CN115025788A - TiO 2 2 /CeO 2 /In 2 S 3 Heterostructure and preparation method and application thereof - Google Patents
TiO 2 2 /CeO 2 /In 2 S 3 Heterostructure and preparation method and application thereof Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002121 nanofiber Substances 0.000 claims abstract description 42
- 230000001699 photocatalysis Effects 0.000 claims abstract description 21
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000004098 Tetracycline Substances 0.000 claims description 20
- 229960002180 tetracycline Drugs 0.000 claims description 20
- 229930101283 tetracycline Natural products 0.000 claims description 20
- 235000019364 tetracycline Nutrition 0.000 claims description 20
- 150000003522 tetracyclines Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 6
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PDSFNMKWUYSTLK-UHFFFAOYSA-M [O-2].[O-2].[O-2].[OH-].[Ti+4].[Ce+3] Chemical compound [O-2].[O-2].[O-2].[OH-].[Ti+4].[Ce+3] PDSFNMKWUYSTLK-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/58—Fabrics or filaments
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a TiO compound 2 /CeO 2 /In 2 S 3 A heterostructure and a preparation method and application thereof belong to the technical field of photocatalytic materials. The invention directly prepares TiO by electrostatic spinning method 2 /CeO 2 Nanofibers of In produced by hydrothermal method 2 S 3 Nanosheet Supported on TiO 2 /CeO 2 On the nanofibers. The invention improves the utilization rate of visible light by loading indium sulfide with narrower forbidden band, and can also effectively prevent indium sulfide from carrying carriers due to narrow forbidden bandThe compounding is fast.
Description
Technical Field
The invention relates to a TiO compound 2 /CeO 2 /In 2 S 3 A heterostructure and a preparation method and application thereof belong to the technical field of photocatalytic materials.
Background
In recent years, rapid development of economy and continuous growth of global population are key factors causing energy shortage and environmental pollution. Therefore, in order to ensure the long-term sustainable development of human society, the development of environmental protection and renewable technologies for green energy production and environmental remediation is urgently needed, and in order to find a more effective purification technology, researchers are utilizing solar energy as a clean energy source, such as solar energy for purifying waste water and protecting the environment. Therefore, the photocatalytic technology is one of the most effective ways to produce hydrogen as a clean energy source and degrade pollutants under mild conditions.
TiO 2 Is considered to be one of the best photocatalysts because of its good resistance to photo-corrosion and catalytic activity. CeO (CeO) 2 The catalyst shows better photocatalytic performance due to higher thermal stability, oxygen storage capacity and easy conversion between Ce (III) and Ce (IV) oxidation states. In 2 S 3 Has received much attention because of its excellent photosensitivity and photoconductivity, stable chemical and physical properties, and low toxicity. Because of TiO 2 ，CeO 2 And In 2 S 3 Special band structure, thus preparing TiO 2 /CeO 2 /In 2 S 3 The heterostructure can effectively improve the separation of carriers, thereby improving the photocatalytic performance of the heterostructure.
At present, CN107243340A reports a preparation method of a cerium dioxide nanorod doped titanium dioxide nanoparticle photocatalyst, but a method for preparing titanium dioxide cerium dioxide nanofibers by adopting a one-step electrostatic spinning method is not reported, and compared with a corresponding block material, a one-dimensional nanomaterial has the advantages of large length-diameter ratio, high porosity, large specific surface area and the like, and has excellent physicochemical properties. However, both ceria and titania have large forbidden bandwidths and low utilization rate of visible light.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides TiO 2 /CeO 2 /In 2 S 3 A heterostructure, a method of making the same and applications thereof. The invention improves the utilization rate of visible light by loading indium sulfide with narrower forbidden band, and can also effectively prevent the indium sulfide from fast compounding due to narrow forbidden band current carriers.
The technical scheme of the invention is as follows:
TiO (titanium dioxide) 2 /CeO 2 /In 2 S 3 Heterostructure, direct preparation of TiO by electrospinning 2 /CeO 2 Nanofibers of In produced by hydrothermal method 2 S 3 Nanosheet loading into TiO 2 /CeO 2 On the nanofibers.
Preferably, said TiO is 2 /CeO 2 The diameter of the nanofiber is 90-110 nm.
Preferably, said In 2 S 3 The thickness of the nano-sheet is 10-15 nm.
Preferably, said TiO is 2 /CeO 2 Nanofibers and In 2 S 3 In a molar ratio of 1: (0.3-0.6).
Further, the TiO 2 /CeO 2 /In 2 S 3 The preparation method of the heterostructure comprises the following steps:
(1) dissolving cerium nitrate and tetrabutyl titanate in a mixed solvent composed of DMF and absolute ethyl alcohol, wherein the molar ratio of Ti to Ce is 1: 0.13, adding acetic acid, adding polyvinylpyrrolidone (PVP), and uniformly stirring to obtain spinnable sol;
the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solvent is 1: 1; the weight average molecular weight of the polyvinylpyrrolidone is 4-300 ten thousand;
(2) electrostatic spinning the spinnable sol prepared in the step (1) to prepare precursor fiber;
performing electrostatic spinning on the spinnable precursor sol obtained in the step (1) under the conditions that the temperature is 15-35 ℃, the voltage is 10-30kV, and the ejection rate is 0.1-1.5mL/h to obtain precursor fiber;
(3) drying the precursor fiber prepared in the step (2) at 50-100 ℃ for 12-36h, heating to 500- 2 /CeO 2 A nanofiber;
(4) dissolving indium nitrate and thioacetamide in a mixed solvent consisting of deionized water and absolute ethyl alcohol, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 5: 1, stirring until the TiO is completely dissolved, and then adding the TiO prepared in the step (3) 2 /CeO 2 Nanofibers, TiO 2 /CeO 2 Nanofibers and In 2 S 3 In a molar ratio of 1: (0.3-0.6), stirring for 60 min;
(5) and (4) transferring the solution prepared in the step (4) into a hydrothermal reaction kettle, heating to 160 ℃, preserving heat for 12 hours, cooling to room temperature, then centrifugally washing, drying, and collecting a sample.
In the invention, the volume ratio of DMF to absolute ethyl alcohol in the mixed solvent in the step (1) is 1: 1; not only can ensure the optimal solubility of solute in the precursor sol, but also can ensure the optimal spinnability of the sol.
Preferably, the weight average molecular weight of the polyvinylpyrrolidone in step (1) is 100 to 150 ten thousand, more preferably 130 ten thousand, and an optimal sol can be obtained.
Further, the electrostatic spinning conditions in the step (2) are as follows: the spraying speed of the spinnable sol is 1.0mL/h, the voltage is 20kV, the electrostatic spinning temperature is controlled at 25-30 ℃, and the nano-fiber with uniform diameter and optimal structure can be obtained.
Further, in the step (3), the temperature is raised to 800 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 120min to obtain TiO 2 /CeO 2 And (3) nano fibers.
Further, in the step (4), TiO 2 /CeO 2 Nanofibers and In 2 S 3 In a molar ratio of 1: 0.4, has the optimal performance.
Preparing nano-fiber of titanium dioxide and cerium oxide by adopting an electrostatic spinning method, and preparing TiO by taking indium chloride and thioacetamide as main raw materials through a hydrothermal method 2 /CeO 2 /In 2 S 3 A heterostructure nanomaterial. By reacting with TiO 2 /CeO 2 /In 2 S 3 Characterization and testing of the heterostructure nanomaterials to study its photocatalytic performance.
Further, TiO 2 /CeO 2 /In 2 S 3 The heterostructure is applied to photocatalytic oxidative degradation of tetracycline.
The invention has the beneficial effects that:
1. the invention directly prepares TiO by electrostatic spinning method 2 /CeO 2 The nano-fiber is simple and convenient to prepare TiO 2 /CeO 2 The process of the heterostructure is such that,
2. the invention prepares TiO by 2 /CeO 2 /In 2 S 3 The heterostructure improves the utilization ratio of visible light and improves the photocatalysis efficiency.
Drawings
FIG. 1 is an XRD spectrum of photocatalyst samples prepared according to the present invention from example 1, example 2, example 3, example 4 and example 5;
FIG. 2 is a TiO prepared according to example 1 of the present invention 2 /CeO 2 Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) photographs of the nanofibers;
FIG. 3 is a representation of TiO prepared according to the invention in examples 2, 3, 4 and 5 2 /CeO 2 /In 2 S 3 Scanning Electron Microscope (SEM) photographs of the heterostructure;
FIG. 4 shows TiO prepared in example 1 of the present invention 2 /CeO 2 Absorbance curve of photodegradable tetracycline of nanofibers; the curve in the graph sequentially corresponds to the 0-180min in the graph from top to bottom;
FIG. 5 shows TiO prepared in example 2 of the invention 2 /CeO 2 /In 2 S 3 Absorbance curves of photodegraded tetracycline of heterostructures; the curves in the graph sequentially correspond to the 0-180min in the graph from top to bottom;
FIG. 6 is TiO prepared according to example 3 of the present invention 2 /CeO 2 /In 2 S 3 Absorbance curves of photodegraded tetracycline of heterostructures; the curve in the graph sequentially corresponds to the 0-180min in the graph from top to bottom;
FIG. 7 shows TiO prepared in example 4 of the present invention 2 /CeO 2 /In 2 S 3 Absorbance curves of photodegraded tetracycline of heterostructures; the curve in the graph sequentially corresponds to the 0-180min in the graph from top to bottom;
FIG. 8 shows TiO prepared in example 5 of the present invention 2 /CeO 2 /In 2 S 3 Absorbance curves of photodegraded tetracycline of heterostructures; the curves in the graph sequentially correspond to the 0-180min in the graph from top to bottom;
FIG. 9 is a graph comparing the degradation of tetracycline by the photocatalytic materials prepared in examples 1, 2, 3, 4 and 5;
FIG. 10 is a graph showing the degradation efficiency of tetracycline by 4 cycles in inventive example 3.
Detailed Description
The invention is further described below in conjunction with specific embodiments, and the advantages and features of the invention will become more apparent as the description proceeds. The examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The raw materials used in the examples are all conventional reagents, commercially available products, of which: the polyvinylpyrrolidone is polyvinylpyrrolidone K90, and has a weight average molecular weight of 130 ten thousand.
Example 1A TiO 2 /CeO 2 Preparation of nanofibers
(1) 0.1627g of cerium nitrate and 1mL of tetrabutyl titanate are dissolved in a mixed solvent consisting of 5mL of DMF and 5mL of absolute ethyl alcohol, acetic acid is added, 0.6g of polyvinylpyrrolidone (PVP) is added, and the mixture is stirred uniformly to obtain spinnable sol;
(2) electrostatic spinning is carried out on the spinnable sol prepared in the step (1) to prepare precursor fiber; performing electrostatic spinning on the spinnable precursor sol obtained in the step (1) under the conditions that the temperature is 25 ℃, the voltage is 20kV, and the ejection rate is 1.0mL/h to obtain precursor fibers;
(3) drying the precursor fiber prepared in the step (2) at 60 ℃ for 12h, heating to 800 ℃ at the speed of 2 ℃/min, and preserving heat for 120min to obtain TiO 2 /CeO 2 And (3) nano fibers.
FIG. 1 shows TiO prepared by example 2 /CeO 2 An X-ray diffraction (XRD) spectrum of the nanofiber photocatalytic material;
in FIG. 2, a and b represent TiO prepared in this example 2 /CeO 2 SEM images of nanofiber photocatalytic materials; FIGS. 2c and d are the TiO compounds prepared in this example 2 /CeO 2 TEM images of nanofiber photocatalytic materials; from FIG. 1, it can be seen that TiO 2 /CeO 2 Diffraction peak of nano-fiber and rutile phase TiO 2 (JCPDS No.12-1276) and CeO 2 (JCPDS No.43-1002) corresponds well, indicating successful preparation of TiO 2 /CeO 2 And (3) nano fibers. As can be seen from FIG. 2, TiO 2 /CeO 2 The diameter of the nanofiber is about 100nm and is uniform.
Example 2A TiO 2 /CeO 2 /In 2 S 3 Preparation of heterostructures
(4) 0.0439g of indium chloride and 0.0450g of thioacetamide were dissolved in a mixed solvent composed of 12.5mL of deionized water and 2.5mL of anhydrous ethanol, stirred until completely dissolved, and then 0.0555g of TiO prepared in example 1 was added 2 /CeO 2 Stirring the nano fibers for 60 min;
(5) and (4) transferring the solution prepared in the step (4) into a hydrothermal reaction kettle, heating to 160 ℃, preserving heat for 12 hours, cooling to room temperature, then centrifugally washing, drying, and collecting a sample.
FIG. 1 shows TiO prepared by example 2 /CeO 2 /In 2 S 3 The X-ray diffraction (XRD) spectrum of the heterostructure photocatalytic material shows that TiO is known from figure 1 2 /CeO 2 /In 2 S 3 Diffraction peak of heterostructure and rutile phase TiO 2 (JCPDS No.12-1276)，CeO 2 (JCPDS No.43-1002) and In 2 S 3 (JCPDS No.32-0456) can correspond well. FIG. 2, panel a is an SEM image of the sample prepared in example 2, and it can be seen that in TiO 2 /CeO 2 In is grown on the surface of the nanofiber 2 S 3 Nanosheet, and In 2 S 3 The distribution of the nano-sheets is less.
Example 3A TiO 2 /CeO 2 /In 2 S 3 Preparation of heterostructures
(4) 0.0586g of indium chloride and 0.0600g of thioacetamide were dissolved in a mixed solvent consisting of 12.5mL of deionized water and 2.5mL of anhydrous ethanol, stirred until completely dissolved, and then 0.0555g of the TiO prepared in example 1 was added 2 /CeO 2 Stirring the nano fibers for 60 min;
(5) and (4) transferring the solution prepared in the step (4) into a hydrothermal reaction kettle, heating to 160 ℃, preserving heat for 12 hours, cooling to room temperature, then centrifugally washing, drying, and collecting a sample.
FIG. 1 shows TiO prepared by example 2 /CeO 2 /In 2 S 3 The X-ray diffraction (XRD) spectrum of the heterostructure photocatalytic material shows that TiO is known from figure 1 2 /CeO 2 /In 2 S 3 Diffraction peak of heterostructure and rutile phase TiO 2 (JCPDS No.12-1276)，CeO 2 (JCPDS No.43-1002) and In 2 S 3 (JCPDS No.32-0456) corresponds well. FIG. 2 b is an SEM image of the sample prepared in example 3, and it can be seen that in TiO 2 /CeO 2 In is grown on the surface of the nanofiber 2 S 3 Nanosheets, and the content of nanosheets on the fiber increases as the content of indium sulfide supported increases.
Example 4A TiO 2 /CeO 2 /In 2 S 3 Preparation of heterostructures
(4) 0.0732g of indium chloride and 0.0750g of thioacetamide were dissolved in a mixed solvent composed of 12.5mL of deionized water and 2.5mL of anhydrous ethanol, stirred until completely dissolved, and then 0.0555 was addedg TiO from example 1 2 /CeO 2 Stirring the nano fibers for 60 min;
(5) and (4) transferring the solution prepared in the step (4) into a hydrothermal reaction kettle, heating to 160 ℃, preserving heat for 12 hours, cooling to room temperature, then centrifugally washing, drying, and collecting a sample.
FIG. 1 shows the TiO prepared by example 2 /CeO 2 /In 2 S 3 The X-ray diffraction (XRD) spectrum of the heterostructure photocatalytic material shows that TiO is known from figure 1 2 /CeO 2 /In 2 S 3 Diffraction peak of heterostructure and rutile phase TiO 2 (JCPDS No.12-1276)，CeO 2 (JCPDS No.43-1002) and In 2 S 3 (JCPDS No.32-0456) corresponds well. FIG. 2, panel c, is an SEM image of the sample prepared in example 4, as can be seen in TiO 2 /CeO 2 In is grown on the surface of the nanofiber 2 S 3 Nanosheets, and the content of nanosheets on the fiber increases as the content of indium sulfide supported increases.
Example 5A TiO compound 2 /CeO 2 /In 2 S 3 Preparation of heterostructures
(4) 0.0879g of indium chloride and 0.0900g of thioacetamide were dissolved in a mixed solvent composed of 12.5mL of deionized water and 2.5mL of anhydrous ethanol, and stirred until completely dissolved, after which 0.0555g of TiO prepared in example 1 was added 2 /CeO 2 Stirring the nano fibers for 60 min;
(5) and (4) transferring the solution prepared in the step (4) into a hydrothermal reaction kettle, heating to 160 ℃, preserving heat for 12 hours, cooling to room temperature, then centrifugally washing, drying, and collecting a sample.
FIG. 1 shows TiO prepared by example 2 /CeO 2 /In 2 S 3 The X-ray diffraction (XRD) spectrum of the heterostructure photocatalytic material shows that TiO is known from figure 1 2 /CeO 2 /In 2 S 3 Diffraction peak of heterostructure and rutile phase TiO 2 (JCPDS No.12-1276)，CeO 2 (JCPDS No.43-1002) and In 2 S 3 (JCPDS No.32-0456) corresponds well. FIG. 2, d is a SEM image of the sample prepared in example 5To be seen in TiO 2 /CeO 2 In is grown on the surface of the nanofiber 2 S 3 Nanosheet due to In loading 2 S 3 Too high to give some agglomerates.
Application example
The photocatalyst prepared in example 1, example 2, example 3, example 4 and example 5 is applied to the photocatalytic oxidative degradation of tetracycline, the used simulated light source is a 350W xenon lamp, the concentration of the tetracycline solution is 10mg/L, and the steps are as follows:
firstly, at room temperature, adding 0.03g of photocatalytic material into 50mL of Tetracycline (TC) solution, then placing the solution into a dark box, magnetically stirring the solution for 60min to achieve adsorption-desorption balance, and taking out 4mL of solution after the dark reaction is finished; then, turning on a simulated light source, and taking 4mL of solution every 20 min; centrifuging the solution taken out each time, taking supernatant, and testing the absorbance of the supernatant at the highest peak (357nm) by using a UV-2550 spectrophotometer respectively; and recovering the photocatalytic material. Formula (I):
η＝[(C 0 -C t )/C 0 ]×100％，
in the formula (I), C 0 Absorbance, C, first measured for the solution t Absorbance measured as time t.
FIG. 4 shows TiO prepared in example 1 of the present invention 2 /CeO 2 Under visible light of the nanofiber: (>400nm) of the absorbance curve of the photodegradation tetracycline, and the degradation efficiency is 45.5 percent at 180min shown in figure 4;
FIG. 5 shows TiO prepared in example 2 of the invention 2 /CeO 2 /In 2 S 3 The absorbance curve of the heterostructure for photodegradation of tetracycline under visible light; from FIG. 5, it can be seen that the degradation efficiency is 65.2% at 180min, which is improved compared with the degradation efficiency of the sample of example 2;
FIG. 6 shows TiO prepared in example 3 of the present invention 2 /CeO 2 /In 2 S 3 The absorbance curve of the heterostructure for photodegradation of tetracycline under visible light; from FIG. 6, it can be seen that the degradation efficiency is 95.4% at 180min, and the degradation rate is the highest in all samples;
FIG. 7 shows TiO prepared in example 4 of the present invention 2 /CeO 2 /In 2 S 3 The absorbance curve of the photodegradation tetracycline of the heterostructure under visible light; the degradation efficiency is 86.4% at 180min as shown in FIG. 7;
FIG. 8 shows TiO prepared in example 5 of the present invention 2 /CeO 2 /In 2 S 3 The absorbance curve of the heterostructure for photodegradation of tetracycline under visible light; from FIG. 8, the degradation efficiency is 79.0% at 180 min;
FIG. 9 is a graph comparing the degradation of tetracycline by the photocatalytic materials prepared in the inventive examples 1, 2, 3, 4 and 5, and it can be seen from FIG. 9 that the degradation rate of example 3 is the highest at 180 min;
as can be seen from FIG. 10, TiO is produced in example 3 2 /CeO 2 /In 2 S 3 The heterostructure still keeps 84.7 percent of degradation rate in the experiment of four times of cyclic photodegradation of tetracycline, and the sample is proved to have better stability.
Claims (10)
1. TiO 2 2 /CeO 2 /In 2 S 3 Heterostructure characterized by the direct preparation of TiO by electrostatic spinning 2 /CeO 2 Nanofibers of In prepared by hydrothermal method 2 S 3 Nanosheet loading into TiO 2 /CeO 2 On the nano-fiber to obtain TiO 2 /CeO 2 /In 2 S 3 A heterostructure.
2. The TiO of claim 1 2 /CeO 2 /In 2 S 3 Heterostructure characterized in that said TiO is 2 /CeO 2 The diameter of the nanofiber is 90-110 nm.
3. The TiO of claim 1 2 /CeO 2 /In 2 S 3 The heterostructure is characterized In that In 2 S 3 The thickness of the nano-sheet is 10-15 nm.
4. According toThe TiO of claim 1 2 /CeO 2 /In 2 S 3 Heterostructure characterized in that said TiO is 2 /CeO 2 Nanofibers and In 2 S 3 In a molar ratio of 1: (0.3-0.6).
5. TiO according to any one of claims 1 to 4 2 /CeO 2 /In 2 S 3 The preparation method of the heterostructure is characterized by comprising the following specific steps:
(1) dissolving cerium nitrate and tetrabutyl titanate in a mixed solvent composed of DMF (dimethyl formamide) and anhydrous ethanol, wherein the molar ratio of Ti to Ce is 1: 0.13, adding acetic acid, adding polyvinylpyrrolidone (PVP), and uniformly stirring to obtain spinnable sol;
the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solvent is 1: 1; the weight average molecular weight of the polyvinylpyrrolidone is 4-300 ten thousand;
(2) electrostatic spinning the spinnable sol prepared in the step (1) to prepare precursor fiber;
performing electrostatic spinning on the spinnable precursor sol obtained in the step (1) under the conditions that the temperature is 15-35 ℃, the voltage is 10-30kV, and the ejection rate is 0.1-1.5mL/h to obtain precursor fiber;
(3) drying the precursor fiber prepared in the step (2) at 50-100 ℃ for 12-36h, heating to 500- 2 /CeO 2 A nanofiber;
(4) dissolving indium nitrate and thioacetamide in a mixed solvent consisting of deionized water and absolute ethyl alcohol, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 5: 1, stirring until the TiO is completely dissolved, and then adding the TiO prepared in the step (3) 2 /CeO 2 Nanofibers, TiO 2 /CeO 2 Nanofibers and In 2 S 3 In a molar ratio of 1: (0.3-0.6), stirring for 60 min;
(5) and (4) transferring the solution prepared in the step (4) into a hydrothermal reaction kettle, heating to 160 ℃, preserving heat for 12 hours, cooling to room temperature, then centrifugally washing, drying, and collecting a sample.
6. The production method according to claim 5, wherein the weight average molecular weight of the polyvinylpyrrolidone in the step (1) is 100 to 150 ten thousand.
7. The production method according to claim 6, wherein the weight average molecular weight of the polyvinylpyrrolidone in the step (1) is 130 ten thousand.
8. The production method according to claim 4, wherein the conditions of the electrospinning in the step (2): the spraying speed of the spinnable sol is 1.0mL/h, the voltage is 20kV, and the electrostatic spinning temperature is controlled at 25-30 ℃.
9. The preparation method according to claim 4, wherein the temperature in the step (3) is raised to 800 ℃ at a heating rate of 2 ℃/min, and the temperature is maintained for 120min to obtain TiO 2 /CeO 2 And (3) nano fibers.
10. TiO according to any one of claims 1 to 3 2 /CeO 2 /In 2 S 3 Use of a heterostructure for photocatalytic oxidative degradation of tetracycline.
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