CN111804344B - Calixarene-based titanium oxide cluster compound, preparation method thereof and application thereof in dye photodegradation - Google Patents
Calixarene-based titanium oxide cluster compound, preparation method thereof and application thereof in dye photodegradation Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000001782 photodegradation Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 title abstract description 15
- 239000002178 crystalline material Substances 0.000 claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 6
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 8
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 24
- 239000013077 target material Substances 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000012442 analytical experiment Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J31/226—Sulfur, e.g. thiocarbamates
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Abstract
A method for preparing a calixarene-based titanium oxide cluster, comprising: ligand H 4 BTC4A, sodium nitrate and isopropyl titanate are added into a mixed solution composed of N, N-dimethylacetamide and methanol, the mixed solution is heated and reacted for a period of time in a reaction kettle after being uniformly mixed, colorless block-shaped transparent crystals are obtained, and the transparent crystals are cleaned, filtered and dried to obtain the calixarene-based titanium oxide cluster crystalline material. The titanium-oxygen cluster compound crystalline material of the invention is a kind of crystalline material with Ti 2 Na 4 The core titanium-oxygen cluster compound has good stability and can be stored in the air for a long time; the forbidden band width is low; the synthesis method is simple and rapid, low in cost, high in yield, high in repeatability and easy to produce, popularize and use in mass production; the titanium oxide cluster crystalline material can drive the photodegradation of dye molecules under the irradiation of sunlight, and has important significance for the treatment of the dye molecules in industrial wastewater.
Description
Technical Field
The invention relates to a titanium oxygen cluster crystalline material, in particular to a titanium oxygen cluster based on calixarene, a preparation method thereof and application thereof in dye photodegradation.
Background
Titanium-oxygen clusters (TOCs) are a class of Titanium metal oxygen clusters formed around a plurality of Titanium atoms, the central Titanium atom being bonded to a neutral or other form of oxygen atom in a ligand by a coordinate bond. Compared with titanium dioxide, the titanium oxide cluster compound has the advantages of rich and various structures, adjustable and controllable performance and the like, and has good application prospects in the fields of photocatalysis, photodegradation and the like. In recent years, titanium oxide materials have become one of the research hotspots in the scientific community, and research on the use of titanium oxide cluster crystalline materials for the photodegradation of dye molecules has been advanced. Compared with the traditional physical adsorption dye molecule, the photodegradable dye molecule has the characteristics of simple operation, short reaction time, low treatment cost and the like. However, the titanium dioxide has the characteristics of single structure, high forbidden bandwidth and the like, so that the application of the titanium dioxide in the molecular direction of the photodegradable dye is severely limited. And the titanium-oxygen cluster compound with titanium-oxygen cluster inner core and lower forbidden band width begins to expose the head angle in the direction of the photodegradable dye molecules.
With the rapid development of industry, environmental issues have become one of the most interesting issues. Especially, the rapid development of the dye industry and the printing and dyeing industry, the variety and the amount of the dye discharged into the water body are increasing. Since industrial dyes are basically organic dyes, such dyes have high toxicity, deep chromaticity and difficult degradation, and pose serious threats to human health after being discharged into water, people begin to research a process method for treating dye wastewater. The traditional treatment methods such as an adsorption method, a biological oxidation method and the like have poor treatment effects and cannot achieve the aim of complete treatment. Since the success of the experiments in which titanium dioxide has been used for photocatalytic dye molecules, a great deal of research has been focused in recent years on the modification of titanium dioxide and its photocatalytic degradation of dye wastewater. In view of the harm of the pollution of dye molecules to human bodies, the development of a titanium oxide cluster crystalline material which can photodegrade the dye molecules under natural light with low cost and high efficiency is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a calixarene-based titanium oxide cluster crystalline material with good stability, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a calixarene-based titanium oxide cluster crystalline material comprises the following steps: ligand H 4 BTC4A, sodium nitrate and isopropyl titanate are added into a mixed solution composed of N, N-dimethylacetamide and methanol, the mixed solution is heated and reacted for a period of time in a reaction kettle after being uniformly mixed, colorless block-shaped transparent crystals are obtained, and the transparent crystals are cleaned, filtered and dried to obtain the calixarene-based titanium oxide cluster crystalline material.
Preferably, said H 4 The molar ratio of BTC4A, sodium nitrate and isopropyl titanate is 1:6：100。
preferably, the volume ratio of the N, N-dimethylacetamide to the methanol is 4:2.
preferably, the reaction kettle is a polytetrafluoroethylene reaction kettle, the heating temperature is 80 ℃, and the reaction time is 5 days.
The invention also provides a calixarene-based titanium oxide cluster crystalline material prepared by the preparation method.
The invention also provides application of the calixarene-based titanium oxide cluster crystalline material in dye molecule photodegradation.
Preferably, the application specifically includes: under the condition of solar irradiation, a calixarene-based titanium oxide cluster crystalline material was added to a solution containing methylene blue.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a titanium-oxygen cluster compound crystalline material which is a titanium-oxygen cluster compound crystalline material 2 Na 4 The core titanium-oxygen cluster compound has good stability and can be stored in the air for a long time; the forbidden band width is low;
the synthesis method is simple and rapid, low in cost, high in yield, high in repeatability and easy to produce, popularize and use in mass production;
the titanium oxide cluster crystalline material can drive the photodegradation of dye molecules under the irradiation of sunlight, and has important significance for the treatment of the dye molecules in industrial wastewater.
Drawings
FIG. 1 shows a powder diffraction characterization pattern of sample purity and air stability of a calixarene-based titanyl cluster compound;
FIG. 2 is a molecular structure diagram showing a calixarene-based titanium oxide cluster;
FIG. 3 shows a thermal stability characterization map of a calixarene-based titanyl cluster compound;
fig. 4 shows a band gap characterization map of a calixarene-based titanium oxide cluster compound;
FIG. 5 shows the photodegradation of the dye molecule methylene blue by titanium dioxide (a) and a crystalline material of a calixarene-based titanium oxide cluster (b) under solar irradiation.
The specific implementation mode is as follows:
the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation of crystalline Material of titanium oxide Cluster Compound
36mg (0.05 mmol) of organic ligand p-tert-butylthiaacilix [4 ] were weighed out separately]arene (abbreviated as H) 4 BTC 4A), 26mg (0.3 mmol) of sodium nitrate and 0.5mL (5 mmol) of isopropyl titanate are put in a polytetrafluoroethylene inner container, 4mL of N, N-dimethylacetamide and 2mL of methanol are added into the mixture, after uniform mixing is carried out for 1 hour by ultrasonic treatment, the polytetrafluoroethylene inner container is put in a stainless steel reaction kettle jacket and screwed down, the stainless steel reaction kettle jacket is put in a constant temperature oven at 80 ℃ for reaction for 5 days, the stainless steel reaction kettle jacket is taken out and naturally cooled to room temperature, and the polytetrafluoroethylene inner container is opened to obtain colorless blocky transparent crystals. Washing the crystal with distilled water, filtering to collect crystal, and air drying at room temperature to obtain crystalline titanium oxide cluster material with molecular formula of [ Ti 2 Na 4 (BTC4A) 2 (μ 6 -O 2- )(CH 3 O - ) 2 ·2H 2 O·2DMA]。
Example 2 structural characterization of titanium oxide Cluster Compound crystalline Material
The crystal structure of the target material was resolved using X-ray single crystal diffraction data, and the sample purity and air stability were characterized using X-ray powder diffraction (fig. 1). The single crystal test result shows that the target material is crystallized in a monoclinic system P2 1/ c space group. The asymmetric unit contains 1 titanium ion, 2 sodium ions, half oxygen ions, 1 protonated methanol, 1 BTC4A ligand molecule, and 1 water molecule and 1N, N-dimethylacetamide. Four sodium ions are connected with the lower parts of two BTC4A ligands through coordination to form a dumbbell-shaped structure, and two titanium ions respectively occupy two BTC4 sThe bottom of the A ligand, ti forming octahedron with the four sodium ions 2 Na 4 Core (fig. 2). The specific structure information is shown in a Cambridge crystal structure database in detail, and the CCDC number is 1892637.
Example 3 characterization of the thermal stability of the crystalline titanium oxide Cluster Material
The characterization of the thermal stability of the target material is that a thermogravimetric analyzer is used for heating a sample to 800 ℃ in a nitrogen environment, and the stable temperature range is judged according to the weight loss condition of the sample in the heating process. As shown in fig. 3, the target material gradually loses the crystallization solvent molecules and the coordination solvent molecules before 195 ℃, and the core structure of the target material is always stable. The core structure of the target material begins to collapse after 425 ℃.
Example 4 characterization of forbidden band width of titanium oxide cluster compound crystalline material
The target material forbidden band width is characterized by measuring the forbidden band width band gap of the target material by using a solid ultraviolet spectrometer. When the forbidden band width is smaller, the material can efficiently absorb visible light, thereby improving the speed and efficiency of the material for photodegradation of dye molecules. As shown in fig. 4, the forbidden bandwidth of the target material is 2.87eV, which is smaller than that of titanium dioxide.
EXAMPLE 5 photodegradation of dye molecule methylene blue by crystalline materials of titanium-oxygen cluster under solar irradiation
Configuring 2mL of 10 concentration by ultrasonic method -6 M methylene blue, 5mg of commercially available titanium dioxide P25 was ground into a fine powder by means of a mortar and added to the blue solution. The liquid uv spectrum of the upper layer liquid of the above mixed solution was measured every 5 minutes from the start of the addition of the target material. The above experiment was repeated after replacing the commercially available titanium dioxide P25 with the target material. The results of the analytical experiments show that the titanium dioxide P25 can only be photodegraded by 15% of methylene blue at 20min (FIG. 5 a), and under the same conditions, the target material can be photodegraded by 94% of methylene blue at 10min under the irradiation of sunlight (FIG. 5 b). It can be seen that the titanium oxide cluster crystalline material has good degradation effect on dye molecule methylene blue under the sunlight irradiation condition.
Claims (5)
1. The preparation method of the calixarene-based titanium oxide cluster crystalline material is characterized by comprising the following steps of: ligand H 4 BTC4A, sodium nitrate and isopropyl titanate were added to a mixture of N, N-dimethylacetamide and methanol, and the H was added 4 The molar ratio of BTC4A, sodium nitrate and isopropyl titanate is 1:6:100, respectively; the volume ratio of the N, N-dimethylacetamide to the methanol is 4:2; and after uniformly mixing, heating and reacting for 5 days at 80 ℃ in a reaction kettle to obtain colorless block-shaped transparent crystals, and cleaning, filtering and airing to obtain the calixarene-based titanium oxide cluster crystalline material.
2. The method of claim 1, wherein the reaction vessel is a polytetrafluoroethylene reaction vessel.
3. The calixarene-based titanium oxide cluster crystalline material produced by the production method according to claim 1 or 2.
4. Use of the crystalline material of a calixarene-based titanium oxide cluster according to claim 3 for the photodegradation of dye molecules.
5. The application according to claim 4, wherein the application specifically comprises: under the irradiation of sunlight, a calixarene-based titanium oxide cluster crystalline material is added to a solution containing methylene blue.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721624A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院福建物质结构研究所 | Titanyl cluster compound and its synthetic method and purposes |
| CN110734458A (en) * | 2018-07-19 | 2020-01-31 | 中国科学院福建物质结构研究所 | Macro preparation method of titanium oxide clusters |
| CN111151225A (en) * | 2020-01-09 | 2020-05-15 | 南京大学 | Titanium oxide cluster gel adsorbent and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721624A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院福建物质结构研究所 | Titanyl cluster compound and its synthetic method and purposes |
| CN110734458A (en) * | 2018-07-19 | 2020-01-31 | 中国科学院福建物质结构研究所 | Macro preparation method of titanium oxide clusters |
| CN111151225A (en) * | 2020-01-09 | 2020-05-15 | 南京大学 | Titanium oxide cluster gel adsorbent and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Thiacalix[4]arene-Protected Titanium−Oxo Clusters: Influence of Ligand Conformation and Ti−S Coordination on the Visible-Light Photocatalytic Hydrogen Production;Xin Wang, et al;《Inorg. Chem.》;20200503;第59卷;第7150-7157页 * |
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