CN111774075A - BiOI/MoS2Heterojunction composite photocatalyst and preparation method and application thereof - Google Patents
BiOI/MoS2Heterojunction composite photocatalyst and preparation method and application thereof Download PDFInfo
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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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- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
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- A61L2/08—Radiation
- A61L2/088—Radiation using a photocatalyst or photosensitiser
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention belongs to the field of photocatalysis, and particularly relates to a BiOI/MoS2A heterojunction composite photocatalyst and a preparation method and application thereof. BiOI/MoS2Heterojunction composite photocatalyst composed of MoS2And BiOI, wherein the BiOI and MoS2The mass ratio of (A) to (B) is 0.02: 1-0.1: 1. BiOI/MoS2The heterojunction composite photocatalyst is obtained by two-step operation, and flower-shaped MoS is prepared by hydrothermal synthesis method2Then dispersed and stripped under ultrasonic condition, and Bi (NO) is added3)3·5H2O and KI, and finally obtaining the BiOI/MoS under the hydrothermal condition2A heterojunction composite photocatalyst. The invention constructs the visible light responseBiOI/MoS of2The heterojunction accelerates the separation of photon-generated carriers, has high-efficiency photocatalytic activity and stability under visible light, has high-efficiency killing and degrading effects on harmful microorganisms and dye pollutants in water, and has good practical value and potential application prospect in the fields of water purification, marine antifouling and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a BiOI/MoS2A heterojunction composite photocatalyst and a preparation method and application thereof.
Background
As is well known, global environmental pollution is becoming more serious, and water pollution has become a major problem to human beings. In the ocean, biofouling issues have also limited human exploration of the ocean. To overcome this problem, scientists have conducted a great deal of research. The semiconductor material provides a new method for solving the problems. Semiconductor materials are widely used in human society, and their use in various fields is also being explored. Since the discovery of TiO by Fujishima et al2Since the photocatalytic performance, more and more photocatalyst materials are developed and applied[1,2]. Among them, bismuth oxyiodide (BiOI) is a promising photocatalytic material due to its narrow band gap width (1.7-1.9eV) and two-dimensional layered structure of graphene-like[3]. In addition, the BiOI has the advantages of being inexpensive and easy to manufacture, but the BiOI also has some disadvantages to overcome, such as a strong recombination capability of electrons and holes in the BiOI due to a too small band gap. Furthermore, the conduction band position of the BiOI is more positive than the reduction potential of hydrogen, which prevents the generation of active groups. These factors have all hindered the further development of the BiOI material.
Therefore, in order to improve these defects and thereby enhance the photocatalytic activity of the BiOI, it is necessary to appropriately modify the BiOI.
[1]A.Fujishima,K.Honda.Electrochemical photolysis of water at asemiconductor electrode.Nature,1972,238,37-38.
[2]S.N.Frank,A.J.Bard.Heterogeneous photocatalytic oxidation ofcyanide and sulfite in aqueous solutions at semiconductorpowders.J.Phys.Chem.,1977,81,1484-1488.
[3]J.Su,X.X.Zou,G.D.Li,X.Wei,C.Yan,Y.N.Wang,J.Zhao,L.J.Zhou,J.S.Chen.Macroporous V2O5-BiVO4composites:effect of heterojunction on thebehavior of photogenerated charges.J.Phys.Chem.C,2011,115,8064-8071。
Disclosure of Invention
The invention aims to provide a BiOI/MoS aiming at the problems in the prior art2The heterojunction composite photocatalyst, the preparation method and the application thereof make up for the defects of the prior art.
The BiOI/MoS provided by the invention2A composite photocatalyst is prepared from bismuth oxyiodide (BiOI) and molybdenum disulfide (MoS)2) Composition of BiOI and MoS2The mass ratio of (A) to (B) is 0.02: 1-0.1: 1.
Provided BiOI/MoS2The preparation method of the heterojunction composite photocatalyst comprises the following steps:
1)MoS2the preparation of (1):
ammonium molybdate ((NH) is added into ultrapure water in turn4)6Mo7O24·5H2O) and thioacetamide (CH)4N2S), magnetically stirring until the solution is completely dissolved, transferring the dissolved solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and putting the high-pressure reaction kettle into an electric heating constant-temperature air blast drying oven for heat treatment at 200-240 ℃ for 12-20 hours; then cooling the reaction kettle to room temperature, and obtaining the MoS with the flower-like structure through suction filtration, washing and drying at 60 DEG C2;
2)BiOI/MoS2Preparing a heterojunction composite photocatalyst:
the MoS obtained in the step 1) is treated2Adding into ethylene glycolIn the above-mentioned reaction solution, polyvinylpyrrolidone (PVP) and bismuth nitrate (Bi (NO) are added3)3·5H2O), ultrasonic dispersion to obtain a dispersion liquid A; adding potassium iodide (KI) into ultrapure water to be completely dissolved to obtain a suspension B; dropwise adding the dispersion liquid B into the suspension liquid A under magnetic stirring, continuously carrying out magnetic stirring for 30-90 min, transferring the mixed liquid into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and putting the high-pressure reaction kettle into an electric heating constant-temperature air-blast drying oven for heat treatment at 140-200 ℃ for 24-48 h; after the reaction is finished, cooling the reaction kettle to room temperature, and obtaining the BiOI/MoS after suction filtration, washing and drying for 6h at 60 DEG C2A heterojunction composite photocatalyst.
(NH) in said step 1)4)6Mo7O24·5H2O and CH4N2The molar ratio of S is 1: 20-30;
the ultrasonic dispersion time in the step 2) is 4-8 h;
bi (NO) in the step 2)3)3·5H2The ratio of the amount of O to the amount of KI material was 3: 1.
In another aspect, the invention also provides BiOI/MoS2The application of the heterojunction composite photocatalyst in degrading dyes;
the dye is rhodamine B (RhB);
in another aspect, the invention also provides BiOI/MoS2The application of the heterojunction composite photocatalyst in killing harmful microorganisms.
The harmful microorganism is pseudomonas aeruginosa (P.
The invention has the beneficial effects that:
the invention is realized by combining BiOI and MoS2Compounding, constructing a composite material with a heterostructure, accelerating the separation of photon-generated carriers on the surface of the composite material, further improving the photocatalytic performance, and carrying out the treatment on the BiOI and the MoS2The practical application of the two materials in the field of photocatalysis is of great significance.
(1) The invention adopts the simple hydrothermal synthesis method to prepare the BiOI/MoS2The heterojunction composite photocatalyst can effectively degrade RhB and inactivate P.aeruginosa;
(2) BiOI/MoS prepared by the invention2The heterojunction composite photocatalyst has good visible light absorption performance and photocatalytic performance, and the photocatalytic activity is compared with that of BiOI and MoS2Are all obviously improved;
(3) MoS prepared by the invention2/Bi2WO6The heterojunction composite photocatalyst has good stability and reusability;
(4) BiOI/MoS prepared by the invention2The heterojunction composite photocatalyst has a type II heterostructure, accelerates the separation of photon-generated carriers, improves the visible light catalytic activity, and has good practical value and potential application prospect in the fields of water purification, marine antifouling and the like.
Drawings
FIG. 1 is an XRD pattern of a sample prepared according to the present invention, wherein the abscissa is 2 θ (angle) and the unit is degree; intensity on the ordinate, in a.u. (absolute units);
FIG. 2 is a Field Emission Scanning Electron Microscope (FESEM) photograph of a sample prepared according to the present invention: (A) MoS2,(B)BiOI,(C,D)BiOI/MoS2;
FIG. 3 is a graph of the ultraviolet-visible diffuse reflectance spectrum (UV-DRS) of a sample prepared according to the present invention, wherein the abscissa is the Wavelength (Wavelength) in nm (nanometers) and the ordinate is the Absorbance (Absorbance) in a.u (absolute units);
FIG. 4 shows the variation of RhB concentration with Time (A) and the variation of bacterial survival with Time (B) in the photocatalytic degradation reaction of Pseudomonas aeruginosa in the sample prepared by the present invention, wherein the abscissa of the graph A is Time in min and the ordinate is Ct/C0,C0Initial concentration of RhB before reaction initiation, CtThe RhB concentration at reaction time t; on the graph B, the ordinate represents the survivability ratio in%.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to provide a more complete understanding of the invention by one of ordinary skill in the art, and are not intended to be limiting in any way.
Example 1 BiOI/MoS2Preparation of heterojunction composite photocatalyst
(1)MoS2The preparation of (1): to 80mL of ultrapure water was added 1mmol (NH)4)6Mo7O24·5H2O and 20mmol CH4N2S, stirring for dissolving, transferring to a 100mL polytetrafluoroethylene reaction kettle, reacting for 20h at 200 ℃, cooling to room temperature, filtering and collecting precipitate, washing with deionized water and ethanol for several times, and drying at 60 ℃ under normal pressure to obtain MoS2And (3) sampling.
(2)BiOI/MoS2Preparing a heterojunction composite photocatalyst: 0.16g of MoS2,0.1mmol Bi(NO3)3·5H2Dissolving O and 1g PVP in 30mL of ethylene glycol, and carrying out ultrasonic treatment for 6h to form a solution A; 0.3mmol of KI was dissolved in 10mL of ultrapure water to form a solution B. Dropwise adding the solution B into the solution A while stirring, continuously stirring for 30min after dropwise adding is finished, transferring the solution into a 50mL polytetrafluoroethylene reaction kettle, reacting for 48h at 180 ℃, cooling to room temperature, filtering, collecting precipitate, washing with deionized water and ethanol, drying at 60 ℃ under normal pressure to obtain the BiOI/MoS2A composite material.
Comparative example 1 preparation of monomeric BiOI
0.1mmol Bi(NO3)3·5H2Dissolving O in 30mL of ethylene glycol, performing ultrasonic treatment for 30min, adding 0.3mmol of KI under continuous stirring, continuing stirring for 30min, transferring to a 50mL polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 48h, cooling to room temperature, filtering, collecting precipitate, washing with deionized water and ethanol, and drying at 60 ℃ under normal pressure to obtain a BiOI monomer material, namely BiOI (see figure 1).
Fig. 1 is an XRD pattern of the samples prepared in example 1 and comparative example 1. As can be seen from FIG. 1, all diffraction peaks of pure BiOI can be matched to tetragonal phase BiOI (JCPDS card number 10-0445), indicating high purity and good crystallization. For pure MoS2Three major diffraction peaks were observed at 13.98 °,33.62 ° and 59.08 ° 2 θ, which are MoS2Characteristic peaks of (002), (100) and (110) planes of hexagonal phase (JCPDS card number 37-1492). BiOI/MoS2The pattern of the composite material comprises tetragonal phase BiOI and hexagonal phase MoS2All characteristic peaks of (a). Furthermore, the BiOI/MoS is comparable to pure BiOI2The peak position of the composite material was hardly shifted, indicating that MoS2Has little effect on the lattice structure of the BiOI.
Fig. 2 is a scanning electron micrograph of the samples prepared in example 1 and comparative example 1. As can be seen from FIG. 2, MoS2Is a flower-shaped microsphere structure formed by randomly orienting and interleaving nano sheets with the size of about 200nm and the thickness of about 20nm, and the size of the flower-shaped microsphere structure is about 1 mu m. The BiOI is a plurality of nanosheets having a size of about 0.5 μm. BiOI/MoS2The composite material showed a layered flower-like microspherical structure of about 2 μm. No fragments were seen around or on the surface of the flower-like microspheres, indicating nucleation of BiOI, followed by MoS2Growth on nanoplates resulting in MoS2The nanosheets participate in the growth of the BiOI. Subsequently, under the influence of ostwald ripening and anisotropic growth, the bio i nuclei tend to grow into two-dimensional nanoplatelets. After dissolution and recrystallization, the BiOI nano-sheets pass through MoS2The nano sheets are gradually self-assembled in an edge-to-edge mode in the directional attachment process, and finally a three-dimensional layered flower-shaped microsphere structure is formed.
Fig. 3 is a graph showing the uv-vis diffuse reflectance spectrums of the samples prepared in example 1 and comparative example 1. As shown in FIG. 3, pure MoS2The BiOI shows strong light absorption from ultraviolet light to the visible region, while the BiOI shows good light absorption in the visible region around 450 nm. BiOI/MoS, on the other hand, in comparison with pure BiOI2The composite material has wider light absorption range and stronger visible light responsiveness, which can be attributed to the wide bandgap semiconductor MoS2The formation of a heterostructure of (a). Indicating BiOI/MoS2The heterostructure composite material shows good light absorption performance to visible light, so that the heterostructure composite material has possible application in photocatalysis.
Example 2 BiOI/MoS2Preparation of heterojunction composite photocatalyst
1) Different from embodiment 1Characterized by controlling (NH)4)6Mo7O24·5H2O and CH4N2The molar ratio of S is 1: 30. To 80mL of ultrapure water was added 1mmol (NH)4)6Mo7O24·5H2O and 30mmol CH4N2S, stirring for dissolving, transferring to a 100mL polytetrafluoroethylene reaction kettle, reacting for 20h at 200 ℃, cooling to room temperature, filtering and collecting precipitate, washing with deionized water and ethanol for several times, and drying at 60 ℃ under normal pressure to obtain MoS2And (3) sampling.
2) Then 0.16g MoS was added2,0.1mmol Bi(NO3)3·5H2Dissolving O and 1g PVP in 30mL of ethylene glycol, and carrying out ultrasonic treatment for 6h to form a solution A; 0.3mmol KI was dissolved in 10mL ultrapure water and dispersed ultrasonically for 6h to form solution B. Dropwise adding the solution B into the solution A while stirring, continuously stirring for 30min, transferring into a 50mL polytetrafluoroethylene reaction kettle, reacting for 48h at 180 ℃, cooling to room temperature, filtering, collecting precipitate, washing with deionized water and ethanol, drying at 60 ℃ under normal pressure to obtain the BiOI/MoS2A composite material.
Example 3 BiOI/MoS2Preparation of heterojunction composite photocatalyst
The difference from the embodiment 1 is that MoS is controlled2The ultrasonic time is 4 h. To 80mL of ultrapure water was added 1mmol (NH)4)6Mo7O24·5H2O and 20mmol CH4N2S, stirring for dissolving, transferring to a 100mL polytetrafluoroethylene reaction kettle, reacting for 20h at 200 ℃, cooling to room temperature, filtering, collecting precipitate, washing with deionized water and ethanol, drying at 60 ℃ under normal pressure to obtain MoS2And (3) sampling. Then 0.16g MoS was added2,0.1mmol Bi(NO3)3·5H2Dissolving O and 1g PVP in 30mL of ethylene glycol, and carrying out ultrasonic treatment for 4h to form a solution A; 0.3mmol was dissolved in 10mL of ethanol to form solution B. Dropwise adding the solution B into the solution A while stirring, stirring for 30min, transferring into a 50mL polytetrafluoroethylene reaction kettle, reacting at 180 deg.C for 48h, cooling to room temperature, and collecting the solutionFiltering and collecting the precipitate, washing with deionized water and ethanol, and drying at 60 ℃ under normal pressure to obtain the BiOI/MoS2A composite material.
Example 4 BiOI/MoS2Application of heterojunction composite photocatalyst in visible light catalytic degradation of dye pollutant RhB
50mL of 10-5The RhB solution of M was charged into a 50mL reactor, and 50mg of the BiOI/MoS prepared in example 1 was added2The catalyst uses a 500W xenon lamp as a light source to simulate sunlight, and a 420nm filter is used for filtering ultraviolet light to ensure that light received by the reaction is visible light. Stirring for 30min in a dark state to enable the catalyst and the RhB to reach an adsorption/desorption equilibrium state, then turning on a light source, respectively sampling at certain time intervals in the reaction process under dark state and illumination conditions, centrifuging, taking supernatant, measuring the absorbance of the RhB solution at 552nm wavelength on an ultraviolet visible spectrophotometer, obtaining the residual concentration of the RhB, calculating the degradation rate, and taking a blank experiment and a dark state experiment as control experiments (see figure 4A).
As can be seen from FIG. 4A, RhB was hardly degraded in the blank and dark experiments, and the effect on the experiments was negligible. Under visible light, BiOI/MoS2The heterojunction composite photocatalyst shows good photocatalytic activity, and the photocatalytic performance is obviously superior to that of monomer BiOI and MoS2And the degradation rate of RhB in 60min of photocatalytic reaction time can reach 100%. Therefore, BiOI and MoS having good visible light absorption properties and photocatalytic activity2The composite material forms a II-type heterostructure, so that photoproduction electrons and holes can be effectively separated on the surface of the composite material, the visible light absorption performance and the specific surface area of the composite material are improved, and the visible light catalysis performance of the composite material is enhanced. BiOI/MoS prepared in example 2 and example 32The catalyst also achieves similar results as described above.
Example 5 BiOI/MoS2Visible light killing of heterojunction composite photocatalyst on pseudomonas aeruginosa
Using 500W xenon lamp as light source, and optical filter to filter out ultraviolet light to make its wavelength range be 420-760 nm, using P.aeruginosa (2.0 × 10)8cfu/mL) Evaluation of BiOI/MoS2The visible light catalytic sterilization performance of the heterojunction composite photocatalyst.
Firstly, preparing bacterial suspension, inoculating pseudomonas aeruginosa stock solution into a sterilized LB liquid culture medium, then placing the sterilized LB liquid culture medium into an air constant temperature shaking table with the temperature of 37 ℃ and the rpm of 150, carrying out overnight culture, centrifuging the bacterial suspension obtained by culture, and suspending the bacterial suspension in 0.01mol/L PBS (pH 7.4) buffer solution to obtain the concentration of 2.0 × 10849.5mL of sterilized 0.01mol/L PBS (pH 7.4) buffer was added to a 50mL reactor in a photocatalytic experiment, and 500. mu.L of the bacterial suspension was added to give a bacterial concentration in the reaction solution of 2.0 × 106cfu/mL, 50mg of BiOI/MoS prepared in example 1 was added2A catalyst. Carrying out photocatalytic reaction after the dark state adsorption reaches the balance, sampling at certain time intervals in the reaction process, and determining the survival rate and the sterilization rate of bacteria by a flat plate counting method. The method comprises the following specific steps: after 1.0mL of the reaction mixture was serially diluted with 0.01mol/L PBS (pH 7.4) buffer by several gradients, 100. mu.L of the solution was added to the prepared LB solid medium and the mixture was applied to the LB medium. Inverting the LB culture medium, putting the culture medium into an electric heating constant temperature incubator to be cultured for 24h at 37 ℃, and obtaining the bacterial concentration by counting the number of colonies growing on the culture medium and corresponding dilution times so as to determine the survival rate and the sterilization rate of the bacteria. Each set of experiments was performed 3 times in parallel, and the average was taken as the final result, and the blank experiment and the dark state experiment were used as control experiments (see fig. 4B).
As can be seen from FIG. 4B, there was little change in the number of Pseudomonas aeruginosa in the blank experiment, indicating that the effect of visible light was negligible; in the dark condition, the number of bacteria has no obvious change, which shows that the material used in the experiment has no biological toxicity. And under visible light illumination, BiOI/MoS2The heterojunction composite photocatalyst shows good photocatalytic activity, and the photocatalytic sterilization performance is obviously superior to that of monomer BiOI and MoS2The sterilization rate can reach 99.99 percent after 60min of illumination. Thus, BiOI/MoS2The heterojunction composite photocatalyst has excellent photocatalytic sterilization antifouling performance, and can be classified asDue to BiOI and MoS2The composite material forms a heterostructure, accelerates the separation of photoproduction electrons and holes, and improves the photocatalytic activity of the composite material.
The experimental results show that the BiOI/MoS prepared in example 2 and example 32The catalyst also achieved the BiOI/MoS prepared in example 12The effect of the catalyst.
Claims (9)
1. BiOI/MoS2The heterojunction composite photocatalyst is characterized in that the BiOI/MoS2The heterojunction composite photocatalyst consists of bismuth oxyiodide BiOI and molybdenum disulfide MoS2Composition of BiOI and MoS2The mass ratio of (A) to (B) is 0.02: 1-0.1: 1.
2. The BiOI/MoS of claim 12The heterojunction composite photocatalyst is characterized in that the BiOI/MoS2The preparation method of the heterojunction composite photocatalyst comprises the following steps:
1)MoS2the preparation of (1):
sequentially adding ammonium molybdate NH into ultrapure water4)6Mo7O24·5H2O-Thioacetamide CH4N2S, transferring the dissolved solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and putting the high-pressure reaction kettle into an electric heating constant-temperature air blast drying oven for heat treatment at 200-240 ℃ for 12-20 h; then cooling the reaction kettle to room temperature, and obtaining the MoS with the flower-like structure through suction filtration, washing and drying2;
2)BiOI/MoS2Preparing a heterojunction composite photocatalyst:
the MoS obtained in the step 1) is treated2Adding into ethylene glycol, adding polyvinylpyrrolidone PVP and bismuth nitrate Bi (NO)3)3·5H2O, performing ultrasonic dispersion to obtain a dispersion liquid A; adding potassium iodide KI into ultrapure water to be completely dissolved to obtain a suspension B; dropwise adding the dispersion liquid B into the suspension liquid A, continuously stirring for 30-90 min, transferring the mixed liquid into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and putting the high-pressure reaction kettle into an electric heating constant-temperature blast drying oven for heat treatment at the temperature of 140-200 ℃ to 24 ℃48 h; after the reaction is finished, cooling the reaction kettle to room temperature, and performing suction filtration, washing and drying to obtain the BiOI/MoS2A heterojunction composite photocatalyst.
3. The BiOI/MoS of claim 22The heterojunction composite photocatalyst is characterized in that (NH) in the step 1)4)6Mo7O24·5H2O and CH4N2The molar ratio of S is 1: 20-30.
4. The BiOI/MoS of claim 22The heterojunction composite photocatalyst is characterized in that the ultrasonic dispersion time in the step 2) is 4-8 hours.
5. The BiOI/MoS of claim 22The heterojunction composite photocatalyst is characterized in that Bi (NO) in the step 2)3)3·5H2The ratio of the amount of O to the amount of KI material was 3: 1.
6. The BiOI/MoS of any one of claims 1 to 52Application of the heterojunction composite photocatalyst in degradation of dye.
7. The use of claim 6, wherein the dye is rhodamine B (RhB).
8. The BiOI/MoS of any one of claims 1 to 52The application of the heterojunction composite photocatalyst in killing harmful microorganisms.
9. The use of claim 8, wherein said harmful microorganism is pseudomonas aeruginosa (p.
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