CN110918125A - Preparation method of UiO-66 loaded tin sulfide nanoparticle photocatalyst - Google Patents
Preparation method of UiO-66 loaded tin sulfide nanoparticle photocatalyst Download PDFInfo
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- 239000013207 UiO-66 Substances 0.000 title claims abstract description 96
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 59
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012153 distilled water Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002798 polar solvent Substances 0.000 claims abstract description 16
- 150000003754 zirconium Chemical class 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000004729 solvothermal method Methods 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- 239000004098 Tetracycline Substances 0.000 description 17
- 229960002180 tetracycline Drugs 0.000 description 17
- 229930101283 tetracycline Natural products 0.000 description 17
- 235000019364 tetracycline Nutrition 0.000 description 17
- 150000003522 tetracyclines Chemical class 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 238000013032 photocatalytic reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 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
- 231100000331 toxic Toxicity 0.000 description 1
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- 210000002700 urine Anatomy 0.000 description 1
- 238000005303 weighing Methods 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
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/003—Wastewater from hospitals, laboratories and the like, heavily contaminated by pathogenic microorganisms
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- C—CHEMISTRY; METALLURGY
- 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 preparation method of UiO-66 loaded tin sulfide nanoparticle photocatalyst, which comprises the steps of firstly, taking zirconium salt and organic ligand as precursors, taking a polar solvent as a dispersing agent, and preparing regular octahedron UiO-66 white solid powder by adopting a solvothermal method; then, dispersing octahedral UiO-66 white solid powder into distilled water, and stirring at room temperature to form uniform milky white solution; sequentially adding a tin source and a sulfur source into the milky white solution, ultrasonically dissolving and stirring for 20-50 min, transferring the milky white solution into a polytetrafluoroethylene-lined high-pressure kettle, heating at a constant temperature, cooling to room temperature, and performing centrifugal separation to obtain orangeA product; finally, washing the orange product with absolute ethyl alcohol and distilled water in sequence, and drying overnight to obtain the UiO-66 loaded tin sulfide nanoparticle photocatalyst recorded as SnS2NPS@ UiO-66. The method has the advantages of simple operation, easily obtained raw materials and low cost, and the obtained photocatalyst has excellent photocatalytic degradation performance.
Description
Technical Field
The invention relates to the field of composite material science and the technical field of wastewater treatment, in particular to a preparation method of a UiO-66 loaded tin sulfide nanoparticle photocatalyst.
Background
Tetracycline (TC) is widely used as a broad spectrum antibiotic in the prevention of human and animal infections. Unfortunately, tetracycline that enters the human or animal body is only partially metabolized and the majority is excreted outside the body in the form of urine and feces. It has now been found that tetracycline is present in a variety of water bodies, which can cause significant environmental and human health damage. However, the traditional wastewater treatment method is too costly and time-consuming to effectively remove the residual antibiotics in the water. Therefore, there is a need to develop a new efficient, low cost, short cycle time and pollution-free method to reduce the antibiotic in wastewater. In order to solve this problem, photocatalysis has attracted much attention as a green chemical technology.
In recent years, in view of increasing energy crisis and environmental remediation, great interest has been drawn to the direct response and efficient use of visible light by semiconductor photocatalysts. Among the various semiconductor photocatalysts, metal sulfides have proven to be a class of highly efficient catalysts in photochemical reactions due to their appropriate band gaps and catalytic functions, such as CdS, SnS2、In2S3、MoS2、WS2、Bi2S3And the like. CdS is widely used for various photocatalytic materials due to excellent photocatalytic performance of CdS, but toxic heavy metal (Cd) is released into the environment2+) Thereby causing secondary pollution. At present, tin sulfide (SnS) which has similar band gap energy (2.0-2.5 eV) and is nontoxic and low in material production cost is used2) Instead of, therefore, SnS2Has become one of the promising photocatalysts. However, the rapid recombination of photoinduced electron-hole pairs severely reduces SnS2To promote SnS2Have reported related improved methods, such as: zhao Xiao Hua, etc. (CN 110038593A) TongThe hollow spherical C @ SnO for efficiently reducing Cr (VI) by photocatalysis is prepared by the methods of over-calcination and hydrothermal ion exchange2@SnS2The three-component compound, the synergistic effect of the three components and the appearance of the hollow structure enhance the absorption and utilization capacity of the three-component compound to visible light and promote the separation of photo-generated charges, and the adsorption capacity and the visible light catalytic degradation capacity of the three-component compound to Cr (VI) are obviously enhanced. Sun et al (Materials Chemistry and Physics, 2019, 229: 92-97) will SnS2The nano particles are loaded on the graphene sheet to prepare the photocatalytic material, and the combination of the nano particles and the graphene sheet effectively promotes the separation of photoinduced carriers, so that the photocatalytic capacity is enhanced, and the degradation rate of methyl orange in 120 min reaches 98.7%. However, since single nanoparticles are easily aggregated to form large particles, a reduction in specific surface area and a reduction in effective reaction sites are caused. Therefore, it is necessary to improve SnS2The dispersibility of the nanoparticles, and the selection of a suitable support matrix with a large specific surface area and an energy band structure, improve the photocatalytic activity and stability.
Metal Organic Frameworks (MOFs) are a new class of porous crystalline materials, and have many potential applications due to their unique physicochemical properties, high specific surface area, diverse structures, adjustable pore sizes, and the like. Some MOFs materials are considered promising candidates for photocatalysis due to the behavior of their semiconductors, however, most MOFs respond only to ultraviolet light, limiting their practical applications. Recently, MOFs materials are used as carriers to be combined with nanoparticles to construct heterojunction photocatalytic materials, which is an effective strategy for widening a light absorption range and reducing recombination of electron hole pairs. Among many MOFs, UiO-66(Zr) is widely explored as a very suitable support due to its extremely high thermal and chemical stability.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a UiO-66 loaded tin sulfide nanoparticle photocatalyst, which is simple to operate and low in cost.
In order to solve the problems, the preparation method of the UiO-66 loaded tin sulfide nanoparticle photocatalyst is characterized by comprising the following steps: first, theZirconium salt and an organic ligand are used as precursors, a polar solvent is used as a dispersing agent, and a solvothermal method is adopted to prepare octahedral UiO-66 white solid powder; then dispersing the octahedral UiO-66 white solid powder in distilled water according to the mass which is 20-100 times of that of the octahedral UiO-66 white solid powder, and stirring for 1 hour at room temperature to form uniform milky white solution; sequentially adding a tin source and a sulfur source into the milky white solution, ultrasonically dissolving and stirring for 20-50 min, transferring the milky white solution into an autoclave with a polytetrafluoroethylene lining, heating the milky white solution at a constant temperature of 150-200 ℃ for 10-18 h, cooling the milky white solution to room temperature, and performing centrifugal separation to obtain an orange product; and finally, washing the orange product with absolute ethyl alcohol and distilled water for 2-6 times, and drying at 60-100 ℃ overnight to obtain the UiO-66 loaded tin sulfide nanoparticle photocatalyst recorded as SnS2NPS@ UiO-66; the mass ratio of the regular octahedron UiO-66 white solid powder to the tin source is 1: 0.5-1: 1.5; the mass ratio of the tin source to the sulfur source is 1: 0.2-1: 1.5.
the octahedral UiO-66 white solid powder is prepared by the following preparation method:
⑴, dissolving a zirconium salt and an organic ligand in a polar solvent, stirring for 15-60 min, then dropwise adding acetic acid into the solution to adjust the form of UiO-66, and continuously stirring for 30-100 min to obtain a uniform solution, wherein the mass ratio of the zirconium salt to the organic ligand is 1: 0.5-1: 2.5, the mass volume ratio of the zirconium salt to the polar solvent is 1: 100-1: 600, and the volume ratio of the polar solvent to the acetic acid is 1: 0.05-1: 0.5;
⑵, heating the uniform solution at 100-120 ℃ for 18-36 h, cooling to room temperature, and performing centrifugal separation to obtain a white product;
⑶ washing the white product with distilled water and absolute ethyl alcohol for 2-6 times, and vacuum drying at 50-80 deg.C to constant weight.
The zirconium salt in the step ⑴ is ZrCl4、ZrOCl2·8H2O or Zr (NO)3)4·5H2And O is one of the compounds.
The organic ligand in step ⑴ refers to terephthalic acid or 2-amino terephthalic acid.
The polar solvent in the step ⑴ refers to N, N '-dimethylformamide or distilled water or a mixed solution of N, N' -dimethylformamide and distilled water.
The mixed solution of the N, N '-dimethylformamide and the distilled water is prepared by mixing the N, N' -dimethylformamide and the distilled water according to the weight ratio of 1: the obtained mixed solution was uniformly mixed at a volume ratio of 0.8.
The tin source is SnCl4·5H2O or SnCl2·2H2O。
The sulfur source is CH4N2S、CH3CSNH2Or Na2S·9H2And O is one of the compounds.
The centrifugal separation condition is that the rotating speed is 7500 rpm, and the time is 5 min; or the rotating speed is 8500 rpm, and the time is 10 min.
Compared with the prior art, the invention has the following advantages:
1. the preparation method takes zirconium salt and an organic ligand as precursors, takes a polar solvent as a dispersing agent, and adopts a solvothermal method to prepare the high-specific surface area (the specific surface area is 1045-1347 m)2After the octahedral UiO-66 of/g), the octahedral UiO-66 with high specific surface area is used as a carrier to load tin sulfide nano particles to prepare a novel heterojunction photocatalyst when SnS2When the nanoparticles are uniformly dispersed on the surface of the UiO-66, the UiO-66 with high surface area can provide more active sites and photocatalytic reaction centers, and simultaneously, the recombination of photo-excited charge carriers is effectively prevented through the synergistic effect between MOFs and semiconductor nanoparticles, so that the photocatalytic activity is improved.
2. The morphological and structural analysis of the octahedral UiO-66 load tin sulfide nanoparticle photocatalyst prepared by the invention can find that the edge angle of the UiO-66 crystal is more prominent, and the crystal size is increased to 3.7 times of the original crystal size under the condition of keeping the original octahedral crystal form, and the SnS2The nano particles are uniformly distributed on the surface of the octahedral UiO-66 crystal.
⑴ macro and micro topography:
the octahedral UiO-66 prepared by the invention is loaded and vulcanizedThe macroscopic morphology of the tin nanoparticle photocatalyst is shown in fig. 1. As can be seen, SnS2SnS formed after nano particles are loaded on octahedron UiO-662NPSThe @ UiO-66 composite material is an earthy yellow powdery particle, and has obviously darker color compared with pure UiO-66 and pure SnS2The color is lighter than that of the product, which shows that UiO-66 and SnS are successfully synthesized2The composite material of (1). Secondly, SnS2The change of the color from light to dark after the introduction also indicates the composite SnS to a certain extent2Can improve the absorption of UiO-66 to light, thereby being beneficial to the photocatalysis performance.
Scanning Electron Microscope (SEM) analysis is carried out on the n-octahedron UiO-66 load tin sulfide nanoparticle composite material, and SnS synthesized by a simple solvothermal method is further explored2NPSThe microstructure of the @ UiO-66 composite is shown in FIG. 2. Wherein A is Snless2Pure octahedron UiO-66 (contrast, one unit cell) prepared in the presence of the nanoparticles, wherein B is the octahedron UiO-66 loaded tin sulfide nanoparticles. As can be seen from the scanning electron microscope picture, SnS is added2After the nano-particles are formed, the crystal size of the UiO-66 is increased from the original 250 nm to about 925 nm, the edges and corners of the UiO-66 crystals are more prominent, but the crystal form of the UiO-66 crystals is clearly not changed, the regular octahedral structure is still formed, and SnS2The nanoparticles are distributed on each crystal plane of UiO-66. Description of UiO-66 and SnS2The octahedron UiO-66 load tin sulfide nano-particle composite photocatalytic material is effectively combined and successfully prepared.
⑵ Infrared Spectroscopy (FT-IR):
prepared SnS2NPS @ UiO-66 powder, tableted with potassium bromide, gave an infrared spectrum as shown in FIG. 3. In the figure, 3600-3200 cm-1The broad peak is ascribed to the absorption peak of the hydroxyl group (-OH) in water by stretching vibration. The positions of the UiO-66 absorption peaks correspond to 1704, 1596, 1506, 1391, 750 and 552 cm-1To (3). Wherein, 1704 cm-1The peak of (A) is attributed to the asymmetric stretching vibration peak of terephthalic acid, 1596, 1506 and 1391 cm-1The peak is due to the asymmetric elongation of the carbonyl group of the carboxylate radical in terephthalic acidPeak of contraction vibration and symmetrical expansion vibration, 750 cm-1Peak at (C-H) corresponds to C-H bending vibration of benzene ring, 552 cm-1The band in the vicinity belongs to Zr- (OC) asymmetric stretching vibration. SnS2The characteristic absorption peak of the nano-particles is located at 620 cm-1Here, corresponds to the vibration of the Sn — S bond. Thus, the infrared spectrum shows SnS2The nanoparticles are supported on UiO-66.
⑶ X-ray diffraction (XRD) analysis:
XRD analysis was performed on the prepared photocatalyst to determine SnS2NPSThe information on the crystal structure and crystallinity of the @ UiO-66 composite material is shown in FIG. 4. Characteristic diffraction peaks of UiO-66 appear at 2 θ =7.2 °, 8.5 °, 26 °, 31 °, 44 °, 50.5 ° and 57 °, corresponding to the (111), (200), (600), (731), (933), (955) and (1242) crystal planes of UiO-66 single crystal, respectively. SnS2The positions of the main characteristic diffraction peaks in the material occur at 2 θ =15 °, 28 °, 32 °, 50 ° and 53 °, corresponding to the (001), (100), (101), (110) and (111) crystal planes, respectively. The above characteristic diffraction peaks all appear in the composite material, which shows that SnS2NPSThe @ UiO-66 composite material is formed from UiO-66 and SnS2The components are as follows.
⑷ X-ray photoelectron spectroscopy (XPS) analysis:
the SnS prepared by the invention is further researched by adopting X-ray photoelectron spectroscopy (XPS)2NPSThe surface valence state and chemical composition of the @ UiO-66 composite. As can be seen from the XPS spectrum of fig. 5, the composite material is composed of Sn, S, Zr, C and O elements, i.e. contains: sn 3d, Sn 3p, S2 p, Zr 3d, Zr 3p, C1S (284.8 eV), O1S (532.1 eV), and the like. Wherein, two strong peaks with the binding energy of 486.8 eV and 495.1 eV respectively correspond to Sn 3d5/2And Sn 3d3/2. In addition, the secondary peaks of Sn at 1059.1, 758.3, 720.6 and 29.8 eV are attributed to Sn 3s, 3p, respectively1/2、3p3/2And 4 d. The two peaks at 233.2 and 164.54 eV are attributed to S2S and 2 p. These values and reported values are from SnS2Sn in (1)4+And S2-The binding energy values of (A) were consistent. Shown in the spectrogramShowing Zr 3d5/2And Zr 3d3/2Peaks appear at 182.8 eV and 185.3 eV, indicating the presence of Zr4+They are derived from zirconium in UiO-66. In short, the XPS analysis confirmed SnS2NPS@ UiO-66 SnS in composite material2And UiO-66.
3. The regular octahedron UiO-66 load tin sulfide nanoparticle photocatalyst prepared by the invention is subjected to photodegradation performance test, so that the photocatalyst shows excellent photocatalytic degradation performance on tetracycline, and has good application prospect in the field of photocatalytic degradation of medical wastewater.
In order to investigate the catalytic degradation performance of the octahedral UiO-66 supported tin sulfide nanoparticle photocatalyst, the degradation performance of the photocatalyst under visible light irradiation was tested by taking a common antibiotic (tetracycline) as a target degradation product. The method comprises the following specific steps: weighing 0.02g of photocatalyst, dispersing the photocatalyst into 20 mg/L tetracycline solution, carrying out dark reaction for 40 min to achieve adsorption and desorption balance, then carrying out magnetic stirring for 75 min under an 800 w xenon lamp light source, centrifuging 5 mL samples every 15 min, filtering supernatant liquid by using a 0.22 mu m filter membrane, measuring the concentration of residual tetracycline in the solution by adopting an ultraviolet-visible spectrophotometry method, namely measuring absorbance at 357 nm and calculating the removal rate.
The experimental result shows that the removal rate of the octahedral UiO-66 supported tin sulfide nanoparticle photocatalyst to tetracycline is only 38.7% after dark reaction for 40 min, and the removal rate reaches 89.8% after illumination for 75 min, as shown in FIG. 6. In order to illustrate the improvement of the performance of the composite photocatalyst, a control experiment is carried out, and the result shows that: under the same condition, the removal rate of the octahedral UiO-66 loaded tin sulfide nano particles to tetracycline is higher than that of pure SnS2And UiO-66 increased by 41.0% and 29.1%, respectively. The octahedron UiO-66 load tin sulfide nanoparticle photocatalyst has excellent catalytic degradation performance on tetracycline under the irradiation of visible light.
4. In the invention, UiO-66 and SnS2The interface which is in close contact with the photocatalyst is formed, so that the photocatalyst has excellent structural stability and multiple-cycle use performance. The results of the cycling experiments are shown in figure 7. Heavy metal through photocatalytic degradationAfter the renaturation experiment, the degradation rate of the octahedral UiO-66 loaded tin sulfide nanoparticle photocatalyst on tetracycline is not greatly reduced, the degradation rate can still reach 82.7% after four-cycle experiments, and is only reduced by 7% compared with that after the first photocatalytic degradation. In addition, FT-IR spectral analysis before and after the photocatalytic reaction is carried out on the photocatalytic material, and the characteristic peak is almost not observed to change, which shows that the photocatalytic degradation reaction has no obvious influence on the structure of the composite material.
5. The method has the advantages of simple operation, easily obtained raw materials and low cost.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a macro-morphology diagram of a regular octahedron UiO-66 load tin sulfide nanoparticle photocatalyst.
FIG. 2 is a micro-topography of the regular octahedron UiO-66 load tin sulfide nanoparticle photocatalyst of the invention.
FIG. 3 is a diagram of a normal octahedron UiO-66 load tin sulfide nanoparticle photocatalyst FT-IR.
FIG. 4 is an XRD pattern of the regular octahedron UiO-66 supported tin sulfide nanoparticle photocatalyst.
FIG. 5 shows XPS full spectrum and fine spectrum of octahedral UiO-66 supported tin sulfide nanoparticle photocatalyst.
FIG. 6 is a graph showing the degradation curve of the octahedron UiO-66 loaded tin sulfide nanoparticle photocatalyst of the present invention to tetracycline.
FIG. 7 is a diagram of the reusability of the octahedral UiO-66 supported tin sulfide nanoparticle photocatalyst of the present invention.
Detailed Description
Example 1 preparation of UiO-66 supported tin sulfide nanoparticle photocatalyst:
firstly, taking zirconium salt and an organic ligand as precursors, taking a polar solvent as a dispersing agent, and preparing octahedral UiO-66 white solid powder by adopting a solvothermal method. The specific process is as follows:
⑴ 0.5000 g ZrCl4And 02507 g of terephthalic acid is dissolved in 50 mL of N, N' -dimethylformamide and stirred for 35 min, then 2.5 mL of acetic acid is added dropwise to the solution to adjust the form of UiO-66, and stirring is continued for 70 min to obtain a uniform solution;
⑵ heating the homogeneous solution at 110 deg.C for 24 h, cooling to room temperature, and centrifuging at 7500 rpm for 5min to obtain white product;
⑶ washing the white product with distilled water and absolute ethyl alcohol for 3 times, and vacuum drying at 60 deg.C to constant weight.
Then 2.5000 g of octahedral UiO-66 white solid powder is dispersed in 50 mL of distilled water under stirring, and stirred for 1 hour at room temperature to form uniform milky white solution; 1.2505 g of SnCl were added to the milky white solution2·2H2O and 0.2503 g CH4N2And S, ultrasonically dissolving, stirring for 20 min, transferring to a polytetrafluoroethylene-lined high-pressure kettle, heating at the constant temperature of 160 ℃ for 18h, cooling to room temperature, and centrifugally separating at 7500 rpm for 5min to obtain an orange product.
Finally, washing the orange product with absolute ethyl alcohol and distilled water for 4 times, and drying in an oven at 70 ℃ overnight to obtain the UiO-66 loaded tin sulfide nanoparticle photocatalyst recorded as SnS2NPS@UiO-66。
The removal rate of the photocatalyst to tetracycline is 83.8%.
Example 2 preparation of UiO-66 supported tin sulfide nanoparticle photocatalyst:
firstly, taking zirconium salt and an organic ligand as precursors, taking a polar solvent as a dispersing agent, and preparing octahedral UiO-66 white solid powder by adopting a solvothermal method. The specific process is as follows:
⑴ 0.2009 g ZrOCl2·8H2Dissolving O and 0.2016 g 2-amino terephthalic acid in 60 mL distilled water, stirring for 15 min, then dropwise adding 12.0 mL acetic acid into the solution to adjust the form of UiO-66, and continuously stirring for 100 min to obtain a uniform solution;
⑵ heating the homogeneous solution at 120 deg.C for 36 h, cooling to room temperature, and centrifuging at 8500 rpm for 10min to obtain white product;
⑶ washing the white product with distilled water and absolute ethyl alcohol for 2 times, and vacuum drying at 60 deg.C to constant weight.
Then 1.2524 g of octahedral UiO-66 white solid powder is dispersed in 50 mL of distilled water under stirring, and stirred for 1 hour at room temperature to form uniform milky white solution; 0.8767 g of SnCl were added to the milky white solution4·5H2O and 0.4384 g CH3CSNH2Ultrasonically dissolving, stirring for 50 min, transferring into an autoclave with a polytetrafluoroethylene lining, heating at the constant temperature of 200 ℃ for 10 h, cooling to room temperature, and centrifuging at 8500 rpm for 10min to obtain an orange product.
Finally, washing the orange product with absolute ethyl alcohol and distilled water for 6 times, and drying in an oven at 60 ℃ overnight to obtain the UiO-66 loaded tin sulfide nanoparticle photocatalyst recorded as SnS2NPS@UiO-66。
The removal rate of the photocatalyst to tetracycline is 80.7%.
Example 3 preparation of UiO-66 supported tin sulfide nanoparticle photocatalyst:
firstly, taking zirconium salt and an organic ligand as precursors, taking a polar solvent as a dispersing agent, and preparing octahedral UiO-66 white solid powder by adopting a solvothermal method. The specific process is as follows:
⑴ mixing 0.0778 g Zr (NO)3)4·5H2Dissolving O and 0.1556 g 2-amino terephthalic acid in 35 mL of mixed solution of N, N' -dimethylformamide and distilled water, stirring for 60 min, then dropwise adding 12.3 mL of acetic acid into the solution to adjust the form of UiO-66, and continuously stirring for 30 min to obtain a uniform solution; the mixed solution of N, N '-dimethylformamide and distilled water is prepared by mixing N, N' -dimethylformamide and distilled water in a ratio of 1: uniformly mixing the obtained mixed solution in a volume ratio (mL/mL) of 0.8;
⑵ heating the homogeneous solution at 100 deg.C for 18h, cooling to room temperature, and centrifuging at 7500 rpm for 5min to obtain white product;
⑶ washing the white product with distilled water and absolute ethyl alcohol for 6 times, and vacuum drying at 80 deg.C to constant weight.
Then stirringDispersing 0.5625 g of white solid powder of octahedron UiO-66 in 45 mL of distilled water, and stirring for 1 hour at room temperature to form uniform milky white solution; 0.5631 g of SnCl were added to the milky white solution2·2H2O and 0.4505 g Na2S·9H2And O, ultrasonically dissolving, stirring for 40 min, transferring to an autoclave with a polytetrafluoroethylene lining, heating at the constant temperature of 150 ℃ for 18h, cooling to room temperature, and centrifuging at 7500 rpm for 5min to obtain an orange product.
Finally, washing the orange product with absolute ethyl alcohol and distilled water for 2 times, and drying in an oven at 100 ℃ overnight to obtain the UiO-66 loaded tin sulfide nanoparticle photocatalyst recorded as SnS2NPS@UiO-66。
The removal rate of tetracycline by the photocatalyst is 76.3%.
Example 4 preparation of UiO-66 supported tin sulfide nanoparticle photocatalyst:
firstly, taking zirconium salt and an organic ligand as precursors, taking a polar solvent as a dispersing agent, and preparing octahedral UiO-66 white solid powder by adopting a solvothermal method. The specific process is as follows:
⑴ 0.0833 g ZrCl40.2083 g of terephthalic acid is dissolved in 50 mL of N, N' -dimethylformamide and stirred for 30 min, then 25 mL of acetic acid is dropwise added into the solution to adjust the form of UiO-66, and stirring is continued for 60 min to obtain a uniform solution;
⑵ heating the homogeneous solution at 120 deg.C for 24 h, cooling to room temperature, and centrifuging at 8500 rpm for 10min to obtain white product;
⑶ washing the white product with distilled water and absolute ethyl alcohol for 3 times, and vacuum drying at 50 deg.C to constant weight.
Then, 0.1503 g of octahedral UiO-66 white solid powder is dispersed in 15 mL of distilled water under stirring, and stirred for 1 hour at room temperature to form uniform milky white solution; 0.2255 g of SnCl were added to the milky white solution4·5H2O and 0.3382 g CH3CSNH2Ultrasonic dissolving, stirring for 30 min, transferring into autoclave with polytetrafluoroethylene lining, heating at 180 deg.C for 12 hr, cooling to room temperature, and 8500 rpm centrifugation for 10min gave an orange product.
Finally, washing the orange product with absolute ethyl alcohol and distilled water for 3 times, and drying in an oven at 80 ℃ overnight to obtain the UiO-66 loaded tin sulfide nanoparticle photocatalyst recorded as SnS2NPS@UiO-66。
The removal rate of the photocatalyst to tetracycline is 88.6%.
Claims (9)
- A preparation method of UiO-66 loaded tin sulfide nanoparticle photocatalyst is characterized by comprising the following steps: firstly, taking zirconium salt and an organic ligand as precursors and a polar solvent as a dispersing agent, and preparing octahedral UiO-66 white solid powder by a solvothermal method; then dispersing the octahedral UiO-66 white solid powder in distilled water according to the mass which is 20-100 times of that of the octahedral UiO-66 white solid powder, and stirring for 1 hour at room temperature to form uniform milky white solution; sequentially adding a tin source and a sulfur source into the milky white solution, ultrasonically dissolving and stirring for 20-50 min, transferring the milky white solution into an autoclave with a polytetrafluoroethylene lining, heating the milky white solution at a constant temperature of 150-200 ℃ for 10-18 h, cooling the milky white solution to room temperature, and performing centrifugal separation to obtain an orange product; and finally, washing the orange product with absolute ethyl alcohol and distilled water for 2-6 times, and drying at 60-100 ℃ overnight to obtain the UiO-66 loaded tin sulfide nanoparticle photocatalyst recorded as SnS2NPS@ UiO-66; the mass ratio of the regular octahedron UiO-66 white solid powder to the tin source is 1: 0.5-1: 1.5; the mass ratio of the tin source to the sulfur source is 1: 0.2-1: 1.5.
- 2. the method of claim 1 for preparing a UiO-66 supported tin sulfide nanoparticle photocatalyst, wherein: the octahedral UiO-66 white solid powder is prepared by the following preparation method:⑴, dissolving a zirconium salt and an organic ligand in a polar solvent, stirring for 15-60 min, then dropwise adding acetic acid into the solution to adjust the form of UiO-66, and continuously stirring for 30-100 min to obtain a uniform solution, wherein the mass ratio of the zirconium salt to the organic ligand is 1: 0.5-1: 2.5, the mass volume ratio of the zirconium salt to the polar solvent is 1: 100-1: 600, and the volume ratio of the polar solvent to the acetic acid is 1: 0.05-1: 0.5;⑵, heating the uniform solution at 100-120 ℃ for 18-36 h, cooling to room temperature, and performing centrifugal separation to obtain a white product;⑶ washing the white product with distilled water and absolute ethyl alcohol for 2-6 times, and vacuum drying at 50-80 deg.C to constant weight.
- 3. The method for preparing UiO-66 supported tin sulfide nanoparticle photocatalyst as claimed in claim 2, wherein the zirconium salt in the step ⑴ is ZrCl4、ZrOCl2·8H2O or Zr (NO)3)4·5H2And O is one of the compounds.
- 4. The method for preparing the UiO-66 supported tin sulfide nanoparticle photocatalyst of claim 2, wherein the organic ligand in the step ⑴ is terephthalic acid or 2-amino terephthalic acid.
- 5. The method for preparing the UiO-66 supported tin sulfide nanoparticle photocatalyst of claim 2, wherein the polar solvent in the step ⑴ is N, N '-dimethylformamide or distilled water or a mixture of N, N' -dimethylformamide and distilled water.
- 6. The method of claim 5, wherein the preparation of the UiO-66 supported tin sulfide nanoparticle photocatalyst comprises: the mixed solution of the N, N '-dimethylformamide and the distilled water is prepared by mixing the N, N' -dimethylformamide and the distilled water according to the weight ratio of 1: the obtained mixed solution was uniformly mixed at a volume ratio of 0.8.
- 7. The method of claim 1 for preparing a UiO-66 supported tin sulfide nanoparticle photocatalyst, wherein: the tin source is SnCl4·5H2O or SnCl2·2H2O。
- 8. As claimed inThe preparation method of the UiO-66 loaded tin sulfide nanoparticle photocatalyst in the claim 1 is characterized by comprising the following steps: the sulfur source is CH4N2S、CH3CSNH2Or Na2S·9H2And O is one of the compounds.
- 9. A method of preparing the UiO-66 supported tin sulfide nanoparticle photocatalyst of claim 1 or 2, wherein: the centrifugal separation condition is that the rotating speed is 7500 rpm, and the time is 5 min; or the rotating speed is 8500 rpm, and the time is 10 min.
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