CN114100635A - Indium zinc sulfide/zinc ferrite composite photocatalyst and preparation method and application thereof - Google Patents
Indium zinc sulfide/zinc ferrite composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN114100635A CN114100635A CN202111533888.1A CN202111533888A CN114100635A CN 114100635 A CN114100635 A CN 114100635A CN 202111533888 A CN202111533888 A CN 202111533888A CN 114100635 A CN114100635 A CN 114100635A
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 99
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011701 zinc Substances 0.000 claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 45
- 239000002121 nanofiber Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052738 indium Inorganic materials 0.000 claims abstract description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000004729 solvothermal method Methods 0.000 claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 230000001699 photocatalysis Effects 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 4
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical group O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 10
- 239000002114 nanocomposite Substances 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000003916 acid precipitation Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
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- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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Images
Classifications
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/40—
-
- B01J35/51—
-
- B01J35/58—
Abstract
The invention provides an indium zinc sulfide/zinc ferrite composite photocatalyst and a preparation method and application thereof; the preparation method comprises the following steps: a) mixing an iron source, a zinc source and polyvinylpyrrolidone in the presence of a first solvent, carrying out electrostatic spinning, and calcining to obtain ZnFe2O4A nanofiber; b) mixing a zinc source, an indium source and a sulfur source in the presence of a second solvent, and adding the ZnFe obtained in the step a)2O4Nano fiberVitamin, carrying out solvent thermal reaction to obtain ZnIn2S4The nano sheet is loaded on ZnFe2O4And (3) obtaining the indium zinc sulfide/zinc ferrite composite photocatalyst on the nano fibers. Compared with the prior art, the preparation method provided by the invention prepares the two-dimensional ZnIn2S4The nano-sheet photocatalyst is loaded to one-dimensional zinc ferrite (ZnFe) by a low-temperature solvothermal method2O4) On a nanofiber to obtain ZnIn2S4/ZnFe2O4The nano composite material can carry out photocatalytic degradation on waste gas so as to achieve effective treatment on the waste gas.
Description
Technical Field
The invention relates to the technical field of inorganic functional materials, in particular to an indium zinc sulfide/zinc ferrite composite photocatalyst and a preparation method and application thereof.
Background
With the rapid development of social industrialization and economy, a large amount of industrial exhaust gas causes serious pollution, and great harm is brought to human beings, animals and plants. Meanwhile, the exhaust gas in the atmosphere causes serious environmental pollution problems such as acid rain, acid mist and photochemical smog. Therefore, the search for a cheap, efficient and energy-saving method for degrading and treating the exhaust gas has become a hot problem for researchers in ophthalmology.
At present, the semiconductor photocatalysis technology has the advantages of no toxicity, high degradation efficiency, strong oxidation-reduction capability and the like, and is considered to be one of economic and effective methods for treating waste gas pollution. Among the many photocatalysts currently available, indium zinc sulfide (ZnIn)2S4) The photocatalyst is a metal sulfide semiconductor photocatalyst which is widely researched, and has the advantages of good light absorption capacity under visible light, controllable morphology and structure and the like. However, ZnIn2S4There are also many disadvantages, such as the photo-generated electrons and holes, which are generated after light irradiation, are easily and rapidly recombined, reducing the photocatalytic activity. Therefore, for ZnIn2S4Different modification methods, such as doping of transition metal ions, coupling with other semiconductors, and the like, are adopted to further improve the photocatalytic activity, which is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention aims to provide an indium zinc sulfide/zinc ferrite composite photocatalyst, and a preparation method and an application thereof2S4The nano-sheet photocatalyst is loaded to one-dimensional zinc ferrite (ZnFe) by a low-temperature solvothermal method2O4) On a nanofiber to obtain ZnIn2S4/ZnFe2O4The nano composite material can carry out photocatalytic degradation on waste gas so as to achieve effective treatment on the waste gas.
The invention provides a preparation method of an indium zinc sulfide/zinc ferrite composite photocatalyst, which comprises the following steps:
a) mixing iron source and zinc sourceMixing with polyvinylpyrrolidone in the presence of a first solvent, performing electrostatic spinning, and calcining to obtain ZnFe2O4A nanofiber;
b) mixing a zinc source, an indium source and a sulfur source in the presence of a second solvent, and adding the ZnFe obtained in the step a)2O4Nano-fiber, carrying out solvent thermal reaction to obtain ZnIn2S4The nano sheet is loaded on ZnFe2O4And (3) obtaining the indium zinc sulfide/zinc ferrite composite photocatalyst on the nano fibers.
Preferably, the iron source in step a) is ferric nitrate nonahydrate, the zinc source is zinc nitrate hexahydrate, and the first solvent is N, N-dimethylformamide.
Preferably, the molar ratio of the iron source to the zinc source in the step a) is (1-10): 1; the dosage of the polyvinylpyrrolidone is calculated by zinc source, and 1g to 5g of polyvinylpyrrolidone is added in per mmol of zinc source; the dosage of the first solvent is calculated by zinc source, and 1ml to 20ml of the first solvent is added into each mmol of the zinc source.
Preferably, the voltage of the electrostatic spinning in the step a) is 5kV to 30kV, and the injection rate is 0.1mm/min to 0.3 mm/min.
Preferably, the calcining temperature in the step a) is 100-800 ℃, the heating rate is 0.5-2 ℃/min, and the time is 1-5 h.
Preferably, in the step b), the zinc source is zinc chloride, the indium source is indium chloride tetrahydrate, the sulfur source is thioacetamide, and the second solvent is a mixture of zinc chloride and indium chloride tetrahydrate, wherein the volume ratio of the second solvent is (2-6): 1, a mixed solvent of glycerol and an aqueous acetic acid solution.
Preferably, the molar ratio of the zinc source, the indium source and the sulfur source in step b) is 1: (2-5): (4-10); the dosage of the second solvent is calculated by zinc source, and 10ml to 30ml of the second solvent is added into each mmol of the zinc source.
Preferably, the temperature of the solvothermal reaction in the step b) is 10-100 ℃, and the time is 0.5-5 h.
The invention also provides an indium zinc sulfide/zinc ferrite composite photocatalyst prepared by the preparation method of the technical scheme.
The invention also provides a method for treating waste gas by photocatalysis, which comprises the following steps:
and (2) enabling the gas containing the waste gas to flow through a visible light responding photocatalyst, and realizing the photocatalytic treatment of the waste gas under the illumination condition, wherein the visible light responding photocatalyst is the indium zinc sulfide/zinc ferrite composite photocatalyst in the technical scheme.
The invention provides an indium zinc sulfide/zinc ferrite composite photocatalyst and a preparation method and application thereof; the preparation method comprises the following steps: a) mixing an iron source, a zinc source and polyvinylpyrrolidone in the presence of a first solvent, carrying out electrostatic spinning, and calcining to obtain ZnFe2O4A nanofiber; b) mixing a zinc source, an indium source and a sulfur source in the presence of a second solvent, and adding the ZnFe obtained in the step a)2O4Nano-fiber, carrying out solvent thermal reaction to obtain ZnIn2S4The nano sheet is loaded on ZnFe2O4And (3) obtaining the indium zinc sulfide/zinc ferrite composite photocatalyst on the nano fibers. Compared with the prior art, the preparation method provided by the invention prepares the two-dimensional ZnIn2S4The nano-sheet photocatalyst is loaded to one-dimensional zinc ferrite (ZnFe) by a low-temperature solvothermal method2O4) On a nanofiber to obtain ZnIn2S4/ZnFe2O4The nano composite material can carry out photocatalytic degradation on waste gas so as to achieve effective treatment on the waste gas. Experimental results show that the indium zinc sulfide/zinc ferrite composite photocatalyst provided by the invention has high catalytic degradation activity on nitric oxide, can be repeatedly used and has good chemical stability.
Meanwhile, the preparation method provided by the invention has the advantages of simple process, low energy consumption, economy, environmental protection and the like, and is low in cost, so that the preparation method has good application prospect and potential in waste gas treatment.
Drawings
FIG. 1 shows ZnFe prepared in example 12O4Scanning electron microscope images of nanofibers;
FIG. 2 is a ZnIn with visible light response prepared in example 12S4/ZnFe2O4Transmission electron micrographs of the composite catalyst;
FIG. 3 shows the flower-ball-shaped ZnIn prepared in example 12S4Scanning electron micrographs of the material;
FIG. 4 is the ZnFe prepared in example 12O4、ZnIn2S4And ZnIn prepared in examples 1 to 42S4/ZnFe2O4A catalytic effect diagram for treating the exhaust gas;
FIG. 5 is the ZnIn prepared in example 12S4/ZnFe2O4And (3) a circular degradation effect diagram for waste gas degradation.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of an indium zinc sulfide/zinc ferrite composite photocatalyst, which comprises the following steps:
a) mixing an iron source, a zinc source and polyvinylpyrrolidone in the presence of a first solvent, carrying out electrostatic spinning, and calcining to obtain ZnFe2O4A nanofiber;
b) mixing a zinc source, an indium source and a sulfur source in the presence of a second solvent, and adding the ZnFe obtained in the step a)2O4Nano-fiber, carrying out solvent thermal reaction to obtain ZnIn2S4The nano sheet is loaded on ZnFe2O4And (3) obtaining the indium zinc sulfide/zinc ferrite composite photocatalyst on the nano fibers.
Firstly, mixing an iron source, a zinc source and polyvinylpyrrolidone in the presence of a first solvent, then carrying out electrostatic spinning, and then calcining to obtain ZnFe2O4And (3) nano fibers. In the present invention, the iron source is preferably iron nitrate nonahydrate (Fe (NO)3)3·9H2O), the zinc source is preferably zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), the first solvent is preferably N, N-Dimethylformamide (DMF); the present invention is not particularly limited in terms of the source and solvent of the above-mentioned raw materials, and commercially available products known to those skilled in the art may be used.
In the present invention, the molar ratio of the iron source to the zinc source is preferably (1 to 10): 1, more preferably 2: 1; the dosage of the polyvinylpyrrolidone is calculated by a zinc source, and preferably: 1g to 5g of polyvinylpyrrolidone per mmol of zinc source is added, more preferably: adding 2g of polyvinylpyrrolidone into each mmol of zinc source; the first solvent is preferably used in an amount of zinc source: adding 1ml to 20ml of a first solvent per mmol of zinc source, more preferably: for each mmol of zinc source, 10ml of the first solvent was added.
In the present invention, the mixing process preferably includes:
dissolving a zinc source and an iron source in the first solution, stirring for 1-3 h at room temperature, adding polyvinylpyrrolidone above the solution, and continuously magnetically stirring the mixture for 10-15 h to obtain a brownish red uniform precursor solution;
more preferably:
dissolving a zinc source and an iron source in the first solution, stirring for 2 hours at room temperature, adding polyvinylpyrrolidone above the solution, and continuously magnetically stirring the mixture for 12 hours to obtain a brownish red uniform precursor solution.
In the present invention, the electrospinning is preferably carried out by transferring the precursor solution into a plastic syringe equipped with a steel needle having a diameter of preferably 0.1mm to 1mm, more preferably 0.5mm, and the present invention is not particularly limited thereto.
In the present invention, the voltage of the electrostatic spinning is preferably 5kV to 30kV, more preferably 20 kV; the injection rate of the electrospinning is preferably 0.1mm/min to 0.3mm/min, and more preferably 0.2 mm/min.
In the present invention, the temperature of the calcination is preferably 100 to 800 ℃, more preferably 600 ℃; the heating rate of the calcination is preferably 0.5 ℃/min to 2 ℃/min, more preferably 1 ℃/min; the calcination time is preferably 1 to 5 hours, more preferably 2 hours.
Obtaining the ZnFe2O4After the nano-fiber is processed, the zinc source, the indium source and the sulfur source are mixed in the presence of a second solvent, and the obtained ZnFe is added2O4Nano-fiber, carrying out solvent thermal reaction to obtain ZnIn2S4The nano sheet is loaded on ZnFe2O4And (3) obtaining the indium zinc sulfide/zinc ferrite composite photocatalyst on the nano fibers.
In the present invention, the zinc source is preferably zinc chloride (ZnCl)2) The indium source is preferably indium chloride tetrahydrate (InCl)3·4H2O), the sulfur source is preferably Thioacetamide (TAA), and the second solvent is preferably a mixture of (2-6): 1, more preferably a mixed solvent of Glycerol (Glycerol) and an aqueous acetic acid solution, in a volume ratio of 4: 1, a mixed solvent of glycerol and an aqueous solution of acetic acid; the sources of the raw materials and the solvent are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the pH value of the acetic acid aqueous solution is preferably 1-5, and more preferably 2.5.
In the present invention, the molar ratio of the zinc source, the indium source and the sulfur source is preferably 1: (2-5): (4-10), more preferably 1: 2: 4; the second solvent is preferably used in an amount, based on the zinc source, of: adding 10ml to 30ml of a second solvent per mmol of the zinc source, and preferably: 20ml of the second solvent were added per mmol of the zinc source.
In the present invention, the mixing process preferably includes:
adding acetic acid aqueous solution and glycerol into a round-bottom flask simultaneously under stirring to form a uniform mixed solution (a second solvent), dissolving a zinc source, an indium source and a sulfur source into the solution, and continuously magnetically stirring for 0.5-1.5 h to obtain a mixture;
more preferably:
an aqueous acetic acid solution and glycerol were simultaneously added to a round-bottom flask with stirring to form a uniformly mixed solution (second solvent), and then a zinc source, an indium source and a sulfur source were dissolved in the above solution, followed by continuous magnetic stirring for 1 hour to obtain a mixture.
In the present invention, the solvothermal reaction may be heated by an oil bath well known to those skilled in the art; the temperature of the solvothermal reaction is preferably 10-100 ℃, and more preferably 60 ℃; the solvothermal reaction time is preferably 0.5h to 5h, more preferably 2 h.
After the solvothermal reaction is finished, the method preferably further comprises the following steps:
when the system is naturally cooled to room temperature, repeatedly washing the obtained solid product with deionized water and ethanol for a plurality of times, and drying in an oven at 50-70 ℃ to obtain ZnIn2S4/ZnFe2O4Composite material, namely indium zinc sulfide/zinc ferrite composite photocatalyst;
more preferably:
when the system is naturally cooled to room temperature, repeatedly washing the obtained solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 60 ℃ to obtain ZnIn2S4/ZnFe2O4The composite material is an indium zinc sulfide/zinc ferrite composite photocatalyst.
The invention adopts simple electrostatic spinning and low-temperature solvothermal method to prepare ZnIn2S4/ZnFe2O4The preparation method of the composite photocatalyst is simple and easy to operate, the cost of raw materials is low, the reduction of the preparation cost is facilitated, and the large-scale production is easy to realize.
The invention also provides an indium zinc sulfide/zinc ferrite composite photocatalyst prepared by the preparation method of the technical scheme. In the invention, ZnFe is contained in the indium zinc sulfide/zinc ferrite composite photocatalyst2O4The content is preferably 5 to 50 wt%, more preferably 10 to 40 wt%, most preferably 30 wt%.
The preparation method provided by the invention prepares the two-dimensional ZnIn2S4The nano-sheet photocatalyst is loaded to one-dimensional zinc ferrite (ZnFe) by a low-temperature solvothermal method2O4) On a nanofiber to obtain ZnIn2S4/ZnFe2O4Nanocomposites, i.e.The indium zinc sulfide/zinc ferrite (ZnIn)2S4/ZnFe2O4) The composite photocatalyst is a nano composite material capable of responding in a visible light region.
The ZnIn provided by the invention2S4/ZnFe2O4The nano composite photocatalyst promotes ZnIn2S4And ZnFe2O4The separation efficiency of the photogenerated electrons and the holes in the two is improved, the survival life of the photogenerated electrons is effectively prolonged, and the photocatalytic activity of the catalyst is promoted; the composite material can improve the absorption and utilization of visible light, and can effectively carry out photocatalytic degradation on waste gas so as to effectively treat the waste gas.
The invention also provides a method for treating waste gas by photocatalysis, which comprises the following steps:
and (2) enabling the gas containing the waste gas to flow through a visible light responding photocatalyst, and realizing the photocatalytic treatment of the waste gas under the illumination condition, wherein the visible light responding photocatalyst is the indium zinc sulfide/zinc ferrite composite photocatalyst in the technical scheme.
In the present invention, the waste gas is preferably nitric oxide (nitrogen gas equilibrium), and the illumination condition is preferably xenon lamp light source illumination; the dosage of the visible light response photocatalyst is preferably 50 mg-150 mg, and more preferably 100 mg; the corresponding exhaust gas flow rate is preferably from 0.5L/min to 2L/min, more preferably 1.2L/min.
The invention provides an indium zinc sulfide/zinc ferrite composite photocatalyst and a preparation method and application thereof; the preparation method comprises the following steps: a) mixing an iron source, a zinc source and polyvinylpyrrolidone in the presence of a first solvent, carrying out electrostatic spinning, and calcining to obtain ZnFe2O4A nanofiber; b) mixing a zinc source, an indium source and a sulfur source in the presence of a second solvent, and adding the ZnFe obtained in the step a)2O4Nano-fiber, carrying out solvent thermal reaction to obtain ZnIn2S4The nano sheet is loaded on ZnFe2O4And (3) obtaining the indium zinc sulfide/zinc ferrite composite photocatalyst on the nano fibers. Compared with the prior art, the preparation method provided by the invention is toTwo-dimensional ZnIn2S4The nano-sheet photocatalyst is loaded to one-dimensional zinc ferrite (ZnFe) by a low-temperature solvothermal method2O4) On a nanofiber to obtain ZnIn2S4/ZnFe2O4The nano composite material can carry out photocatalytic degradation on waste gas so as to achieve effective treatment on the waste gas. Experimental results show that the indium zinc sulfide/zinc ferrite composite photocatalyst provided by the invention has high catalytic degradation activity on nitric oxide, can be repeatedly used and has good chemical stability.
Meanwhile, the preparation method provided by the invention has the advantages of simple process, low energy consumption, economy, environmental protection and the like, and is low in cost, so that the preparation method has good application prospect and potential in waste gas treatment.
To further illustrate the present invention, the following examples are provided for illustration. In order to observe the morphology of the material, the products prepared in the following examples were characterized by scanning electron microscopy and transmission electron microscopy.
Example 1
(1)ZnFe2O4Preparing the nano-fibers: first, 2mmol of Zn (NO)3)2·6H2O and 4mmol of Fe (NO)3)3·9H2Dissolving O in 20mL of DMF solution; after stirring at room temperature for 2 hours, 4g of polyvinylpyrrolidone (PVP, K90) was added above the solution and the mixture was stirred magnetically for 12 hours continuously to give a reddish-brown homogeneous precursor solution. Then, the precursor solution was transferred to a 5mL plastic syringe equipped with a steel needle having a diameter of about 0.5mm for electrospinning (voltage: 20kV, injection rate: 0.2 mm/min). Finally, calcining the obtained nano-fiber in the air at 600 ℃ for 2 hours at the heating rate of 1 ℃/min to obtain ZnFe2O4And (3) nano fibers.
The morphology characterization is shown in fig. 1; FIG. 1 shows ZnFe prepared in this example2O4Scanning Electron Micrographs (SEM) of nanofibers, where (a) and (b) represent ZnFe prepared in this example2O4And (3) nano fibers.
(2)ZnIn2S4/ZnFe2O4Preparing a composite material: first, 8mL of an aqueous acetic acid solution (pH 2.5) and 32mL of glycerin were simultaneously added to a 150mL round-bottom flask with stirring to form a uniformly mixed solution. Then, 272mg of ZnCl was added2，586mg InCl3·4H2O and 300mg of TAA were dissolved in the above solution, respectively, and magnetic stirring was continued for 1 hour. Then, ZnFe prepared in the step (1) is put into2O4The nanofibers are added and mixed evenly under stirring. Finally, transferring the obtained solution into an oil bath, heating to 80 ℃ and reacting for 2 h; when the system is naturally cooled to room temperature, repeatedly washing the obtained solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 60 ℃ to obtain ZnIn2S4/ZnFe2O4(simply labeled ZIS/ZFO) composite material.
According to the addition of ZnFe2O4The quality is different, so that ZnFe can be obtained2O4ZnIn with different contents2S4/ZnFe2O4A composite material; this example yielded 30 wt% ZFO of ZIS/ZFO composite.
The topography is shown in FIG. 2; FIG. 2 shows a visible light response ZnIn prepared in this example2S4/ZnFe2O4Transmission Electron Micrograph (TEM) of the composite catalyst, wherein (a) and (b) represent ZnIn prepared in this example2S4/ZnFe2O4And (3) compounding a catalyst.
In addition, step (2) is carried out without adding ZnFe2O4Under the condition of the nano-fiber, directly transferring the solution obtained by continuous magnetic stirring for 1 hour into an oil bath, heating to 80 ℃ and reacting for 2 hours; when the system is naturally cooled to room temperature, repeatedly washing the obtained solid product with deionized water and ethanol for several times, and drying in an oven at 60 ℃ to obtain the flower-ball-shaped ZnIn2S4A material.
The topography is shown in FIG. 3; FIG. 3 shows a flower-ball-shaped ZnIn prepared in this example2S4Scanning Electron Microscopy (SEM) of the Material, wherein (a) represents the flower-spherical ZnIn prepared in this example2S4A material.
As can be seen from FIG. 1(a), ZnFe was produced2O4The shape of the fiber is a one-dimensional nanofiber state, the diameter is 100 nm-200 nm, and the length is several microns long; as can be seen from FIGS. 2(a) and (b), ZnIn2S4The nano-sheet is uniformly loaded on ZnFe2O4On the nano-fiber; FIG. 3(a) shows ZnIn in the form of rosette2S4Is composed of large amount of ZnIn2S4The nano sheets are combined.
Example 2
The preparation process provided in example 1 was used with the difference that: this example yielded 10 wt% ZFO of ZIS/ZFO composite.
Example 3
The preparation process provided in example 1 was used with the difference that: this example yielded 20 wt% ZFO of ZIS/ZFO composite.
Example 4
The preparation process provided in example 1 was used with the difference that: this example yielded 40 wt% ZFO of ZIS/ZFO composite.
Application examples
The method for treating the waste gas through photocatalysis comprises the following specific steps: spreading 100mg of catalyst to be detected on a wood board in a closed cylindrical detection chamber with the volume of 2.26L, and vertically placing a 300W xenon lamp above the wood board; controlling the gas flow concentration to be 600ppb by mixing air and nitric oxide in the compression bottle, and enabling the gas flow to pass through the reaction chamber at the flow rate of 1.2L/min; when the catalyst reached the adsorption-desorption equilibrium (about 0.5h), the xenon lamp was turned on and the catalyst was in the NO statexStarting photocatalytic measurement on an analyzer; the measurement time is 30min, the sampling time interval is 1min, and 30 groups of data are obtained in total.
FIG. 4 is the ZnFe prepared in example 12O4、ZnIn2S4And ZnIn prepared in examples 1 to 42S4/ZnFe2O4An effect graph of treating the waste gas; as can be seen from FIG. 4, ZnIn2S4/ZnFe2O4The catalytic efficiency of the catalyst to waste gas is obviously better than that of ZnFe2O4(24%) and ZnIn2S4(32%); and by regulating the ZnF addede2O4The content of (example 2-4) can achieve a degradation effect of 55% at most; description of ZnIn2S4/ZnFe2O4The compound has higher catalytic degradation activity on nitric oxide.
FIG. 5 is the ZnIn prepared in example 12S4/ZnFe2O4A circulation effect graph for waste gas degradation; as can be seen from the figure, after 5 cycles, the degradation effect is not obviously changed, and the good nitric oxide degradation effect is still shown. Therefore, the catalyst can be repeatedly used and has good chemical stability.
In conclusion, the invention successfully prepares ZnIn by combining easy-to-operate electrostatic spinning and a low-temperature solvothermal method2S4/ZnFe2O4A nanocomposite; meanwhile, the composite material provided by the invention has excellent visible light catalytic degradation performance on waste gas; in addition, the preparation method has the advantages of simple process, low energy consumption, economy, environmental protection and the like, and is low in cost, so that the preparation method has good application prospect and potential in waste gas treatment.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of an indium zinc sulfide/zinc ferrite composite photocatalyst comprises the following steps:
a) mixing an iron source, a zinc source and polyvinylpyrrolidone in the presence of a first solvent, carrying out electrostatic spinning, and calcining to obtain ZnFe2O4A nanofiber;
b) the zinc source, the indium source and the sulfur source are in the second solventAfter downmixing, ZnFe obtained in step a) is added2O4Nano-fiber, carrying out solvent thermal reaction to obtain ZnIn2S4The nano sheet is loaded on ZnFe2O4And (3) obtaining the indium zinc sulfide/zinc ferrite composite photocatalyst on the nano fibers.
2. The method of claim 1, wherein the iron source in step a) is ferric nitrate nonahydrate, the zinc source is zinc nitrate hexahydrate, and the first solvent is N, N-dimethylformamide.
3. The preparation method according to claim 1, wherein the molar ratio of the iron source to the zinc source in step a) is (1-10): 1; the dosage of the polyvinylpyrrolidone is calculated by zinc source, and 1g to 5g of polyvinylpyrrolidone is added in per mmol of zinc source; the dosage of the first solvent is calculated by zinc source, and 1ml to 20ml of the first solvent is added into each mmol of the zinc source.
4. The method according to claim 1, wherein the electrospinning voltage in step a) is 5 to 30kV, and the injection rate is 0.1 to 0.3 mm/min.
5. The preparation method according to claim 1, wherein the calcination in step a) is performed at a temperature of 100 ℃ to 800 ℃, at a heating rate of 0.5 ℃/min to 2 ℃/min, and for a time of 1h to 5 h.
6. The preparation method according to claim 1, wherein the zinc source in step b) is zinc chloride, the indium source is indium chloride tetrahydrate, the sulfur source is thioacetamide, and the second solvent is a mixture of (2-6): 1, a mixed solvent of glycerol and an aqueous acetic acid solution.
7. The method of claim 1, wherein the molar ratio of the zinc source, indium source, and sulfur source in step b) is 1: (2-5): (4-10); the dosage of the second solvent is calculated by zinc source, and 10ml to 30ml of the second solvent is added into each mmol of the zinc source.
8. The preparation method according to claim 1, wherein the temperature of the solvothermal reaction in the step b) is 10-100 ℃ and the time is 0.5-5 h.
9. An indium zinc sulfide/zinc ferrite composite photocatalyst, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. A method of photocatalytic treatment of exhaust gas comprising the steps of:
passing a gas containing exhaust gas through a visible light-responsive photocatalyst to effect photocatalytic treatment of the exhaust gas under light conditions, wherein the visible light-responsive photocatalyst is the indium zinc sulfide/zinc ferrite composite photocatalyst of claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114768831A (en) * | 2022-05-30 | 2022-07-22 | 中国海洋大学 | Novel zinc ferrite and nickel doped zinc indium sulfide heterojunction photoelectrocatalysis anode material and preparation method thereof |
| CN114768831B (en) * | 2022-05-30 | 2023-08-29 | 中国海洋大学 | Photoelectrocatalysis anode material of zinc ferrite and nickel doped zinc indium sulfide heterojunction and preparation method thereof |
| CN115282983A (en) * | 2022-07-14 | 2022-11-04 | 金陵科技学院 | Indium zinc sulfide supported noble metal photocatalyst and preparation method and application thereof |
| CN115282983B (en) * | 2022-07-14 | 2023-08-22 | 金陵科技学院 | Photocatalyst of indium zinc sulfide loaded with noble metal, preparation method and application thereof |
| CN115178278A (en) * | 2022-07-15 | 2022-10-14 | 中国海洋大学 | Novel photoelectric catalyst material of zinc ferrite and cobalt doped zinc indium sulfide heterojunction and preparation method thereof |
| CN115178278B (en) * | 2022-07-15 | 2023-08-04 | 中国海洋大学 | Novel photoelectric catalyst material of zinc ferrite and cobalt doped zinc indium sulfur heterojunction and preparation method thereof |
| CN116899589A (en) * | 2023-06-09 | 2023-10-20 | 常州大学 | Yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics and preparation method and application thereof |
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