytic tests in a multi-position photochemical reactor under irradiation of 300w xenon lamp simulated sunlight (lambda. Gtoreq.420 nm). The concentration of sulfonamide was determined using a high performance liquid chromatography system of Japanese LC-20AT using a tunable ultraviolet absorption detector and a Roc-C18 column (150 mm. Times.4.6 mm,5 μm) AT 275 nm.
Example 1
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weigh 2mmol Bi (NO) 3 ) 3 ·5H 2 O powder (0.97 g), 2mmolNaCl powder (0.117g) Dissolving in 10mL of absolute ethyl alcohol, adding 70mL of deionized water to obtain bismuth-based precursor solution, adding the gleditsia sinensis powder with the mass ratio of the bismuth-based precursor salt to the bismuth-based precursor solution being 0.1:1, and then vigorously stirring for 30min. The solution was transferred to a 150mL autoclave lined with polytetrafluoroethylene and heated at 160℃for 18h before cooling. After centrifugation with ethanol and deionized water three times at room temperature, drying in vacuum at 70℃for 8h to obtain SA-BiOCl.
As can be seen from FIG. 1, SA-BiOCl prepared in this example has a flower-sphere structure with a diameter of 300-500 nm.
As can be seen from FIG. 2, SA-BiOCl prepared in this example is a structure formed by stacking nanosheets having a diameter of 80-100 nm.
Example 2
A bismuth-based photocatalytic material was produced by the same method as in example 1 except that the temperature of the hydrothermal reaction was adjusted to 180 ℃.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 3
A bismuth-based photocatalytic material was produced by the same method as in example 1 except that the temperature of the hydrothermal reaction was adjusted to 200 ℃.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 4
A bismuth-based photocatalytic material was produced by the same method as in example 1 except that the time of the hydrothermal reaction was adjusted to 16 hours.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 5
A bismuth-based photocatalytic material was produced by the same method as in example 1 except that the time of the hydrothermal reaction was adjusted to 24 hours.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 6
The preparation method of the bismuth-based photocatalytic material is the same as in example 1, except that the mass ratio of the bismuth-based precursor salt to the fructus Gleditsiae Abnormalis powder is adjusted to 1:0.05.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 7
The preparation method of the bismuth-based photocatalytic material is the same as in example 1, except that the mass ratio of the bismuth-based precursor salt to the fructus Gleditsiae Abnormalis powder is adjusted to 1:0.2.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 8
The preparation method of the bismuth-based photocatalytic material is the same as in example 1, except that the mass ratio of the bismuth-based precursor salt to the fructus Gleditsiae Abnormalis powder is adjusted to 1:0.5.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 9
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weigh 2mmol Bi (NO) 3 ) 3 ·5H 2 O powder (0.97 g), 2 mmole KBr powder (0.238 g) were dissolved in 10mL of absolute ethanol, 70mL of deionized water was added to obtain a bismuth-based precursor solution, and the mixture was vigorously stirred for 30 minutes after adding the powder of Gleditsia sinensis having a mass ratio of 0.1:1 with respect to the bismuth-based precursor salt. The solution was transferred to a 150mL autoclave lined with polytetrafluoroethylene and heated at 160℃for 18h before cooling. After centrifugation with ethanol and deionized water three times at room temperature, drying in vacuum at 70℃for 8 hours to obtain SA-BiOBr.
As can be seen from FIG. 3, the SA-BiOBr prepared in this example has a flower-ball structure with a diameter of 800-1000 nm.
As can be seen from FIG. 4, SA-BiOBr prepared in this example is a structure formed by stacking nanosheets having a diameter of 80-100 nm.
Example 10
A bismuth-based photocatalytic material was produced by the same method as in example 9 except that the temperature of the hydrothermal reaction was adjusted to 180 ℃.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 11
A bismuth-based photocatalytic material was produced by the same method as in example 9 except that the temperature of the hydrothermal reaction was adjusted to 200 ℃.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 12
A bismuth-based photocatalytic material was produced by the same method as in example 9 except that the time of the hydrothermal reaction was adjusted to 16 hours.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 13
A bismuth-based photocatalytic material was produced by the same method as in example 9 except that the time of the hydrothermal reaction was adjusted to 24 hours.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 14
The preparation method of the bismuth-based photocatalytic material is the same as in example 9, except that the mass ratio of the bismuth-based precursor salt to the powdered soap is adjusted to 1:0.05.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 15
The preparation method of the bismuth-based photocatalytic material is the same as in example 9, except that the mass ratio of the bismuth-based precursor salt to the powdered soap is adjusted to 1:0.2.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 16
The preparation method of the bismuth-based photocatalytic material is the same as in example 9, except that the mass ratio of the bismuth-based precursor salt to the powdered soap is adjusted to 1:0.5.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 17
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weigh 2mmol Bi (NO) 3 ) 3 ·5H 2 O powder (0.97 g), 2mmol KI powder (0.332 g) are dissolved in 10mL absolute ethanol, 70mL deionized water is added to obtain bismuth-based precursor solution, and the mixture is vigorously stirred for 30min after the soap powder with the mass ratio of 0.05:1 with respect to the bismuth-based precursor salt is added. The solution was transferred to a 150mL autoclave lined with polytetrafluoroethylene and heated at 160℃for 18h before cooling. After centrifugation with ethanol and deionized water three times at room temperature, drying in vacuum at 70 ℃ for 8 hours to obtain SA-BiOI.
As can be seen from FIG. 5, the SA-BiOI prepared in this example has a flower-sphere structure with a diameter of 1.5-2. Mu.m.
As can be seen from FIG. 6, the SA-BiOI prepared in this example is a structure formed by stacking nanosheets having a diameter of 150-200 nm.
Example 18
A bismuth-based photocatalytic material was produced by the same method as in example 17 except that the temperature of the hydrothermal reaction was adjusted to 180 ℃.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 19
A bismuth-based photocatalytic material was produced by the same method as in example 17 except that the temperature of the hydrothermal reaction was adjusted to 200 ℃.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 20
A bismuth-based photocatalytic material was produced by the same method as in example 17 except that the time of the hydrothermal reaction was adjusted to 16 hours.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 21
A bismuth-based photocatalytic material was produced by the same method as in example 17 except that the time of the hydrothermal reaction was adjusted to 24 hours.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 22
The preparation method of the bismuth-based photocatalytic material is the same as in example 17, except that the mass ratio of the bismuth-based precursor salt to the powdered soap is adjusted to 1:0.1.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 23
The preparation method of the bismuth-based photocatalytic material is the same as in example 17, except that the mass ratio of the bismuth-based precursor salt to the powdered soap is adjusted to 1:0.2.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Example 24
The preparation method of the bismuth-based photocatalytic material is the same as in example 17, except that the mass ratio of the bismuth-based precursor salt to the powdered soap is adjusted to 1:0.5.
The bismuth-based photocatalytic material prepared by the method is of a flower-ball structure formed by stacking nano sheets.
Comparative example 1
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weigh 2mmol Bi (NO) 3 ) 3 ·5H 2 O powder (0.97 g) and 2 mmole of NaCl powder (0.117 g) were dissolved in 10mL of absolute ethanol, 70mL of deionized water was added, and after stirring for 30min, the mixed solution was transferred to a 150mL polytetrafluoroethylene-lined autoclave, heated at 160℃for 18 hours, and then cooled. Washing and centrifuging with ethanol and deionized water at room temperature for three times, and vacuum drying at 70 ℃ for 6 hours to obtain nano-sheet BiOCl.
Comparative example 2
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weigh 2mmol Bi (NO) 3 ) 3 ·5H 2 O powder (0.97 g) and 2 mmole KBr powder (0.238 g) were dissolved in 10mL of absolute ethanol, 70mL of deionized water was added, and after stirring for 30min, the mixed solution was transferred to a 150mL polytetrafluoroethylene-lined autoclave, heated at 160℃for 18 hours, and then cooled. In the roomAnd (3) washing and centrifuging with ethanol and deionized water at the temperature for three times, and drying in vacuum at 70 ℃ for 6 hours to obtain the nano-sheet BiOBr.
Comparative example 3
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weigh 2mmol Bi (NO) 3 ) 3 ·5H 2 O powder (0.97 g) and 2mmol KI powder (0.332 g) were dissolved in 10mL absolute ethanol, 70mL deionized water was added, and after stirring for 30min, the mixed solution was transferred to a 150mL polytetrafluoroethylene-lined autoclave, heated at 160℃for 18h, and then cooled. Washing and centrifuging with ethanol and deionized water at room temperature for three times, and vacuum drying at 70 ℃ for 6 hours to obtain the nano-sheet BiOI.
Some test analyses
(one) the infrared spectrograms of the photocatalytic material SA-BiOCl prepared in comparative example 1 and the photocatalytic material BiOCl prepared in comparative example 1 and pure Chinese honeylocust fruit powder (shown in FIG. 7).
The infrared spectrograms of the photocatalytic material SA-BiOBr prepared in comparative example 9 and the photocatalytic material BiOBr prepared in comparative example 2 (shown in FIG. 8).
Infrared spectrograms of the photocatalytic material SA-BiOI obtained in comparative example 17 and the photocatalytic material BiOI obtained in comparative example 3 (as shown in FIG. 9)
As can be seen from FIG. 7, at 3550-3416cm -1 The peak at this point may be the-OH stretching frequency due to intramolecular hydrogen bonding, or may be the N-H stretching vibration peak, where the primary amine is two bands, and the secondary amine is one band of imine. At 1616cm -1 The deformation vibration peak of N-H is shown, and SA-BiOCl is 2922cm -1 And 1384cm -1 The peak at the site was significantly stronger than that of BiOCl, indicating more NH 3+ The groups attach to the SA-BiOCl surface due to the alkaline substances in the powder of the soap. At 1056cm -1 Is the cyclic vibration peak caused by C-H deformation in nitrogen-containing heteroaromatic ring. At 527cm -1 The peak at the peak is Bi-O stretching vibration peak, confirming the existence of Bi-O bond in SA-BiOCl and BiOCl materials. The groups and hydroxyl groups of the nitrogen-containing compound belong to hydrophilic free radicals, and exist on the surface of the SA-BiOCl materialMore hydrophilic free radicals, indicating that the surface free energy of SA-BiOCl is smaller and the hydrophilicity is stronger.
As can be seen by comparing FIG. 7, FIG. 8 and FIG. 9, the infrared spectra of SA-BiOBr and SA-BiOI are similarly changed, and the surfaces of the SA-BiOBr and SA-BiOI are hydrophilic-OH and-NH 2 The amount increases, thereby decreasing the surface free energy of the catalytic material.
(II) fluorescence spectra of the photocatalytic material SA-BiOCl obtained in comparative example 1 and the photocatalytic material BiOCl obtained in comparative example 1 (see FIG. 10).
As can be seen from FIG. 10, the fluorescence signal of SA-BiOCl is significantly reduced compared with that of BiOCl, which indicates that the hole-electron recombination rate of SA-BiOCl surface is reduced, i.e. the preparation method of example 1 can significantly improve the photocatalytic activity of the bismuth-based catalytic material.
(III) XRD patterns of the photocatalytic material SA-BiOCl obtained in comparative example 1, the photocatalytic material SA-BiOBr obtained in example 9, the photocatalytic material SA-BiOI obtained in example 17, the photocatalytic material BiOCl obtained in comparative example 1, the photocatalytic material BiOBr obtained in comparative example 2, and the photocatalytic material BiOI obtained in comparative example 3 (as shown in FIG. 11).
As can be seen from fig. 11, the positions of the characteristic peaks of SA-BiOCl, SA-BiOBr, and SA-BiOI were not changed relative to the bulk photocatalytic material prepared in the comparative example, which indicates that the crystal structure of the material after induction of the honey locust powder was not changed, i.e., the preparation methods of example 1, example 9, and example 17 did not change the crystal structure of the bismuth-based catalytic material.
Test example 1: the bismuth-based catalytic material is used for photocatalytic degradation of sulfanilamide.
Experimental group: 1) 25mg of SA-BiOCl prepared in example 1 is added into 50mL of 5ppm sulfanilamide aqueous solution, ultrasonic treatment is carried out for 0.5h, the temperature is set to 25 ℃, and stirring is carried out for 0.5h, so that the solution is a uniform mixed solution, and the adsorption equilibrium is achieved;
2) And (3) taking the concentration of the mixed solution as the initial concentration, carrying out photodegradation on the mixed solution by utilizing visible light with the wavelength lambda of more than or equal to 420nm for 2 hours, taking a sample every 0.3 hour, sampling about 1.5ml, centrifuging the sample at the rotating speed of 3000 rpm for 15 minutes, taking the supernatant after centrifugation, and placing the supernatant into a brown liquid-phase vial which is stored in a refrigerator at the temperature of 4 ℃ for standby. All samples were tested by high performance liquid chromatography, mobile phase: methanol/0.1% formic acid aqueous solution=60/40 (V/V); the flow rate is 1.0mL/min; column temperature 40 ℃; the sample injection amount is 10 mu L; an ultraviolet detector detects 270nm wavelength. When the photodegradation time was 120min, the degradation rate reached 51.1% (as shown in FIG. 12).
Control group: the procedure was identical to that of the experimental group except that SA-BiOCl was replaced with BiOCl prepared in comparative example 1, and as a result, the degradation rate was 4.0% when the photodegradation time was 120min (as shown in FIG. 12).
Test example 2: the bismuth-based catalytic material is used for photocatalytic degradation of sulfanilamide.
Experimental group: 1) 25mg of SA-BiOBr prepared in example 9 is added into 50mL of 5ppm sulfanilamide aqueous solution, ultrasonic treatment is carried out for 0.5h, the temperature is set to 25 ℃, and stirring is carried out for 0.5h, so that the solution is a uniform mixed solution, and the adsorption equilibrium is achieved;
2) And (3) taking the concentration of the mixed solution as the initial concentration, carrying out photodegradation on the mixed solution by utilizing visible light with the wavelength lambda of more than or equal to 420nm for 2 hours, taking a sample every 0.3 hour, sampling about 1.5ml, centrifuging the sample at the rotating speed of 3000 rpm for 15 minutes, taking the supernatant after centrifugation, and placing the supernatant into a brown liquid-phase vial which is stored in a refrigerator at the temperature of 4 ℃ for standby. All samples were tested by high performance liquid chromatography, mobile phase: methanol/0.1% formic acid aqueous solution=60/40 (V/V); the flow rate is 1.0mL/min; column temperature 40 ℃; the sample injection amount is 10 mu L; an ultraviolet detector detects 270nm wavelength. When the photodegradation time was 120min, the degradation rate reached 61.9% (as shown in FIG. 13).
Control group: the procedure was identical to that of the experimental group except that SA-BiOBr was changed to BiOBr prepared in comparative example 2, and as a result, the degradation rate was 52.1% when the photodegradation time was 120min (as shown in FIG. 13).
Test example 3: the bismuth-based catalytic material is used for photocatalytic degradation of sulfanilamide.
Experimental group: 1) Adding 25mg of SA-BiOI prepared in example 17 into 50mL of 5ppm sulfanilamide aqueous solution, performing ultrasonic treatment for 0.5h, setting the temperature to 25 ℃, and stirring for 0.5h to form a uniform mixed solution so as to reach adsorption balance;
2) And (3) taking the concentration of the mixed solution as the initial concentration, carrying out photodegradation on the mixed solution by utilizing visible light with the wavelength lambda of more than or equal to 420nm for 2 hours, taking a sample every 0.3 hour, sampling about 1.5ml, centrifuging the sample at the rotating speed of 3000 rpm for 15 minutes, taking the supernatant after centrifugation, and placing the supernatant into a brown liquid-phase vial which is stored in a refrigerator at the temperature of 4 ℃ for standby. All samples were tested by high performance liquid chromatography, mobile phase: methanol/0.1% formic acid aqueous solution=60/40 (V/V); the flow rate is 1.0mL/min; column temperature 40 ℃; the sample injection amount is 10 mu L; an ultraviolet detector detects 270nm wavelength. When the photodegradation time was 120min, the degradation rate reached 12.1% (as shown in FIG. 14).
Control group: the procedure was identical to that of the experimental group except that SA-BiOI was changed to BiOI prepared in comparative example 3, and as a result, the degradation rate was 7.1% when the photodegradation time was 120min (as shown in FIG. 14).
Test example 4: bismuth-based catalytic material for producing H by photocatalysis 2 O 2
Experimental group: 1) 50mg of SA-BiOCl prepared in example 1 was added to 50mL of deionized water solution, followed by sonication for 0.5h at 25℃and stirring for 0.5h to give a homogeneous mixture of O 2 Adsorption balance;
2) Taking the concentration of the mixed solution as the initial concentration, then carrying out illumination on the mixed solution for 1.5 hours by utilizing visible light with the wavelength lambda being more than or equal to 420nm, taking a sample every 0.5 hour, sampling about 2mL, centrifuging the sample at the speed of 3000 rpm for 15 minutes, taking the supernatant after centrifugation, and storing in a refrigerator at the temperature of 4 ℃ for later use. All samples taken were developed by iodometry, absorbance was measured at a wavelength of 350nm using an ultraviolet spectrophotometer, and yield was calculated against the reticle, wherein the yield was 100.3. Mu. Mol/L when the illumination time was 60min (as shown in FIG. 15).
Control group: the procedure was as in the experimental group except that SA-BiOCl was changed to BiOCl obtained in comparative example 1, and as a result, the yield was 15.0. Mu. Mol/L when the light irradiation time was 60 minutes (as shown in FIG. 15).
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (17)
1. A method for inducing self-assembly of bismuth-based photocatalytic material by using biosurfactant, which is characterized by comprising the following steps:
dispersing the Chinese honeylocust fruit powder in bismuth-based precursor solution by ultrasonic, and carrying out hydrothermal reaction after fully stirring;
the solute of the bismuth-based precursor solution is A salt and bismuth salt; the A salt comprises one of halogen salt, tungstate, molybdate and metavanadate.
2. The method according to claim 1, wherein the mass ratio of total mass of the a salt and the bismuth salt to the powder of gleditsia sinensis is 1:0.05-0.5.
3. The method of claim 1, wherein the molar ratio of a salt to bismuth salt is 1:1-2.
4. The method of claim 1, wherein the solvent of the bismuth-based precursor solution is water and an alcohol.
5. The method of claim 4, wherein the alcohol is ethanol or ethylene glycol.
6. The method of claim 4, wherein the volume ratio of alcohol to water is 1:5-10.
7. The method of claim 1, wherein the halide salt is one of sodium chloride, potassium bromide, potassium iodide;
the bismuth salt is bismuth nitrate pentahydrate; the tungstate is sodium tungstate;
the molybdate is sodium molybdate;
the metavanadate is ammonium metavanadate.
8. The method of claim 1, wherein the stirring is for a period of 0.5 to 1 hour.
9. The method according to claim 1, wherein the hydrothermal reaction is carried out at 160-200 ℃ for 16-24 hours.
10. The method of claim 1, further comprising washing and drying after the hydrothermal reaction.
11. The method of claim 10, wherein the drying is drying under vacuum.
12. The method according to claim 11, wherein the drying is performed in a vacuum environment at a temperature of 70-105 ℃ for 6-8 hours.
13. The method according to claim 1, wherein the honey locust powder is nano-sized and/or micro-sized honey locust powder.
14. A bismuth-based photocatalytic material produced by the method of any one of claims 1-13.
15. A bismuth-based photocatalytic material as set forth in claim 14 for producing H in photocatalysis 2 O 2 Or in the photocatalytic degradation of antibiotics.
16. The use according to claim 15, wherein the antibiotic comprises one or more of sulfanilamide, diclofenac sodium, tetracycline, acyclovir.
17. The use according to claim 15, wherein the bismuth-based photocatalytic material is used for photocatalytic H production 2 O 2 The application comprises the following steps:
ultrasonically dispersing the bismuth-based photocatalytic material into deionized water for illumination;
the light source of illumination is visible light with the wavelength of more than or equal to 420 nm;
the bismuth-based photocatalytic material is used for photocatalytic degradation of antibiotics, and the application comprises the following steps:
dispersing the bismuth-based photocatalytic material into an aqueous solution of an antibiotic, and performing illumination;
the light source of illumination is visible light with the wavelength of more than or equal to 420 nm.
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