CN111943976B - Crystalline material of hexanuclear titanium-oxygen cluster compound, preparation method thereof and application thereof in photodegradation of rhodamine B - Google Patents
Crystalline material of hexanuclear titanium-oxygen cluster compound, preparation method thereof and application thereof in photodegradation of rhodamine B Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 6
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- 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
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- 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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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
A preparation method of a hexanuclear titanium oxide cluster crystalline material comprises the following steps: adding ligand 2,2' -biphenyldicarboxylic acid and isopropyl titanate into a mixed solution consisting of N, N-dimethylformamide and isopropanol, uniformly mixing, heating and reacting in a reaction kettle for a period of time to obtain yellow prismatic transparent crystals, cleaning, filtering and airing to obtain the novel hexanuclear titanium oxide cluster crystalline material. The invention relates to a titanium-oxygen cluster compound crystalline material which is a titanium-oxygen cluster compound crystalline material 6 The core novel titanium oxide cluster compound has good stability and can be stored in the air for a long time; the dye has low forbidden band width, can catalyze the photodegradation of rhodamine B under the irradiation of sunlight, and has important significance for the treatment of dye molecules in industrial wastewater. 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.
Description
Technical Field
The invention relates to a hexanuclear titanium-oxygen cluster crystalline material, a preparation method thereof and application thereof in photodegradation of rhodamine B.
Background
The metal cluster chemistry has a history of more than two hundred years so far, and is an extremely important research field in the disciplines of physics, chemistry, materials and the like, wherein the titanium oxygen cluster compound is one of the important research fields in the metal oxygen cluster chemistry. A titanium oxygen cluster is a titanium metal cluster compound formed with a plurality of titanium atoms as the center, and the central titanium atom is bonded to a ligand or other ions through a coordinate bond. Recently, the synthesis and characterization of titanium-oxygen cluster compound has become a research hotspot in the research field of inorganic and material chemistry, and has received much attention from scientists. The solvothermal synthesis method is the most commonly used method for synthesizing the titanium oxide cluster compound, and the method has simple operation and short reaction time. The titanium-oxygen cluster compound has the advantages of various adjustable structures and performances and the like, and has good application prospects in the fields of photocatalysis, photodegradation and the like. 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. The structure of the titanium-oxygen cluster compound is various and can be regulated, and the forbidden band width is low, so that the titanium-oxygen cluster compound is more and more useful in the molecular direction of the photodegradable dye.
Rhodamine B (rhodamine B), also known as rose bengal B, is an artificially synthesized dye with a bright peach red color. Rhodamine B has strong fluorescence in solution and is used as a cell fluorescent dye in laboratories, colored glass, special fireworks and crackers and other industries. The rhodamine B has great harm to human bodies and can cause the symptoms of red staining of human skin and internal organs, mild extravasated blood of blood vessels between brains, rupture of myocardial fibers, fuzzy and disappearance of transverse striations and the like; when the rhodamine B is eaten, pulmonary edema, renal interstitial blood stasis and tubulous cavities are formed, and death can be caused by long-term eating. According to the world health organization international agency for research on cancer (IARC) chemical carcinogenic risk assessment: uptake of rhodamine dye and exposure of the skin to this substance can cause acute and chronic toxic injury. The Ministry of health of China lists the food in the famous single lot of non-edible substances which can be illegally added into food and food additives which are easy to abuse, and strictly prohibits the use of the food. In view of the harm of rhodamine B molecules to human bodies and the environment, the development of a novel titanium-oxide cluster crystalline material for rapidly and efficiently photodegrading rhodamine B under natural light is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a novel hexanuclear 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 method for preparing a dissimilar metal titanium oxygen cluster crystalline material comprises the following steps: adding ligand 2,2' -biphenyldicarboxylic acid and isopropyl titanate into a mixed solution consisting of N, N-dimethylformamide and isopropanol, uniformly mixing, heating and reacting in a reaction kettle for a period of time to obtain yellow prismatic transparent crystals, cleaning, filtering and airing to obtain the novel hexanuclear titanium oxide cluster crystalline material.
Further, the molar ratio of the 2,2' -biphenyl dicarboxylic acid to the isopropyl titanate is 1: 17.
further, the volume ratio of the N, N-dimethylformamide to the isopropanol is 11: 1.
further, the reaction kettle is a polytetrafluoroethylene reaction kettle, the heating temperature is 90 ℃, and the reaction time is 4 days.
The invention also provides a crystalline material of the hexanuclear titanium oxide cluster compound prepared by the synthesis method.
The invention also provides application of the crystalline material of the hexanuclear titanium oxide cluster compound in photodegradation of dye molecules.
Further, the photodegradation dye molecule is used for photodegradation of rhodamine B in the environment.
Further, the application specifically includes: the rhodamine B is dispersed in water and stirred by magnetons to prepare a solution. Under the daylight condition, crystal powder of a novel hexanuclear titanium-oxygen cluster compound is added into the purple red solution, and the color of the rhodamine B solution is lightened along with the change of time; and detecting the concentration of the rhodamine B in the mixed solution through liquid ultraviolet spectrum, thereby determining the degradation percentage of the rhodamine B. The above experiment was repeated with commercially available titanium dioxide P25 instead of the crystal powder of the hexanuclear titanyl cluster compound in order to examine the rapidity and high efficiency of photodegradation of rhodamine B by the target material under sunlight.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a titanium-oxygen cluster crystalline material which is a Ti-containing crystalline material 6 The core novel titanium oxide 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 novel crystalline material of the hexanuclear titanium-oxygen cluster compound catalyzes the photodegradation of rhodamine B under the irradiation of sunlight, and has important significance for the treatment of dye molecules in industrial wastewater.
Drawings
FIG. 1 shows a structural diagram of an asymmetric unit of a hexanuclear titanyl cluster compound (a), a diagram of a coordination environment of titanium ion (b), and Ti 6 A core structure diagram (c) and a structure diagram (d) of a hexanuclear titanium oxide cluster molecule;
FIG. 2 shows a powder diffraction characterization plot of sample purity and air stability of the hexanuclear titanyl cluster compound;
FIG. 3 shows a thermal stability characterization map of a hexanuclear titanium oxide cluster;
FIG. 4 shows a spectrum of band gap characterization for a hexanuclear titanium oxide cluster;
FIG. 5 shows the liquid ultraviolet absorption spectrum (a) of rhodamine B catalyzed by titanium dioxide P25 under sunlight irradiation, the liquid ultraviolet absorption spectrum (B) of rhodamine B catalyzed by a hexanuclear titanium oxygen cluster compound, and the photodegradation effect (c) of dye molecule rhodamine B by titanium dioxide P25 and the hexanuclear titanium oxygen cluster compound.
Detailed Description
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 method of crystalline Material of Hexa-Nuclear TiOx-titanium Cluster Compound
72mg (0.3mmol) of 2,2' -biphenyldicarboxylic acid (H) were weighed out separately 2 bpdc) and 0.5mL (5mmol) of isopropyl titanate are put into a polytetrafluoroethylene inner container, 5.5mL of N, N-dimethylformamide and 0.5mL of isopropanol are added into the mixture, after uniform mixing is carried out for 1 hour by ultrasonic treatment, the polytetrafluoroethylene inner container is put into a stainless steel reaction kettle jacket and screwed, the stainless steel reaction kettle jacket is put into a constant temperature oven at 90 ℃ for reaction for 4 days, the polytetrafluoroethylene inner container is taken out and naturally cooled to the room temperature, and the yellow prismatic transparent crystal is obtained by opening the polytetrafluoroethylene inner container. Washing the crystal with distilled water, filtering and drying to obtain the crystalline hexanuclear titanium oxide cluster material with the molecular formula of [ Ti 6 (bpdc) 2 (μ 2 -O 2- )(μ 3 -O 2- ) 2 ( i PrO - ) 14 ]。
Example 2 structural characterization of crystalline materials of hexagonal TiOx cluster Compound
The crystal structure of the target material is obtained by analyzing X-ray single crystal diffraction data. The single crystal test result shows that the target material is crystallized in the orthorhombic system P2 1 2 1 2 1 And (4) space group. The asymmetric unit contained 6 titanium ions, 3 oxygen ions, 2 bpdc ligand molecules, and 14 isopropanol molecules (fig. 1 a). Four titanium ions are in a six-coordinate deformed octahedral configuration, and two titanium ions are in a five-coordinate deformed triangular bipyramid configuration (fig. 1 b). Two hexacoordinate titanium ions are linked to one pentacoordinate titanium ion via a central oxygen ion to form a triangular Ti3 secondary building block (fig. 1 c). Two Ti3 secondary structural units are connected through two 2,2' -biphenyl dicarboxylic acid ligands to form a hexanuclear titanium oxide cluster molecular structure (FIG. 1 d). The purity and air stability of the target material samples were characterized by X-ray powder diffraction (fig. 2), and simulations were matched to the diffraction pattern of the samples to show a crystalline pure phase of the target material.
Example 3 characterization of the thermal stability of crystalline materials of hexagonal TiOx clusters
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 298 ℃, and the core structure of the target material is always stable. The core structure of the target material begins to collapse after 385 ℃.
Example 4 characterization of forbidden band width of crystalline Material of Hexa-nuclear titanium oxide Cluster
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 is beneficial to efficiently absorbing visible light, so that the speed and the efficiency of the material for photodegradation of dye molecules are improved. As shown in fig. 4, the forbidden bandwidth of the target material is 3.07eV, which is slightly smaller than that of titanium dioxide.
Example 5 photodegradation of dye molecule rhodamine B by crystalline hexagonal titanium oxide Cluster Material under solar irradiation
3mL of 10 concentration was prepared by sonication -5 M aqueous solution of rhodamine B, 5mg of commercially available titanium dioxide P25 was ground into a fine powder by means of a mortar, and then added to the above-mentioned mauve solution. The liquid uv spectrum of the upper layer liquid of the above mixed solution was measured every 15 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 analysis experiment result shows that titanium dioxide P25 can only photodegrade 4% of rhodamine B at 15min (FIG. 5 a). Under the same conditions, the target material can be photodegraded by 93% of rhodamine B in 15min under the irradiation of sunlight (FIG. 5B). The research result shows that the hexanuclear titanium-oxygen cluster compound crystalline material can rapidly and efficiently photodegrade rhodamine B molecules under the sunlight irradiation condition, and the speed and the efficiency are much better than those of titanium dioxide (figure 5 c).
Claims (6)
1. The application of the hexanuclear titanium oxygen cluster crystalline material in dye molecule photodegradation is characterized in that the dye molecule photodegradation is the photodegradation performance of rhodamine B in dye molecules under the irradiation of sunlight, and the molecular formula of the hexanuclear titanium oxygen cluster crystalline material is [ Ti 6 (bpdc) 2 (μ 2 -O 2- )(μ 3 -O 2- ) 2 ( i PrO - ) 14 ]The crystalline material of the hexanuclear titanium oxide cluster compound is an orthorhombic systemP2 1 2 1 2 1 The space group comprises 6 titanium ions, 3 oxygen ions, 2 bpdc ligand molecules and 14 isopropanol molecules in asymmetric units, wherein four titanium ions are in a six-coordination deformed octahedral configuration, two titanium ions are in a five-coordination deformed triangular bipyramid configuration, the two six-coordination titanium ions and one five-coordination titanium ion are connected through a central oxygen ion to form a triangular Ti3 secondary structure unit, and the two Ti3 secondary structure units are connected through two 2,2' -biphenyl dicarboxylic acid ligands to form a hexanuclear titanium dioxide cluster molecular structure.
2. The use according to claim 1, wherein the crystalline material of the hexanuclear titanium oxide cluster is prepared by the following method: adding ligand 2,2' -biphenyldicarboxylic acid and isopropyl titanate into a mixed solution consisting of N, N-dimethylformamide and isopropanol, uniformly mixing, heating and reacting in a reaction kettle for a period of time to obtain yellow prismatic transparent crystals, cleaning, filtering and airing to obtain the hexanuclear titanium oxide cluster crystalline material.
3. Use according to claim 2, characterized in that the molar ratio between 2,2' -biphenyldicarboxylic acid and isopropyl titanate is 1: 17.
4. use according to claim 2, wherein the volume ratio of N, N-dimethylformamide to isopropanol is 11: 1.
5. the use according to claim 2, wherein the reaction vessel is a polytetrafluoroethylene reaction vessel, the heating temperature is 90 ℃, and the reaction time is 4 days.
6. The use according to claim 1, wherein the hexanuclear titanium-oxygen cluster compound crystalline material has photodegradability to rhodamine B in dye molecules under sunlight irradiation.
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| 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 |
| CN109248638A (en) * | 2018-08-27 | 2019-01-22 | 华南理工大学 | A kind of nuclear case structure hybridization material and the preparation method and application thereof with anti-ultraviolet property |
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