CN115739125A - Cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst and preparation method and application thereof - Google Patents
Cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst and preparation method and application thereof Download PDFInfo
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- WRSVIZQEENMKOC-UHFFFAOYSA-N [B].[Co].[Co].[Co] Chemical compound [B].[Co].[Co].[Co] WRSVIZQEENMKOC-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 98
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011593 sulfur Substances 0.000 claims abstract description 78
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 78
- 239000002105 nanoparticle Substances 0.000 claims abstract description 50
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- 230000002950 deficient Effects 0.000 claims abstract description 42
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- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 5
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- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 8
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- 239000012279 sodium borohydride Substances 0.000 claims description 7
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 30
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- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 5
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- 239000000047 product Substances 0.000 description 19
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- 239000000126 substance Substances 0.000 description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
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- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
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- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 2
- 229940039790 sodium oxalate Drugs 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
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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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- 239000005083 Zinc sulfide Substances 0.000 description 1
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- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
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- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a cobalt boride-loaded sulfur-deficient indium zinc sulfide photocatalyst, and a preparation method and application thereof, wherein the cobalt boride-loaded sulfur-deficient indium zinc sulfide photocatalyst is formed by electrostatic self-assembly of cobalt boride nanoparticles and sulfur-deficient indium sulfide nanosheets, the cobalt boride nanoparticles are loaded on the surfaces of the sulfur-deficient indium sulfide nanosheets, the cobalt boride nanoparticles are highly dispersed on the surfaces of the sulfur-deficient indium sulfide nanosheets to form close interface contact, and the mass ratio of the sulfur-deficient indium sulfide nanosheets to the cobalt boride nanoparticles is 100-4. The nano-particle/nano-sheet structure of the photocatalyst has the advantages of large specific surface area, more active sites, close interface contact, stable structure and the like, the photocatalytic sterilization efficiency is high, the sterilization product has no secondary pollution, and the photocatalyst can effectively adapt to the pH value of a solution and the interference of high-concentration inorganic salt ions, and meanwhile, the photocatalyst also has good recycling performance and good market popularization and application prospects.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst and a preparation method and application thereof.
Background
At present, water source pathogenic microorganisms represented by escherichia coli are frequently detected in surface water, underground water, even drinking water and other water bodies in China. According to statistics, escherichia coli infection in polluted drinking water can cause various diseases including fever, hepatitis, meningitis, respiratory tract infection and the like, and great harm is generated to human health. Therefore, finding an efficient and low-cost method for inactivating escherichia coli is an important subject of the scientific and engineering community.
Various treatment technologies such as membrane filtration, chemical disinfection (ozone and chlorine dioxide) and Ultraviolet (UV) disinfection have been used to disinfect escherichia coli in drinking water, but in practice, these technologies have some limitations. For example, in the case of a nanofiltration membrane and ultrafiltration membrane removal method, although the membrane pore size is small relative to pathogenic microorganisms and pathogenic microorganisms can be effectively eliminated, the use of nanofiltration membranes and ultrafiltration membranes on a large scale leads to high treatment costs. Chemical disinfection using free chlorine, chlorine dioxide and ozone as strong oxidants, while exhibiting excellent inactivation efficiency for e.coli, the application of reagent chemical oxidation in practical water disinfection remains a significant challenge due to the complex operation, the need for additional reagents and the generation of carcinogenic disinfection by-products (e.g. chlorite and chlorate in chlorine dioxide and bromate in ozone). Today, water disinfection technology is moving towards the use of ultraviolet light to control the generation of disinfection byproducts. However, long-term uv irradiation makes escherichia coli highly resistant to uv inactivation, resulting in high energy consumption and high operating costs. From the perspective of green and sustainable development, the solar disinfection technology has great prospect and has been advocated vigorously. However, studies have shown that solar irradiation alone does not completely inactivate E.coli in a short time, and that complete inactivation of E.coli requires a long period of light. Therefore, technical innovation is needed for the water disinfection process induced by sunlight to realize the process of inactivating escherichia coli in water body efficiently, economically and rapidly.
The photocatalysis technology is a novel water disinfection technology, and can effectively improve the virus disinfection performance on overcoming the limitation of the traditional disinfection method. The semiconductor photocatalyst is excited by absorbing sunlight, and electrons in the valence band jump to the conduction band to generate photogenerated carriers. After separation and transfer, the photon-generated carriers can migrate to the surface of the catalyst to participate in redox reaction. Wherein the photoproduced electrons can generate a plurality of high-energy active oxygen substances by combining with dissolved oxygen, and the high-energy active oxygen substances can inactivate escherichia coli together with photoproduced holes. In addition, due to the extremely strong oxidation-reduction capability, the active oxygen substances can also degrade disinfection byproducts, and the generation of toxic and harmful byproducts is reduced.
In recent years, tiO has been included 2 Various photocatalysts such as ZnO and carbon nitride are used in water disinfection. However, almost all of these photocatalysts have the disadvantages of low light energy utilization rate, low sterilization performance, and the like. In order to solve this problem, it is urgently required to develop a visible light photocatalyst having a high disinfecting activity. Indium zinc sulfide (ZnIn), an important ternary chalcogenide 2 S 4 ) Has good electronic structure and chemical stability. ZnIn with relatively narrow forbidden band width (2.1-2.6 eV) 2 S 4 Can effectively absorb visible light, thereby displaying huge visible lightCatalytic disinfection potential. However, practice has shown that the initial ZnIn 2 S 4 The electron transfer rate in the process is low, and the carrier separation efficiency is low, so that the photocatalytic sterilization performance of the process is weak.
Researches show that the cocatalyst can effectively inhibit the recombination of photon-generated carriers by capturing electrons, so that the photocatalytic performance of the composite catalyst is improved. Cobalt boride (CoB) exhibits excellent electron transfer properties due to its metallicity, and has attracted considerable attention as a promoter in photoelectrochemical applications. However, coB is not in effective contact with the semiconductor photocatalyst, and agglomeration of CoB sometimes occurs. Therefore, how to highly uniformly disperse CoB in ZnIn 2 S 4 The surface forms a stable structure, and has important significance for the visible light catalytic inactivation of escherichia coli in practical water.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cobalt boride-loaded sulfur-deficient indium zinc sulfide photocatalyst, and a preparation method and application thereof.
In order to achieve the above object, the present invention firstly provides a cobalt boride-supported sulfur-deficient indium zinc sulfide photocatalyst, which is formed by electrostatic self-assembly of cobalt boride nanoparticles and sulfur-deficient indium sulfide nanosheets, wherein the cobalt boride nanoparticles are supported on the surfaces of the sulfur-deficient indium sulfide nanosheets, the cobalt boride nanoparticles are highly dispersed on the surfaces of the sulfur-deficient indium sulfide nanosheets to form close interfacial contact, and the mass ratio of the sulfur-deficient indium sulfide nanosheets to the cobalt boride nanoparticles is 100.
Preferably, the size of the sulfur-defect indium sulfide nanosheet is 0.2-1 μm, and the size of the cobalt boride nanoparticle is 20-50 nm.
Based on a general inventive concept, the invention also provides a preparation method of the cobalt boride supported sulfur defect indium zinc sulfide photocatalyst, which comprises the following steps:
s1, adding zinc acetate, indium chloride and thioacetamide into a mixed solution of ethanol and deionized water, performing ultrasonic dispersion to obtain a transparent solution, and placing the transparent solution into a reaction kettle to perform hydrothermal reaction to obtain ZnIn 2 S 4 -S nanosheets;
s2, adding polyvinylpyrrolidone and cobalt chloride into deionized water, continuously introducing nitrogen, then placing the solution in an ice water bath, adding a sodium borohydride solution, and continuously stirring for reaction to obtain a cobalt boride precursor; placing the cobalt boride precursor in a tube furnace, continuously introducing nitrogen, and calcining at high temperature to obtain CoB nano particles;
s3, znIn obtained in the step S1 2 S 4 Respectively dispersing the-S nanosheets and the CoB nanoparticles obtained in the step S2 in ethanol, and ultrasonically treating ZnIn 2 S 4 The S and the CoB are uniformly dispersed, and the CoB suspension is added to ZnIn 2 S 4 And (4) continuously stirring the suspension in the S, and then carrying out centrifugal separation and drying to obtain the cobalt boride supported sulfur defect indium zinc sulfide photocatalyst.
Preferably, the molar ratio of zinc acetate, indium chloride and thioacetamide in the step S1 is 1:2:8, the volume ratio of the ethanol to the deionized water is 1-3: 1, the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 12-36 h.
Preferably, the zinc acetate in step S1 is zinc acetate dihydrate Zn (AC) 2 ·2H 2 O, indium chloride is anhydrous indium chloride InCl 3 。
Preferably, the cobalt chloride in the step S2 is cobalt chloride hexahydrate, the dosage of the cobalt chloride hexahydrate is 0.1 to 0.6mol per liter of deionized water, and the dosage of the polyvinylpyrrolidone is 6 to 10g per liter of deionized water.
Preferably, the concentration of sodium borohydride in the step S2 is 0.1-0.3 mol/L, and the amount of sodium borohydride used is 0.1-0.3L per liter of deionized water.
Preferably, in the step S2, the temperature rise rate of the tubular furnace is 5-15 ℃/min, the calcination temperature is 300-500 ℃, and the calcination time is 1-3 h.
Preferably, the ultrasonic time in the step S3 is 0.5 to 2 hours, and the stirring time is 4 to 12 hours.
Based on a general inventive concept, the invention also provides an application of the cobalt boride-loaded sulfur-deficient indium zinc sulfide photocatalyst in photocatalytic inactivation of escherichia coli in a water body, which comprises the following steps: adding the cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst into a water body containing escherichia coli, stirring uniformly, starting a xenon lamp light source to react for 50-150 min to complete escherichia coli inactivation, wherein the dosage of the cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst is 0.2-1 g per liter of water body.
The invention provides a cobalt boride-loaded sulfur-defect indium zinc sulfide photocatalyst CoB/ZnIn 2 S 4 The main principle of S inactivation of E.coli in water is as follows:
the invention adopts CoB/ZnIn 2 S 4 the-S composite photocatalyst inactivates the water body chrysanthemum grandiflorum under the condition of illumination, and the photocatalyst ZnIn 2 S 4 Under illumination, S generates electrons and holes, the electrons have reducibility, the holes have oxidizability, but the electrons and the holes are easy to recombine and annihilate. CoB has strong electron-withdrawing ability and can rapidly transfer ZnIn 2 S 4 The photogenerated electrons in S, causing the spatial separation of electrons and holes. The electrons after space separation can react with dissolved oxygen in water to generate superoxide radical (O) 2 - ) Hydrogen peroxide (H) 2 O 2 ) And active oxygen substances such as hydroxyl free radical (. OH) and the like, which have stronger oxidizability and can inactivate Escherichia coli in the water body together with the cavity.
The scheme of the invention has the following beneficial effects:
(1) The invention provides a novel composite photocatalyst CoB/ZnIn 2 S 4 -S, wherein ZnIn 2 S 4 S is a two-dimensional nanosheet structure, coB is a nanoparticle structure, znIn 2 S 4 the-S two-dimensional nanosheet and the CoB nanoparticle can realize stable interface close contact connection through simple electrostatic self-assembly, have stable structure and realizeCoB and ZnIn which are difficult to effectively contact with semiconductor photocatalyst 2 S 4 The stable connection structure of the S, the nanoparticle/nanosheet structure has the advantages of large specific surface area, more active sites, close interface contact, stable structure and the like.
(2) The invention provides CoB/ZnIn 2 S 4 S is a novel visible light catalyst, and the composite photocatalyst CoB/ZnIn is formed by sulfur-deficient indium zinc sulfide and cocatalyst CoB 2 S 4 And the visible light absorption capacity of the strain is enhanced, the photo-generated carrier yield is high, the separation rate is high, the hole electron oxidation reduction capacity is strong, the active oxygen substance yield is high, the inactivation speed of escherichia coli is high, the performance is strong, and the cost for inactivating the escherichia coli in the water body can be obviously reduced.
(3) The invention provides a CoB/ZnIn 2 S 4 Application of-S photocatalyst in inactivation of escherichia coli in water body and application of-S photocatalyst in CoB/ZnIn 2 S 4 In the-S photocatalytic reaction system, photogenerated electrons generate active oxygen species superoxide radical (. O) by activating molecular oxygen 2 - ) Hydrogen peroxide (H) 2 O 2 ) And active oxygen substances such as hydroxyl free radical (. OH) and the like, which have strong oxidizability and can inactivate Escherichia coli, coB/ZnIn and the like in the water body together with a cavity 2 S 4 the-S photocatalysis sterilization efficiency is high, the sterilization product has no secondary pollution, and the method can effectively adapt to the pH value of the solution and the interference of high-concentration inorganic salt ions.
(4) The invention provides CoB/ZnIn 2 S 4 the-S photocatalyst has good recycling performance, and after multiple cycles, the inactivation performance of escherichia coli is not obviously reduced. The product of the invention provides an effective way for the inactivation of escherichia coli in practical water body, and has good commercial application prospect.
(5) The invention provides CoB/ZnIn 2 S 4 S by CoB and ZnIn 2 S 4 The preparation method is safe and efficient, green and pollution-free, low in cost and easy in obtaining of raw materials; the reaction conditions in the synthetic process are mild, the product yield is high, and the method can be suitable for large-scale industrializationProduction and application prospect is wide.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the results of electron microscopic observation of each component obtained in example 1 of the present invention, wherein FIG. 1 (a) is a sulfur-deficient indium zinc sulfide nanosheet (ZnIn) 2 S 4 -S) scanning electron microscopy, fig. 1 (b) scanning electron microscopy of cobalt boride (CoB) nanoparticles, fig. 1 (c) scanning electron microscopy of cobalt boride/sulfur deficient indium zinc sulfide (2 CB/ZIS-S), fig. 1 (d) transmission electron microscopy of 2 CB/ZIS-S;
FIG. 2 shows ZnIn prepared in example 1 of the present invention 2 S 4 -X-ray diffraction patterns of S nanoplates, coB nanoparticles, and 2 CB/ZIS-S;
FIG. 3 shows ZnIn prepared in example 1 of the present invention 2 S 4 -S and 2CB/ZIS-S, wherein fig. 3 (a) is a photoluminescence spectrum and fig. 3 (b) is a time resolved photoluminescence spectrum;
FIG. 4 is a UV-visible diffuse reflectance chart of cobalt boride/sulfur deficient indium zinc sulfide (1 CB/ZIS-S, 2CB/ZIS-S, 3CB/ZIS-S, 4 CB/ZIS-S) prepared in examples 1 to 4 of the present invention;
FIG. 5 is a graph showing the inactivation performance of different cobalt boride/sulfur deficient indium zinc sulfide (1 CB/ZIS-S, 2CB/ZIS-S, 3CB/ZIS-S, 4 CB/ZIS-S) composite photocatalysts on Escherichia coli in experimental example 3 of the present invention;
FIG. 6 is a scanning electron microscope image of Escherichia coli subjected to photocatalytic reaction of cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) for different time periods in Experimental example 3 of the present invention, wherein FIG. 6 (a) is a scanning electron microscope image of Escherichia coli after catalytic reaction for 0min, FIG. 6 (b) is a catalytic reaction for 60min, and FIG. 6 (c) is a scanning electron microscope image of Escherichia coli after catalytic reaction for 100 min;
FIG. 7 is a drawing showingIn the experimental example 3 of the invention, the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) and the contrast photocatalyst CoB/ZnIn 2 S 4 And CoB/In 2 S 3 -inactivation performance profile of S on e.coli;
FIG. 8 shows a CoB/ZnIn composite photocatalyst (2 CB/ZIS-S) and a control photocatalyst in Experimental example 3 of the present invention 2 S 4 And CoB/In 2 S 3 -baud phase spectrum of S;
FIG. 9 shows the effect of different factors on the inactivation performance of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst on Escherichia coli in Experimental example 4, wherein FIG. 9 (a) is a graph of the inactivation performance of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli under the action of different capture agents; FIGS. 9 (b) to 9 (d) show superoxide radical addition compounds (DMPO-. O) produced by 2CB/ZIS-S under light conditions 2 - ) Hydroxyl radical addition compound (DMPO-OH) and hydrogen peroxide adduct (DMPO-H) 2 O 2 ) Electron paramagnetic resonance spectrum;
FIG. 10 is a graph showing the inactivation performance of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli under different pH effects in experimental example 5 of the present invention;
FIG. 11 is a graph showing the inactivation performance of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli under the action of different inorganic salt ions in experimental example 5 of the present invention;
FIG. 12 is a graph showing the circular inactivation performance of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli in experimental example 6 of the present invention;
FIG. 13 is an X-ray diffraction pattern of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) before and after a cycle reaction in Experimental example 6 of the present invention.
Detailed Description
To make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention.
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art; all reagents used in the examples are commercially available unless otherwise specified.
Example 1
Preparation of cobalt boride nanoparticle modified sulfur defect indium zinc sulfide nanosheet composite photocatalyst
The cobalt boride/sulfur deficient indium zinc sulfide (CoB/ZnIn) 2 S 4 -S) composite photocatalytic material is prepared by an electrostatic self-assembly method and comprises CoB nanoparticles and two-dimensional ZnIn 2 S 4 -S nanosheets. Wherein, coB nano particles are highly dispersed in ZnIn 2 S 4 The surface of the S nanosheet forms close interface contact, and the specific preparation method comprises the following steps:
s1, adding 0.5mmol of zinc acetate dihydrate, 1mmol of anhydrous indium chloride and 4mmol of thioacetamide into a mixed solution consisting of 15mL of ethanol and 15mL of deionized water, performing ultrasonic dispersion for 0.5h to obtain a transparent solution, transferring the transparent solution into a 100mL of polytetrafluoroethylene high-pressure reaction kettle, and reacting for 24h at 180 ℃. Then centrifuging the product at the speed of 5000rpm, washing the product for multiple times by deionized water, and drying the product in vacuum to obtain ZnIn 2 S 4 -S nanosheets.
S2, 400mg of polyvinylpyrrolidone and 3mmol of cobalt chloride hexahydrate are added to a round-bottomed flask containing 50mL of deionized water, and nitrogen with a purity of >99.999% is continued for 1h into the above solution. And then, transferring the solution to an ice bath at 2 ℃, injecting 10mL of 0.15mol/L sodium borohydride solution, and continuously stirring for 1h to obtain a cobalt boride precursor. And (3) placing the cobalt boride precursor in a tube furnace, heating to 400 ℃ at the speed of 5 ℃/min under the condition of continuously introducing nitrogen, and maintaining at the temperature for 2 hours to obtain the CoB nano-particles.
S3, 200mg of ZnIn obtained in the step S1 2 S 4 Dispersing the-S nanosheet and 4mg of CoB nanoparticles obtained in the step S2 in 60mL of ethanol and 10mL of ethanol respectivelyAnd carrying out ultrasonic treatment for 1h to obtain a uniformly mixed suspension. Slow injection of CoB suspension into ZnIn 2 S 4 In the-S suspension, after continuously stirring for 8h, centrifuging the product at the speed of 5000rpm, washing the product for multiple times by deionized water, and drying the product in vacuum at the temperature of 60 ℃ for 8h to obtain CoB/ZnIn 2 S 4 -S composite photocatalyst, number 2CB/ZIS-S.
Experimental example 1
Investigating the CoB/ZnIn produced in example 1 2 S 4 -S composite photocatalyst (2 CB/ZIS-S) structure and performance
The electron microscopic observation of each component prepared in the examples was carried out, and the results are shown in fig. 1: FIG. 1 (a) is a sulfur-deficient indium zinc sulfide nanosheet (ZnIn) prepared in example 1 of the present invention 2 S 4 -S) scanning electron microscopy, fig. 1 (b) scanning electron microscopy of cobalt boride (CoB) nanoparticles, fig. 1 (c) scanning electron microscopy of cobalt boride/sulfur deficient indium zinc sulfide (2 CB/ZIS-S), and fig. 1 (d) transmission electron microscopy of 2CB/ZIS-S. As can be seen from FIG. 1, znIn 2 S 4 The S nanosheets show a uniform two-dimensional sheet structure with a size of between 0.2 and 1 mu m; the CoB nanoparticles showed typical nanoparticle structure with dimensions of 20-50 nm. The 2CB/ZIS-S composite catalyst shows a typical nanoparticle/nanosheet structure, wherein the CoB nanoparticles are uniformly dispersed in ZnIn 2 S 4 -the surface of S nanosheets, forming an intimate interfacial contact.
FIG. 2 shows ZnIn prepared in example 1 of the present invention 2 S 4 -S nanoplatelets, coB nanoparticles and 2CB/ZIS-S. As can be seen from FIG. 2, znIn 2 S 4 the-S nanosheets exhibit a standard hexagonal crystal structure. Wherein diffraction peaks at 21.5 °, 27.6 °, 39.7 °, 47.1 °, and 55.5 ° correspond to the (006), (102), (108), (110), and (202) planes, respectively. For the CoB nanoparticles, a typical boride diffraction peak was detected at 44 °. In the 2CB/ZIS-S composite photocatalyst, the diffraction peak of CoB is not detected due to the low load, but all ZnIn 2 S 4 Diffraction peaks of-S were all detected and no impurity peak, indicating CoB/ZnIn 2 S 4 -S recombinationThe photocatalyst was successfully prepared.
FIG. 3 shows ZnIn prepared in example 1 of the present invention 2 S 4 Luminescence spectra of-S and 2CB/ZIS-S, where FIG. 3 (a) is the photoluminescence spectrum and FIG. 3 (b) is the time resolved photoluminescence spectrum. As can be seen from FIG. 3, znIn 2 S 4 S shows a strong fluorescence peak at 480nm, indicating ZnIn 2 S 4 There is a severe electron hole recombination process in S. After CoB modification, the fluorescence peak intensity of 2CB/ZIS-S is obviously weakened, which indicates that the recombination process of the photo-generated electron hole pair in the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst is effectively inhibited. Similarly, it can be seen by applying a bi-exponential fit to the time-resolved photoluminescence spectra that the mean fluorescence lifetime becomes significantly shorter after introducing CoB, as seen by ZnIn 2 S 4 The 5.57ns of-S was reduced to 3.62ns of 2CB/ZIS-S, indicating that the photogenerated carriers in 2CB/ZIS-S were effectively separated.
Example 2
Preparation of cobalt boride nanoparticle modified sulfur-deficient indium zinc sulfide nanosheet composite photocatalyst
In this embodiment, the preparation method is basically the same as that of the cobalt boride nanoparticle modified sulfur-deficient indium zinc sulfide nanosheet in embodiment 1, and the differences only lie in that: the amount of cobalt boride nanoparticles used in example 2 was 2mg.
The cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst prepared in example 2 is numbered 1CB/ZIS-S.
Example 3
Preparation of cobalt boride nanoparticle modified sulfur defect indium zinc sulfide nanosheet composite photocatalyst
In the present embodiment, the preparation method is basically the same as that of the cobalt boride nanoparticle modified sulfur-deficient indium zinc sulfide nanosheet in embodiment 1, and the differences are only that: the amount of cobalt boride nanoparticles used in example 3 was 6mg.
The cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst prepared in example 3 is numbered 3CB/ZIS-S.
Example 4:
preparation of cobalt boride nanoparticle modified sulfur defect indium zinc sulfide nanosheet composite photocatalyst
In the present embodiment, the preparation method is basically the same as that of the cobalt boride nanoparticle modified sulfur-deficient indium zinc sulfide nanosheet in embodiment 1, and the differences are only that: the amount of cobalt boride nanoparticles used in example 4 was 8mg.
The cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst prepared in example 4 is numbered 4CB/ZIS-S.
Experimental example 2
The ultraviolet-visible diffuse reflection spectra of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalysts prepared in examples 1 to 4 were respectively determined, and the specific results are shown in fig. 4. As can be seen from FIG. 4, the initial ZnIn 2 S 4 The light absorption boundary of S is about 520nm, and the CoB nano-particles have stronger absorption capacity to the whole visible light region. When using CoB nanoparticles to modify ZnIn 2 S 4 after-S nanosheet, it can be seen that the contrast to ZnIn is high 2 S 4 The absorption boundary of the-S, CB/ZIS-S composite material is subjected to red shift, and the absorption strength is obviously improved, which shows that the absorption and utilization capacity of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst to light is improved.
Comparative example 1
Preparation of cobalt boride/indium Zinc sulfide (CoB/ZnIn) 2 S 4 ) And cobalt boride/sulfur deficient indium sulfide (CoB/In) 2 S 3 -S) photocatalyst
Adding 0.5mmol of zinc acetate dihydrate, 1mmol of anhydrous indium chloride and 4mmol of thioacetamide into 30mL of deionized water, carrying out ultrasonic dispersion for 0.5h to obtain a transparent solution, transferring the transparent solution into a 100mL polytetrafluoroethylene high-pressure reaction kettle, and carrying out reaction for 24h at 180 ℃. Centrifuging the product at 5000rpm, washing the product with deionized water for multiple times, and drying the product in vacuum to obtain indium zinc sulfide (ZnIn) 2 S 4 ) A nanosheet. 200mgZnIn 2 S 4 The nanosheets and 4mg of the CoB nanoparticles obtained in example 1 were dispersed in 60mL of ethanol and 10mL of ethanol, respectively, and subjected to ultrasound for 1h to obtain a uniformly mixed suspension. Slow injection of CoB suspension into ZnIn 2 S 4 In suspension, after stirring for 8h, the product was centrifuged at 5000rpm and removedRepeatedly washing with ionized water, and vacuum drying at 60 deg.C for 8 hr to obtain CoB/ZnIn 2 S 4 A composite photocatalyst.
Adding 1mmol of anhydrous indium chloride and 3mmol of thioacetamide into a mixed solution consisting of 15mL of ethanol and 15mL of deionized water, performing ultrasonic dispersion for 0.5h to obtain a transparent solution, transferring the transparent solution into a 100mL of polytetrafluoroethylene high-pressure reaction kettle, and reacting at 180 ℃ for 24h. Centrifuging the product at 5000rpm, washing the product with deionized water for multiple times, and drying the product In vacuum to obtain the sulfur-deficient indium sulfide (In) 2 S 3 -S) nanosheets. 200mgIn is added 2 S 3 And (4) dispersing the-S nanosheet and the CoB nanoparticles obtained in the example 1 in 60mL of ethanol and 10mL of ethanol respectively, and performing ultrasonic treatment for 1 hour to obtain a uniformly mixed suspension. Slowly infusing CoB suspension into In 2 S 3 In the-S suspension, after continuously stirring for 8h, centrifuging the product at the speed of 5000rpm, washing the product for multiple times by deionized water, and drying the product In vacuum at the temperature of 60 ℃ for 8h to obtain CoB/In 2 S 3 -S composite photocatalyst.
Experimental example 3
The application of the composite photocatalyst in inactivating escherichia coli in a water body comprises the following steps:
respectively weighing cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (1 CB/ZIS-S, 2CB/ZIS-S, 3CB/ZIS-S, 4 CB/ZIS-S) and control photocatalyst (CoB/ZnIn) 2 S 4 ，CoB/In 2 S 3 -S) 30mg each, respectively, in 49.5mL of deionized water, uniformly ultrasonically dispersing, and then adding 0.5mL of deionized water with an initial concentration of 1.5X 10 8 CFU/mL of Escherichia coli stock solution to make the concentration of Escherichia coli waste water solution about 1.5X 10 6 CFU/mL. And then, turning on a 300W xenon lamp light source, carrying out constant-temperature water bath at 25 ℃, and carrying out light irradiation for 100min under a 420nm filter plate to carry out photocatalytic inactivation reaction on the escherichia coli. In the reaction process, 100mL of reaction solution is extracted every 20min, the reaction solution is uniformly coated on eosin methylene blue agar culture medium, and the mixture is cultured for 24h in a constant temperature incubator at 37 ℃. And finally, counting the number of escherichia coli on the eosin methylene blue agar culture medium by using a plate counting method, and calculating the inactivation performance of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst on the escherichia coli.
FIG. 5 is a graph showing the inactivation performance of different cobalt boride/sulfur-deficient indium zinc sulfide (1 CB/ZIS-S, 2CB/ZIS-S, 3CB/ZIS-S, 4 CB/ZIS-S) composite photocatalysts for Escherichia coli. As can be seen from FIG. 5, the concentration of E.coli hardly changed after the addition of CoB. After ZnIn is added 2 S 4 S, after 100min of light reaction, 3.16-log of Escherichia coli was inactivated. After the introduction of the CoB nano-particles, the sterilization efficiency of the CB/ZIS-S composite photocatalyst can change along with the change of CoB loading. Wherein 1CB/ZIS-S, 2CB/ZIS-S, 3CB/ZIS-S and 4CB/ZIS-S can inactivate 4.88-log, 6.18-log, 4.08-log and 3.63-log of E.coli, respectively. It can be seen that 2CB/ZIS-S has the highest sterilization efficiency and can remove 100% of Escherichia coli from the solution. This is because CoB has an extremely strong electron extracting ability and accelerates ZnIn 2 S 4 Separating electron-hole pairs in the-S, thereby improving the photocatalytic sterilization performance of the CB/ZIS-S. However, too high CoB loading can overwhelm ZnIn 2 S 4 Active site on the surface of S, limiting the contact of CB/ZIS-S with E.coli, resulting in reduced sterilization performance. Therefore, the optimal mass mixing ratio of the cobalt boride to the sulfur-deficient indium zinc sulfide in the cobalt boride/sulfur-deficient indium zinc sulfide composite photocatalyst is 1.
FIG. 6 is a scanning electron microscope image of Escherichia coli after undergoing photocatalytic reaction for different time periods by a cobalt boride/sulfur-deficient indium zinc sulfide composite photocatalyst (2 CB/ZIS-S), wherein FIG. 6 (a) is a scanning electron microscope image of Escherichia coli after 0min of catalytic reaction, FIG. 6 (b) is 60min of catalytic reaction, and FIG. 6 (c) is 100min of catalytic reaction, and it can be seen from FIG. 6 that the initial Escherichia coli shows a short rod shape with a smooth surface. After 60min of photocatalytic reaction, the surface of the Escherichia coli became rough and showed obvious wrinkle, indicating that the cell membrane of the Escherichia coli was damaged. After 100min of reaction, it can be seen that the cell structure of E.coli has been completely deformed, indicating that E.coli is effectively inactivated.
FIG. 7 shows a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) and a control photocatalyst CoB/ZnIn 2 S 4 And CoB/In 2 S 3 -inactivation performance profile of S on E.coli. From the figure7 it can be seen that compared to CoB/ZnIn 2 S 4 (3.19-log) and CoB/In 2 S 3 the-S (3.85-log), 2CB/ZIS-S has higher Escherichia coli inactivation performance, 6.18-log Escherichia coli can be completely inactivated within 100min, which shows that the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) has higher application value in the same photocatalyst.
FIG. 8 shows a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) and a control photocatalyst CoB/ZnIn 2 S 4 And CoB/In 2 S 3 -baud phase spectrum of S. As can be seen from FIG. 8, in comparison with CoB/ZnIn 2 S 4 And CoB/In 2 S 3 The lowest frequency of-S, 2CB/ZIS-S indicates that the photogenerated electrons and holes in 2CB/ZIS-S can be separated more efficiently, thus allowing 2CB/ZIS-S to exhibit stronger performance in the photocatalytic inactivation of E.coli, consistent with the results of FIG. 7.
Experimental example 4
Investigating the reaction mechanism of the cobalt boride/sulfur defect indium-zinc sulfide composite photocatalyst
30mg of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) prepared in example 1 is weighed, placed in 49.5mL of deionized water, added with 0.5mL of deionized water with initial concentration of 1.5X 10 after being uniformly dispersed by ultrasonic 8 CFU/mL of Escherichia coli stock solution to make the concentration of Escherichia coli waste water solution about 1.5X 10 6 CFU/mL. Subsequently, the electron trapping agent potassium bromate (KBrO) was added separately 3 1 mmol/L) of sodium oxalate (Na) as hole trapping agent 2 C 2 O 4 1 mmol/L), a superoxide radical trapping agent 4-hydroxy-2,2,6,6-tetramethylpiperidinol oxide (TEMPOL, 2 mmol/L), a hydroxyl radical trapping agent tert-butyl alcohol (TBA, 1 mmol/L) and a hydrogen peroxide trapping agent (Fe (II) -EDTA,0.5 mmol/L), turning on a 300W xenon lamp light source, performing constant temperature water bath at 25 ℃, and performing light irradiation under a 420nm filter for 100min to perform a photocatalytic inactivation reaction on escherichia coli. In the reaction process, 100mL of reaction solution is extracted every 20min, the reaction solution is uniformly coated on eosin methylene blue agar culture medium, and the mixture is cultured for 24h in a constant temperature incubator at 37 ℃. Finally, the number of escherichia coli on the eosin methylene blue agar culture medium is counted by a plate counting methodThe amount is counted, and the inactivation performance of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst on escherichia coli is calculated, and the result is shown in fig. 9.
FIG. 9 (a) is a graph showing the inactivation performance of a cobalt boride/sulfur-deficient indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli under the action of different trapping agents; FIGS. 9 (b) to 9 (d) show superoxide radical addition compounds (DMPO-. O) produced by 2CB/ZIS-S under light conditions 2 - ) Hydroxyl radical addition compound (DMPO-OH) and hydrogen peroxide adduct (DMPO-H) 2 O 2 ) Electron paramagnetic resonance spectrum. As can be seen from FIG. 9 (a), the inactivation of E.coli was significantly inhibited after the addition of the electron trapping agent potassium bromate and the hole trapping agent sodium oxalate, indicating that the electrons and holes play an important role in the reaction process. Similarly, the efficiency of 2CB/ZIS-S for photocatalytic inactivation of E.coli was inhibited to varying degrees after the addition of the superoxide radical scavenger, 4-hydroxy-2,2,6,6-tetramethylpiperidinol oxide (TEMPOL), the hydroxyl radical scavenger, tert-butanol (TBA), and the hydrogen peroxide scavenger, fe (II) -EDTA, indicating O.O. 2 - OH and H 2 O 2 All participate in the inhibition reaction of Escherichia coli. Furthermore, as can be seen from FIGS. 9 (b) to 9 (d), DMPO-O 2 - DMPO-OH and DMPO-H 2 O 2 All electron spin electron paramagnetic resonance spectra were detected, explanation.O 2 - OH and H 2 O 2 Is generated in the reaction process. Therefore, in the 2CB/ZIS-S photocatalytic reaction system, photogenerated electrons generate active oxygen substances (O) by activating molecular oxygen 2 →·O 2 - →H 2 O 2 → OH), these reactive oxygen species participate in the inactivation reaction of escherichia coli along with the holes.
Experimental example 5
And (3) inspecting the performance of the cobalt boride/sulfur defect indium zinc sulfide photocatalyst in inactivating escherichia coli in a complex water body environment.
30mg of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) in example 1 is weighed, placed in 49.5mL of deionized water, added with 0.5mL of deionized water with initial concentration of 1.5X 10 after being uniformly dispersed by ultrasonic 8 CFU/mL of Escherichia coli stock solution to make the concentration of Escherichia coli waste water solution about 1.5X 10 6 CFU/mL. Subsequently, the mixture is passed through a 0.1mol/L NaOH solution or 0.1mol/L H 2 SO 4 The solution adjusts the pH of the reaction solution, respectively adjusts the pH of the reaction solution to 4.0, 6.0 (initial pH), 8.0 and 10.0, then opens a 300W xenon lamp light source, performs constant temperature water bath at 25 ℃, performs light irradiation for 100min under a 420nm filter, and performs photocatalytic inactivation reaction on the escherichia coli.
30mg of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) in example 1 is weighed, placed in 49.5mL of deionized water, added with 0.5mL of deionized water with initial concentration of 1.5X 10 after being uniformly dispersed by ultrasonic 8 CFU/mL of Escherichia coli stock solution to make the concentration of Escherichia coli waste water solution about 1.5X 10 6 CFU/mL. Subsequently, by adding NaNO 3 、Na 2 SO 4 、NaHCO 3 And NaH 2 PO 4 And (3) solidifying, turning on a 300W xenon lamp light source after the concentration of inorganic salt ions in the reaction liquid reaches 5mmol/L, performing constant temperature water bath at 25 ℃, and performing light irradiation under a 420nm filter for 100min to perform photocatalytic inactivation reaction on escherichia coli.
In the reaction process, 100mL of reaction solution is extracted every 20min, the reaction solution is uniformly coated on eosin methylene blue agar medium, and the mixture is cultured for 24h in a constant temperature incubator at 37 ℃. And finally, counting the number of escherichia coli on the eosin methylene blue agar culture medium by using a plate counting method, and calculating the inactivation performance of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst on the escherichia coli, wherein the results are shown in fig. 10-11.
FIG. 10 is a diagram of the inactivation performance of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli under the action of different pH values. As can be seen from FIG. 10, the sterilization performance of 2CB/ZIS-S is significantly inhibited when the solution is alkaline (pH 8.0, pH 10.0) compared to the initial pH of 6.0, and only 4.64-log (pH 8.0) and 3.60-log (pH 10.0) of E.coli is inactivated. When the pH is acidic (pH 4.0), the sterilization performance of 2CB/ZIS-S is greatly improved, and 6.18-log escherichia coli can be completely inactivated within 80 min. This is because of the large amount of H under acidic conditions + The presence of (A) accelerates the superoxide radical and peroxygen of the active oxygen speciesThe generation of hydrogen peroxide, these active oxygen species can effectively inactivate Escherichia coli.
FIG. 11 is a diagram of the inactivation performance of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli under the action of different inorganic salt ions. As can be seen from FIG. 11, when coexisting SO 4 2- And NO 3 - In this case, the performance of 2CB/ZIS-S for photocatalytic inactivation of E.coli was almost unchanged. And when H is present 2 PO 4 - And HCO 3 - In time, the inactivation of E.coli is inhibited to some extent. This is because H 2 PO 4 - And HCO 3 - Will react with hydroxyl radical (. OH) to form. H 2 PO 4 And HCO 3 Compared with. OH,. H 2 PO 4 And. HCO 3 The redox ability of (A) is weaker, resulting in a decrease in the efficiency of 2CB/ZIS-S photocatalytic inactivation of E.coli.
Experimental example 6
Investigation of sterilization effect and structural stability of cobalt boride/sulfur defect indium zinc sulfide photocatalyst after recycling
30mg of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) obtained in example 1 is weighed and placed in 49.5mL of deionized water, and 0.5mL of deionized water with the initial concentration of 1.5X 10 is added after uniform ultrasonic dispersion 8 CFU/mL of Escherichia coli stock solution to make the concentration of Escherichia coli waste water solution about 1.5X 10 6 CFU/mL. And then, turning on a 300W xenon lamp light source, carrying out constant temperature water bath at 25 ℃, and carrying out light irradiation for 100min under a 420nm filter plate to carry out photocatalytic inactivation reaction on the escherichia coli. After the reaction is finished, 2CB/ZIS-S is separated out, and the next photocatalytic inactivation reaction is continuously repeated for five times.
In the process of the photocatalytic reaction, 100mL of reaction solution is extracted every 20min, the reaction solution is uniformly coated on an eosin methylene blue agar culture medium, and the mixture is cultured in a constant-temperature incubator at 37 ℃ for 24h. And finally, counting the number of escherichia coli on the eosin methylene blue agar culture medium by using a plate counting method, and calculating the inactivation performance of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst on the escherichia coli, wherein the result is shown in fig. 12.
FIG. 12 is a diagram of the circular inactivation performance of a cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) on Escherichia coli. As can be seen from FIG. 12, 2CB/ZIS-S showed good cycling stability, and E.coli was completely inactivated even after 5 cycles.
X-ray diffraction patterns of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst are respectively measured before and after five times of cyclic inactivation reactions, and the result is shown in FIG. 13. As can be seen from FIG. 13, after 5 cycles of sterilization reaction, the diffraction peak intensity and position of the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst (2 CB/ZIS-S) are not obviously changed compared with those before reaction, which indicates that 2CB/ZIS-S has excellent structural stability in the process of photocatalytic degradation and inactivation of Escherichia coli.
In conclusion, the cobalt boride/sulfur defect indium zinc sulfide composite photocatalyst prepared by the invention has the advantages of strong light absorption capacity, many exposed reaction sites, tight interface contact, high carrier separation rate, strong hole electron redox capacity and the like, is a novel visible light photocatalyst which can be produced in batches, is green and pollution-free, has high synthesis rate, low cost and high reaction performance, can be widely applied to natural water body disinfection, and has extremely high commercial application value.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The cobalt boride-loaded sulfur-deficient indium zinc sulfide photocatalyst is formed by electrostatic self-assembly of cobalt boride nanoparticles and sulfur-deficient indium sulfide nanosheets, the cobalt boride nanoparticles are loaded on the surfaces of the sulfur-deficient indium sulfide nanosheets, the cobalt boride nanoparticles are highly dispersed on the surfaces of the sulfur-deficient indium sulfide nanosheets to form close interfacial contact, and the mass ratio of the sulfur-deficient indium sulfide nanosheets to the cobalt boride nanoparticles is 100.
2. The cobalt boride supported sulfur-deficient indium zinc sulfide photocatalyst of claim 1 wherein the size of the sulfur-deficient indium sulfide nanosheets is 0.2 to 1 μ ι η and the cobalt boride nanoparticle size is 20 to 50nm.
3. A method of preparing a cobalt boride supported sulfur deficient indium zinc sulfide photocatalyst as claimed in any one of claims 1 to 2 comprising the steps of:
s1, adding zinc acetate, indium chloride and thioacetamide into a mixed solution of ethanol and deionized water, performing ultrasonic dispersion to obtain a transparent solution, and placing the transparent solution into a reaction kettle to perform hydrothermal reaction to obtain ZnIn 2 S 4 -S nanosheets;
s2, adding polyvinylpyrrolidone and cobalt chloride into deionized water, continuously introducing nitrogen, then placing the solution in an ice water bath, adding a sodium borohydride solution, and continuously stirring for reaction to obtain a cobalt boride precursor; placing the cobalt boride precursor in a tube furnace, continuously introducing nitrogen, and calcining at high temperature to obtain CoB nano particles;
s3, znIn obtained in the step S1 2 S 4 Respectively dispersing the-S nanosheets and the CoB nanoparticles obtained in the step S2 in ethanol, and ultrasonically treating ZnIn 2 S 4 The S and the CoB are uniformly dispersed, and the CoB suspension is added to ZnIn 2 S 4 And (4) continuously stirring the suspension in the S form, and then carrying out centrifugal separation and drying to obtain the cobalt boride supported sulfur defect indium zinc sulfide photocatalyst.
4. The method according to claim 3, wherein the molar ratio of zinc acetate, indium chloride and thioacetamide in step S1 is 1:2:8, the volume ratio of the ethanol to the deionized water is 1-3: 1, the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 12-36 h.
5. The method according to claim 3, wherein the zinc acetate in step S1 is zinc acetateDihydrate Zn (AC) 2 ·2H 2 O, indium chloride is anhydrous indium chloride InCl 3 。
6. The preparation method according to claim 3, wherein the cobalt chloride in step S2 is cobalt chloride hexahydrate, the amount of the cobalt chloride hexahydrate is 0.1 to 0.6mol per liter of deionized water, and the amount of the polyvinylpyrrolidone is 6 to 10g per liter of deionized water.
7. The preparation method according to claim 3, wherein the concentration of sodium borohydride in step S2 is 0.1-0.3 mol/L, and the amount of sodium borohydride used is 0.1-0.3L per liter of deionized water.
8. The preparation method according to claim 3, wherein the temperature rise rate of the tube furnace in the step S2 is 5-15 ℃/min, the calcination temperature is 300-500 ℃, and the calcination time is 1-3 h.
9. The preparation method according to claim 3, wherein the ultrasonic time in the step S3 is 0.5-2 h, and the stirring time is 4-12 h.
10. The application of the cobalt boride supported sulfur-deficient indium zinc sulfide photocatalyst as defined in any one of claims 1 to 2 or the cobalt boride supported sulfur-deficient indium zinc sulfide photocatalyst prepared by the preparation method as defined in any one of claims 3 to 9 in photocatalytic inactivation of escherichia coli in a water body is characterized by comprising the following steps: adding the cobalt boride supported sulfur defect indium zinc sulfide photocatalyst into a water body containing escherichia coli, uniformly stirring, starting a xenon lamp light source to react for 50-150 min to complete escherichia coli inactivation, wherein the dosage of the cobalt boride supported sulfur defect indium zinc sulfide photocatalyst is 0.2-1 g per liter of the water body.
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