CN111573773B - Application of titanium-based coordination polymer in photocatalytic degradation of dye wastewater - Google Patents
Application of titanium-based coordination polymer in photocatalytic degradation of dye wastewater Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 51
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 49
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 48
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 24
- 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 abstract description 18
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 18
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 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 claims abstract description 13
- 229940012189 methyl orange Drugs 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 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 description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 19
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 239000007857 degradation product Substances 0.000 abstract description 4
- 238000003911 water pollution Methods 0.000 abstract description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 6
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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
-
- 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
- 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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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The present invention belongs to the application of crystal materialThe technical field, in particular to application of a titanium-based coordination polymer in photocatalytic degradation of dye wastewater. The concentration of the titanium-based coordination polymer material pair is 2 multiplied by 10 ‑4 Degrading with mol/L methylene blue, rhodamine B and methyl orange water solution, wherein the degradation rate reaches 100% in 8min, 12min and 8min respectively; for the concentration of 3X 10 ‑4 Degrading methylene blue, rhodamine B and methyl orange water solution in mol/L, wherein the degradation rate reaches 100% in 16min, 24min and 17min respectively; for concentration of 4X 10 ‑ 4 The degradation rates of the mol/L methylene blue, rhodamine B and methyl orange aqueous solutions reach 100% in 25min, 38min and 27min respectively, and the titanium-based coordination polymer material has the characteristics of high degradation efficiency, thorough degradation product, no secondary pollution, cyclic utilization and the like in a dye wastewater degradation test, and has wide application prospects in the field of water pollution treatment.
Description
Technical Field
The invention belongs to the technical field of crystal material application, and particularly relates to application of a titanium-based coordination polymer in photocatalytic degradation of dye wastewater.
Background
With the rapid development of economic construction in China, wastewater generated by the production and manufacturing industry is increased year by year, and the problem of water environment pollution caused by the wastewater is serious day by day. The textile pollution is one of the important factors causing the water environment pollution, and the dye wastewater has the characteristics of complex components, deep chromaticity, large water quality change, poor biodegradability and the like, and is one of the wastewater which is difficult to treat. The photocatalysis technology can utilize light energy to oxidize and decompose organic pollutants, and is an important method for treating various dye wastewater. Nano titanium dioxide (TiO) 2 ) Materials are considered to be one of the most potential photocatalysts due to their low cost, high efficiency, and environmental friendliness. However, such TiO 2 The material also has some non-negligible defects, such as wider energy band gap, faster recombination rate of photogenerated electron-hole pairs, shorter service life of photogenerated carriers and the like, which seriously limit the practical application of the material in the field of photocatalysis.
The titanium-based coordination polymer is one of the most attractive coordination polymers reported so far because of the application prospect in photocatalysis. With semi-conducting TiO 2 Compared with photocatalytic materials, titanium-based coordination polymers have many advantages, such as precise atomic layer structure information, a definite ligand-cluster core connection mode, an adjustable topological structure, easy modification and the like. However, the research on titanium-based coordination polymers has been in the initial stage, and there is much less research on their application in dye wastewater treatment. In view of the above, the titanium-based coordination polymer is used for photocatalytic degradation of dye wasteWater has become an important research topic.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the application of the titanium-based coordination polymer in the photocatalytic degradation of dye wastewater, and the titanium-based coordination polymer material has the characteristics of high degradation efficiency, complete degradation products, no secondary pollution, cyclic utilization and the like in the degradation test of the photocatalytic degradation of the dye wastewater.
In order to realize the purpose, the invention adopts the technical scheme that:
the application of the titanium-based coordination polymer in photocatalytic degradation of dye wastewater is characterized in that the titanium-based coordination polymer material is used for degrading methylene blue, rhodamine B and methyl orange aqueous solution.
Further, the photocatalytic degradation of the dye wastewater adopts the following steps: dispersing the titanium-based coordination polymer in a dye aqueous solution, placing the dye aqueous solution under a 300W xenon lamp with an optical filter (420 nm) for illumination, continuously stirring, taking out 2mL of solution every 2min, filtering, and analyzing the solution by an ultraviolet absorption spectrometer.
Further, the ratio of the amount of the methylene blue substance in the added titanium-based coordination polymer and the dye wastewater is as follows: 1: (2-4); the ratio of the added titanium-based coordination polymer to the amount of rhodamine B substance in the dye wastewater is as follows: 1: (2-4); the ratio of the added titanium-based coordination polymer to the amount of the methyl orange substance in the dye wastewater is as follows: 1: (2-4).
The molecular formula of the titanium oxide cluster-based coordination polymer is Ti 3 O 12 C 30 N 3 H 47 CuBr。
Further, the crystal structure of the titanium-based coordination polymer is as follows: the crystal belongs to monoclinic system and has space group ofC2/ cThe unit cell parameters are a =17.3730 a, b =19.2330 a, c =18.5000 a, α is 90 °, β is 109 °, γ is 90 °.
Further, the titanium-based coordination polymer is synthesized by the following steps: adding isopropyl titanate, cuprous bromide, isonicotinic acid ligand and acetonitrile solvent into a reaction kettle, stirring for 0.5-1.5 h at room temperature, reacting for 48-96 h at 80-120 ℃, cooling to 25 ℃, separating out blocky crystals in a system, separating, washing and drying to obtain the titanium-based coordination polymer.
Further, the mass-to-volume ratio of the isopropyl titanate, the cuprous bromide, the isonicotinic acid ligand and the acetonitrile solvent is as follows: (0.1-0.2) mL: (0.15-0.20) g: 0.1 g: (4-6) mL.
Further, the temperature is reduced by adopting a program temperature control mode, and the temperature reduction rate is controlled to be 3-10 ℃/h; the washing is carried out for three times by adopting isopropanol; the drying is natural drying.
Advantageous effects
The invention provides an application of a titanium-based coordination polymer in photocatalytic degradation of dye wastewater, and the titanium-based coordination polymer material has the characteristics of high degradation efficiency, complete degradation products, no secondary pollution and cyclic utilization in a dye wastewater degradation test.
Drawings
FIG. 1 is a structural diagram of a titanium-based coordination polymer;
FIG. 2 is a test chart of photocatalytic degradation of methylene blue in example 1;
FIG. 3 is a test chart of photocatalytic degradation of rhodamine B in example 2;
FIG. 4 is a test chart of photocatalytic degradation of methyl orange in example 3;
FIG. 5 is a graph of the cycle test of photocatalytic degradation of methylene blue, rhodamine B and methyl orange in examples 1-3.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The raw materials and reagents used in the invention are commercially available.
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to examples.
Example 1
10mg of titanium-based coordination polymer was dispersed in 100mL of methylene blue aqueous solution (2X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the light to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution were taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, the methylene blue solution is completely degraded in 8min, and three circulation experiments show good photocatalytic degradation performance.
Example 2
10mg of titanium-based coordination polymer was dispersed in 100mL of rhodamine B aqueous solution (2X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the sun to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution was taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, 12min rhodamine B solution is completely degraded, and three circulation experiments show good photocatalytic degradation performance.
Example 3
10mg of the titanium-based coordination polymer was dispersed in 100mL of an aqueous methyl orange solution (2X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the sun to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution were taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, the methyl orange solution is completely degraded in 8min, and three circulation experiments show good photocatalytic degradation performance.
Example 4
Mixing 10mg titanium baseThe polymer was dispersed in 100mL of methylene blue aqueous solution (3X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the light to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution was taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, the methylene blue solution is completely degraded in 16min, and three circulation experiments show good photocatalytic degradation performance.
Example 5
10mg of titanium-based coordination polymer was dispersed in 100mL of rhodamine B aqueous solution (3X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the light to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution was taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, 25min rhodamine B solution is completely degraded, and three circulation experiments show good photocatalytic degradation performance.
Example 6
10mg of titanium-based coordination polymer was dispersed in 100mL of methyl orange aqueous solution (3X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the sun to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution were taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, the methyl orange solution is completely degraded in 17min, and three circulation experiments show good photocatalytic degradation performance.
Example 7
10mg of the titanium-based coordination polymer was dispersed in 100mL of an aqueous methylene blue solution (4X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the sun to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) under constant irradiation and stirring, taking out 2mL of solution every 2min, filtering,analysis was performed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, the methylene blue solution is completely degraded in 25min, and three circulation experiments show good photocatalytic degradation performance.
Example 8
10mg of titanium-based coordination polymer was dispersed in 100mL of rhodamine B aqueous solution (4X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the sun to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution were taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, the rhodamine B solution is completely degraded in 38min, and three times of circulation experiments show good photocatalytic degradation performance.
Example 9
10mg of the titanium-based coordination polymer was dispersed in 100mL of an aqueous methyl orange solution (4X 10) -4 mol/L), continuously stirring for 2h under the condition of keeping out of the sun to reach adsorption saturation, and placing the mixture into a 300W xenon lamp (A)>420nm) and stirred, 2mL of solution were taken out every 2min, filtered and analyzed by uv absorption spectroscopy. The test result is shown in figure 2, the ultraviolet absorption spectrum curve gradually reduces along with the increase of the reaction time, no new absorption peak appears in the whole measuring wave band, the methyl orange solution is completely degraded in 27min, and three circulation experiments show good photocatalytic degradation performance.
Examples 1 to 9 above, the titanium-based coordination polymer for photodegradation of dye wastewater having a molecular formula of Ti 3 O 12 C 30 N 3 H 47 CuBr; the crystal structure of the titanium-based coordination polymer is as follows: the crystal belongs to monoclinic system and has space group ofC2/cThe unit cell parameters are a =17.3730 a, b =19.2330 a, c =18.5000 a, α is 90 °, β is 109 °, γ is 90 °.
The titanium-based coordination polymer material is used for photocatalytic degradation of dye wastewater. The test result shows that: the titanium-based coordinationPolymer material pair 2 x 10 -4 Degrading the methylene blue, rhodamine B and methyl orange water solution in mol/L, wherein the degradation rate reaches 100% in 8min, 12min and 8min respectively; for 3X 10 -4 Degrading methylene blue, rhodamine B and methyl orange water solution in mol/L, wherein the degradation rate reaches 100% in 16min, 25min and 17min respectively; for 4 x 10 -4 The degradation rates of the methylene blue, rhodamine B and methyl orange aqueous solution of mol/L reach 100 percent in 25min, 38min and 27min respectively (figures 2, 3 and 4), and three times of circulation tests show that the photocatalytic material has lasting photocatalytic activity and good light stability (figure 5). The titanium-based coordination polymer material has the characteristics of high degradation efficiency, thorough degradation product, no secondary pollution, cyclic utilization and the like in a dye wastewater degradation test, and has wide application prospect in the field of water pollution treatment.
Claims (6)
1. The application of the titanium-based coordination polymer in photocatalytic degradation of dye wastewater is characterized in that the titanium-based coordination polymer material degrades methylene blue, rhodamine B and methyl orange aqueous solution; the molecular formula of the titanium-based coordination polymer is Ti 3 O 12 C 30 N 3 H 47 CuBr; the crystal structure of the titanium-based coordination polymer is as follows: the crystal belongs to the monoclinic system, the space group is C2/C, the unit cell parameters are a =17.3730 a, b =19.2330 a, C =18.5000 a, α is 90 °, β is 109 °, γ is 90 °.
2. The use of claim 1, wherein the photocatalytic degradation of dye wastewater is carried out by the steps of: dispersing the titanium-based coordination polymer in a dye aqueous solution, placing the dye aqueous solution under a 300W xenon lamp with an optical filter (420 nm) for illumination, continuously stirring, taking out 2mL of the solution, filtering, and analyzing the solution by an ultraviolet absorption spectrometer.
3. The use according to claim 2, wherein the ratio of the amount of methylene blue species in the titanium-based coordination polymer and dye wastewater added is: 1: (2-4); the ratio of the added titanium-based coordination polymer to the amount of rhodamine B substance in the dye wastewater is as follows: 1: (2-4); the ratio of the added titanium-based coordination polymer to the amount of the methyl orange substance in the dye wastewater is as follows: 1: (2-4).
4. Use according to any one of claims 1 to 3, characterized in that the titanium-based coordination polymer is synthesized by the following steps: adding isopropyl titanate, cuprous bromide, isonicotinic acid ligand and acetonitrile solvent into a reaction kettle, stirring for 0.5-1.5 h at room temperature, reacting for 48-96 h at 80-120 ℃, cooling to 25 ℃, precipitating blocky crystals in the system, separating, washing and drying to obtain the titanium-based coordination polymer.
5. The use of claim 4, wherein the mass-to-volume ratio of isopropyl titanate, cuprous bromide, isonicotinic acid ligand and acetonitrile solvent is: (0.1-0.2) mL: (0.15-0.20) g: 0.1 g: (4-6) mL.
6. The application of claim 4, wherein the temperature reduction is carried out by means of program temperature control, and the temperature reduction rate is controlled to be 3-10 ℃/h; the washing is carried out for three times by adopting isopropanol; the drying is natural drying.
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| CN106807413A (en) * | 2017-02-17 | 2017-06-09 | 盐城工学院 | A kind of Ag@AgBr/CaTiO with Plasmon Surface Resonance effect3Photochemical catalyst and preparation method thereof |
| CN109721624B (en) * | 2017-10-31 | 2020-06-30 | 中国科学院福建物质结构研究所 | Titanium-oxygen cluster compound and synthesis method and application thereof |
| CN110734458B (en) * | 2018-07-19 | 2020-12-29 | 中国科学院福建物质结构研究所 | Mass preparation method of titanium oxide cluster compound |
| CN109607663B (en) * | 2018-12-07 | 2021-11-23 | 浙江工业大学 | Titanium oxygen cluster C34H62O13S2Ti3Active carbon composite material, preparation method and application |
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