CN113304783B - Tin-based metal-organic framework photocatalytic material and preparation method and application thereof - Google Patents
Tin-based metal-organic framework photocatalytic material and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 62
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 50
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 239000013110 organic ligand Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006303 photolysis reaction Methods 0.000 claims description 7
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 6
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 6
- 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
- 238000001035 drying Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 239000003513 alkali 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
- 230000031700 light absorption Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 239000003242 anti bacterial agent Substances 0.000 description 9
- 229940088710 antibiotic agent Drugs 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000006213 oxygenation reaction Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000001782 photodegradation Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000013206 MIL-53 Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012984 antibiotic solution Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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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
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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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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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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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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
The invention discloses a tin-based metal-organic framework photocatalytic material and a preparation method thereof, wherein the material is a tin-based metal-organic framework (Sn-MOF), and the Sn-MOF is Sn-TPA, sn-DHTPA, sn-TPA-NH2Or Sn-TPA-NO2. The crystal structure of the Sn-DHTPA is a tetragonal system, the space group is P-421c, and the empirical molecular formula is H4O8Sn6Unit cell parameters a =7.9268 a, b =7.926 a, c =9.1025, α =90, β =90, γ =90, density of 4.9g/cm3Volume of 571.95A3(ii) a The Sn-DHTPA is of a rod-shaped structure, the length of the Sn-DHTPA is 7-9 mu m, and the diameter of the Sn-DHTPA is 1-2 mu m; sn in the Sn-DHTPA is Sn4+/Sn2+Mixed valence state, conductivity of 0.8-1.0 S.m‑1. The Sn-TPA is a two-dimensional sheet structure, the diameter is 4-5 mu m, and the thickness is 0.3-0.5 mu m. The Sn-TPA-NH2Has a two-dimensional sheet stack structure and a thickness of 0.04-0.08 μm. The Sn-MOF shows excellent visible light absorption performance and good conductivity, and can effectively decompose water to generate oxygen and degrade organic matters and the like. The preparation method is simple, mild in condition, simple to operate, low in cost, beneficial to large-scale production and has a certain application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to a tin-based metal-organic framework photocatalytic material, and a preparation method and application thereof.
Background
The chemical industry relying on fossil resources brings about serious problems of resource shortage and environmental pollution while promoting the development and progress of society. The semiconductor photocatalysis technology is combined with renewable energy source solar energy, is expected to realize the raw material-energy-chemical conversion of green, harmonious and sustainable development, is one of effective ways for solving two problems at the same time, and is concerned with. The development of the high-efficiency wide-spectrum-response photocatalytic material is the key, and is an urgent requirement for realizing the medium-and-long-term scientific and technical development planning of the country and promoting the development of the strategic emerging industry of the country.
The metal-organic framework (MOF) material is a crystalline porous material with a periodic network structure formed by covalent coordination of organic ligands and inorganic metal ions or ion clusters, has good designability and tailorability, can obtain the excellent characteristics of adjustable structure, modifiable pore channels, porosity, ultrahigh specific surface area, rich chemical functionalization approaches and the like through reasonable design of the organic ligands and selection of metal centers/metal clusters, and has potential application in various fields such as storage, adsorption/separation, energy storage, drug delivery and the like. Based on the above advantages, MOF is also considered as a potential photocatalytic material, such as MOF-5, MIL-53 (Fe), ZIF-8, etc. are used for degrading organic matters (CN 201910479376.8); NH2MIL-125 (Ti), ZIF-8, etc. were used to reduce Cr (VI) (CN 201811392251.3); uiO-66, ti-MOF-NH2And the like are used for producing hydrogen (DOI: 10.1039/c3ee40507 a); uiO-67, MIL-53 (Fe), etc. were used to reduce carbon dioxide (DOI: 10.1021/ja203564 w). Most of the MOFs are good ultraviolet light catalytic materials, and researchers at home and abroad perform functional modification-NH on organic ligands of the MOFs2After the group is formed, the visible light absorption range can be effectively expanded, and the visible light catalytic activity is improved. However, there are still many issues to be solved by the application of MOFs in photocatalysis so far, such as: narrow visible light response range, low conductivity, low separation and mobility of photon-generated carriers, poor stability, complex preparation process, low catalytic activity and the like. Therefore, the method further expands the visible light absorption range of the MOFs material, simultaneously inhibits the recombination of photon-generated carriers, and is an urgent task for exploring the MOFs photocatalytic material with high efficiency and wide spectral response.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a tin-based metal-organic framework photocatalytic material as well as a preparation method and application thereof. The tin-based metal-organic framework Sn-MOF photocatalytic material has good visible light absorption performance, and has good activities of decomposing water to produce oxygen, degrading organic antibiotics and the like under the irradiation of visible light. The hydrothermal method adopted by the invention has the advantages of simple preparation method, convenient operation, low cost and the like, and is suitable for industrial production.
The specific technical scheme for realizing the purpose of the invention is as follows:
a preparation method of a tin-based metal-organic framework photocatalytic material comprises the following specific steps:
step 1: dispersing inorganic base and organic ligand in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution A;
step 2: dispersing a tin source in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution B;
and 3, step 3: dropwise adding the solution B into the solution A at a constant speed, and uniformly stirring to obtain a uniform mixed solution; heating the mixed solution to 70-110 ℃, reacting at constant temperature for 1-3 h, then cooling to room temperature, continuing stirring for 5-8h, centrifuging, cleaning, and drying in vacuum to obtain the tin-based metal-organic framework photocatalytic material; wherein:
the inorganic alkali is at least one of sodium hydroxide and potassium hydroxide; the organic ligand is at least one of 2,5-dihydroxy-terephthalic acid, 2-amino-terephthalic acid and 2-nitro-terephthalic acid; the tin source is SnSO4、SnCl2、SnCl4At least one of (a);
the concentration of the inorganic base is 0.06-0.1mol/l; the concentration of the organic ligand is 0.02-0.05mol/l; the concentration of the tin source is 0.2-0.3mol/l.
A tin-based metal-organic framework photocatalytic material prepared by the method.
The photocatalytic material is a Sn-MOF material which is a Sn-based metal-organic framework, and the Sn-MOF material is Sn-TPA, sn-DHTPA or Sn-TPA-NH2Or Sn-TPA-NO2。
The crystal structure of the Sn-DHTPA is a tetragonal system, the space group is P-421c, and the empirical molecular formula is H4O8Sn6Cell parameter of
c =9.1025, α =90, β =90, γ =90, density of 4.9g/cm3Volume is
The structure is a rod-shaped structure, the length of the rod is 7-9 mu m, and the diameter of the rod is 1-2 mu m; in the structure, sn is Sn4+/Sn2+Mixed valence state, conductivity of 0.8-1.0 S.m-1。
The Sn-TPA is a two-dimensional sheet structure, the diameter is 4-5 mu m, and the thickness is 0.3-0.5 mu m.
The Sn-TPA-NH2The two-dimensional sheet stacking structure is adopted, and the thickness of the sheet is 0.04-0.08 μm.
The application of the tin-based metal-organic framework photocatalytic material is to use the photocatalytic material for photolysis of water to produce oxygen and degrade organic matters.
The Sn-MOF photocatalytic material provided by the invention has the characteristics of unique porous structure, adjustable pore size, better conductivity and visible light absorption performance, high stability and the like, can be used as a potential broad-spectrum response photocatalytic material, and shows excellent photocatalytic activity when water is decomposed to generate oxygen and organic pollutants are degraded.
Specifically, the preparation method of the Sn-MOF photocatalytic material can adopt the following steps:
firstly, dispersing 0.024mol of NaOH and 0.012mol of 2, 5-dihydroxy-terephthalic acid in 300ml of deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution A;
in the second step, 0.015mol of SnSO is added4Dispersing in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution B;
thirdly, dropwise adding the solution B into the solution A at a constant speed, and uniformly stirring to obtain a uniform mixed solution; and heating the mixed solution to 90 ℃, reacting for 1h at constant temperature, then cooling to room temperature, continuing stirring for 6h, centrifuging, cleaning, and drying in vacuum at 120 ℃ to obtain the Sn-DHTPA MOF photocatalytic material.
Or in the first step, the organic ligand is changed into terephthalic acid, 2-amino-terephthalic acid and 2-nitro-terephthalic acid to obtain Sn-TPA and Sn-TPA-NH2、Sn-TPA-NO2A MOF photocatalytic material.
The preparation method can prepare various products in one method, and the MOF groups and the porous forms are controlled by adjusting the types of the organic ligand materials to obtain the porous Sn-MOF photocatalytic material modified by different groups so as to meet different requirements. The preparation method is simple, the conditions are mild, the operation is convenient, the cost is low, and the prepared material has high-efficiency photocatalytic activity and is suitable for industrial production, popularization and application.
Drawings
FIG. 1 is an X-ray diffraction pattern of Sn-DHTPA MOF synthesized in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of Sn-DHTPA MOF synthesized in example 1 and Sn-TPA MOF synthesized in example 2 according to the present invention;
FIG. 3 is a high resolution X photoelectron spectrum of Sn in Sn-DHTPA MOF synthesized in example 1 of the present invention;
FIG. 4 shows Sn-DHTPA, sn-TPA-NH synthesized in examples 1 to 4 of the present invention2、Sn-TPA-NO2A light absorption spectrum of the MOF;
FIG. 5 shows Sn-DHTPA, sn-TPA-NH synthesized in examples 1 to 4 of the present invention2、Sn-TPA-NO2A graph of the photocatalytic degradation antibiotic efficiency of MOFs;
FIG. 6 shows Sn-DHTPA, sn-TPA-NH synthesized in examples 1 to 4 of the present invention2、Sn-TPA-NO2Photo-decomposition of MOFs yielded a map of oxygen efficiency.
Detailed Description
The technical scheme of the invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, various changes or modifications may be made by one skilled in the art after reading the disclosure of the present invention, and equivalents may fall within the scope of the invention as defined by the claims appended hereto.
Example 1
Dispersing 0.024mol of NaOH and 0.012mol of 2, 5-dicarboxy-terephthalic acid in 300ml of deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution A; adding 0.015mol of SnSO4Dispersing in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution B; dropwise adding the solution B into the solution A at a constant speed, and uniformly stirring to obtain a uniform mixed solution; and heating the mixed solution to 90 ℃, reacting for 1h at constant temperature, then cooling to room temperature, continuing stirring for 6h, centrifuging, cleaning, and drying in vacuum at 120 ℃ to obtain the Sn-DHTPA MOF photocatalytic material.
The test method is as follows: the photocatalytic activity of the prepared Sn-DHTPA MOF photocatalytic material in the processes of photolysis of water to produce oxygen and photodegradation of antibiotics is characterized.
The process of photocatalytic water decomposition to produce oxygen: adding the prepared Sn-DHTPA MOF photocatalytic material (1 g/l) into 100ml of 30% electronic trapping agent solution, transferring the solution into a 200ml sealed glass reactor, vacuumizing, enabling the pressure to be-0.1 MPa, carrying out dark reaction for 30 minutes under the condition of magnetic stirring, and turning on a xenon lamp light source to carry out photocatalytic reaction. The product content was analyzed on-line at intervals by gas chromatography.
The process of photocatalytic degradation of antibiotics: adding the prepared Sn-DHTPA MOF photocatalytic material (1 g/l) into 50mg/l antibiotic solution (50 ml), carrying out dark reaction for 30 minutes under the condition of magnetic stirring, turning on a xenon lamp light source, and placing the material with the cut-off wavelength of 400nm (serving as a visible light source) when using a xenon lamp to carry out photocatalytic reaction. A certain amount of antibiotic solution is taken at intervals, an ultraviolet-visible spectrophotometer is used for testing the absorption spectrum of the solution, and the degradation rate of the antibiotic can be calculated through the change of the intensity of an absorption peak.
Example 2
0.024mol of NaOH and 0.012mol of terephthalic acid are dispersed in 300ml of deionized water, and are subjected to ultrasonic treatment and normal temperature stirring to obtain uniform mixtureSolution A; 0.015mol of SnSO4Dispersing in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution B; dropwise adding the solution B into the solution A at a constant speed, and uniformly stirring to obtain a uniform mixed solution; and heating the mixed solution to 90 ℃, reacting for 1h at constant temperature, then cooling to room temperature, continuing stirring for 6h, centrifuging, cleaning, and vacuum drying at 120 ℃ to obtain the Sn-TPA MOF photocatalytic material.
The photocatalytic activity of the photocatalytic material prepared by the embodiment in the processes of photolysis of water to produce oxygen and photodegradation of antibiotics is tested by the test method described in the embodiment 1.
Example 3
Dispersing 0.024mol of NaOH and 0.012mol of 2-amino-terephthalic acid in 300ml of deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution A; 0.015mol of SnSO4Dispersing in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution B; dropwise adding the solution B into the solution A at a constant speed, and uniformly stirring to obtain a uniform mixed solution; heating the mixed solution to 90 ℃, reacting at constant temperature for 1h, then cooling to room temperature, continuing stirring for 6h, centrifuging, cleaning, and vacuum drying at 120 ℃ to obtain Sn-TPA-NH2A MOF photocatalytic material.
The photocatalytic activity of the photocatalytic material prepared by the embodiment in the processes of photolysis of water to produce oxygen and photodegradation of antibiotics is tested by the test method described in the embodiment 1.
Example 4
Dispersing 0.024mol of NaOH and 0.012mol of 2-nitro-terephthalic acid in 300ml of deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution A; adding 0.015mol of SnSO4Dispersing in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution B; dropwise adding the solution B into the solution A at a constant speed, and uniformly stirring to obtain a uniform mixed solution; heating the mixed solution to 90 ℃, reacting at constant temperature for 1h, then cooling to room temperature, continuing stirring for 6h, centrifuging, cleaning, and vacuum drying at 120 ℃ to obtain Sn-TPA-NO2A MOF photocatalytic material.
The photocatalytic activity of the photocatalytic material prepared by the embodiment in the processes of photolysis of water to produce oxygen and photodegradation of antibiotics is tested by the test method described in the embodiment 1.
FIG. 1 is an X-ray diffraction pattern of Sn-DHTPA MOF synthesized in example 1 of the present invention. As shown in fig. 1, sn-DHTPA MOF exhibited strong diffraction peaks, indicating that it has good crystallinity. Based on Le Bail fitting, we obtained: the crystal structure of the Sn-DHTPA is tetragonal system, the space group is P-421c, and the empirical formula is H4O8Sn6Cell parameter of
c =9.1025, α =90, β =90, γ =90, density of 4.9g/cm3Volume is
FIG. 2 (a) is a scanning electron micrograph of Sn-DHTPAMAF synthesized in example 1 of the present invention. As can be seen from the figure, sn-DHTPA MOF is a rod-shaped structure, the length of the rod is 8 μm, and the diameter of the rod is 1.5 μm. FIG. 2 (b) is a scanning electron micrograph of Sn-TPA MOF synthesized in example 2 of the present invention. As can be seen from the figure, sn-TPA is a two-dimensional sheet structure, the sheet size is 4 to 5 μm, and the thickness is 0.4 μm.
FIG. 3 is a high resolution X photoelectron spectrum of Sn in Sn-DHTPA MOF synthesized in example 1 of the present invention. As can be seen from the figure, sn is tin4+/Sn2+Mixed valence states. The peaks at 495.4 and 486.9eV correspond to Sn 3d, respectively5/2And Sn 3d3/2of Sn4+. The peaks at 494.7 and 486.3eV correspond to Sn 3d, respectively5/2And Sn 3d3/2of Sn2+。
FIG. 4 shows Sn-DHTPA, sn-TPA-NH synthesized in examples 1 to 4 of the present invention2、Sn-TPA-NO2Light absorption spectrum of (a). As can be seen from the figure, all the Sn-MOF photocatalytic materials have strong light absorption in the visible light region and can be used as an efficient wide-spectrum response photocatalytic material. The organic ligand group can regulate and control the visible light absorption range of the Sn-MOF photocatalytic material, and compared with Sn-TPA MOF obtained by taking terephthalic acid as an organic ligand, the Sn-TPA MOF photocatalyst is 2,5-dicarboxy-terephthalic acid organicThe ligand-regulated Sn-DHTPA MOF photocatalytic material has the strongest light absorption in a visible light region, and the photocatalytic performance is favorable.
FIG. 5 shows Sn-DHTPA, sn-TPA-NH synthesized in examples 1 to 4 of the present invention2、Sn-TPA-NO2Graph of the efficiency of photocatalytic degradation of antibiotics. As can be seen from the figure, the photocatalytic activity is significantly improved with the increase of the light irradiation time. Under the irradiation of visible light, sn-DHTPA, sn-TPA-NH2、Sn-TPA-NO2The degradation rates for antibiotics were 80%, 50%, 74% and 67%, respectively. Therefore, compared with Sn-TPA, the effect of the Sn-MOF optimized by the organic ligand based on the radicals in the photocatalytic degradation of antibiotics is obviously improved.
FIG. 6 shows Sn-DHTPA, sn-TPA-NH synthesized in examples 1 to 4 of the present invention2、Sn-TPA-NO2The oxygen efficiency map of the photo-decomposed water. As can be seen from the figure, the oxygen content increases significantly with increasing light exposure time. Sn-DHTPA, sn-TPA-NH2、Sn-TPA-NO2The average yields of oxygen of (a) are 586, 186, 365 and 264. Mu. Mol. H, respectively-1·g-1. Therefore, compared with Sn-TPA, the effect of the Sn-MOF optimized by the organic ligand based on the radicals in the process of photocatalytic decomposition of water to generate oxygen is obviously improved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, and is provided for illustration and description. 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 (5)
1. The application of the tin-based metal-organic framework photocatalytic material in the photolysis of water to produce oxygen is characterized in that the preparation method of the photocatalytic material comprises the following specific steps:
step 1: dispersing inorganic base and organic ligand in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution A;
step 2: dispersing a tin source in deionized water, performing ultrasonic treatment and stirring at normal temperature to obtain a uniform mixed solution B;
and 3, step 3: dropwise adding the solution B into the solution A at a constant speed, and uniformly stirring to obtain a uniform mixed solution; heating the mixed solution to 70-110 ℃, reacting at constant temperature for 1-3 h, then cooling to room temperature, continuing stirring for 5-8h, centrifuging, cleaning, and drying in vacuum to obtain the tin-based metal-organic framework photocatalytic material; wherein:
the inorganic alkali is at least one of sodium hydroxide and potassium hydroxide; the organic ligand is at least one of 2,5-dihydroxy-terephthalic acid, 2-amino-terephthalic acid and 2-nitro-terephthalic acid; the tin source is SnSO4、SnCl2、SnCl4At least one of;
the concentration of the inorganic base is 0.06-0.1mol/L; the concentration of the organic ligand is 0.02-0.05mol/L; the concentration of the tin source is 0.2-0.3mol/L.
2. Use according to claim 1, wherein the photocatalytic material is a tin-based metal-organic framework (Sn-MOF) material, in particular Sn-TPA, sn-DHTPA, sn-TPA-NH2Or Sn-TPA-NO2。
3. The use according to claim 2, wherein the crystalline structure of Sn-DHTPA is tetragonal, the spatial group is P-421c, the unit cell parameters are a =7.9268 a, b =7.926, c =9.1025 a, α =90 °, β =90 °, γ =90 °, and the density is 4.9g/cm3Volume of 571.95A3(ii) a The structure is a rod-shaped structure, the length of the rod is 7-9 mu m, and the diameter of the rod is 1-2 mu m; in the structure, sn is Sn4+/Sn2+Mixed valence state, conductivity of 0.8-1.0 S.m-1。
4. Use according to claim 2, wherein the Sn-TPA is a two-dimensional sheet structure having a diameter of 4~5 μm and a thickness of 0.3-0.5 μm.
5. Use according to claim 2, wherein the Sn-TPA-NH is2The two-dimensional sheet stacking structure is adopted, and the sheet thickness is 0.04-0.08 μm.
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