CN104098614A - Zinc coordination polymer as well as preparation method and application thereof - Google Patents

Zinc coordination polymer as well as preparation method and application thereof Download PDF

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CN104098614A
CN104098614A CN201410352309.7A CN201410352309A CN104098614A CN 104098614 A CN104098614 A CN 104098614A CN 201410352309 A CN201410352309 A CN 201410352309A CN 104098614 A CN104098614 A CN 104098614A
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coordination polymer
zinc
zinc coordination
preparation
thin film
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CN104098614B (en
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郎建平
李端秀
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Suzhou University
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Abstract

The invention discloses a zinc coordination polymer as well as a preparation method and application thereof. According to the method, under a solvothermal condition, a zinc complex is prepared firstly, and then is doped with a small amount of cobalt ions, so that a doped complex is obtained. Compared with conventional method, the method disclosed by the invention has the advantages that a zinc complex catalyst doped with the small amount of cobalt ions is better in the reaction effect of catalyzing and light-degrading Rhodamine B, can realize recycling, and keep relatively high catalytic efficiency.

Description

Zinc coordination polymer, its preparation method and application thereof
Technical field
The present invention relates to the preparation method of ligand polymer and the application in catalysis photodegradation thereof, be specifically related to a kind of zinc coordination polymer, its preparation method and the application in catalysis photodegradation rhodamine B thereof.
Background technology
Along with the reinforcement of people's environmental protection consciousness, catalysis photodegradation pollutent has become a very active research direction of photochemistry field in recent years.Wherein organic dye molecule, as rhodamine B (Rhodamine B), claims again rose red b, or basic rhodamine, is commonly called as pollen red, is a kind of dyestuff with fresh pinkish synthetic.Find through mouse test, rhodamine B can cause subcutis raw meat knurl, and under a cloud is carcinogenic substance.Rhodamine B has strong fluorescence in solution, as industries such as cell fluorescence staining agent, tinted shade, characteristic fireworks and firecrackerss in laboratory.Once be used as foodstuff additive, but experimental results show that afterwards that rhodamine B can be carcinogenic, do not allowed now as food dyeing.The organic dye pollutant of therefore degrading in water body is an important problem.
At present, the main method of degraded water pollutant has physisorphtion, biological degradation method, oxidation reduction process, catalysis photodegradation method etc.Catalysis photodegradation method has the advantages such as processing capacity is large, the redox medicament that the tolerance of environment by force, do not needed to introduce other.
Design synthetic environment close friend's, the gordian technique that the simple photoresponse catalyzer of synthetic method is catalysis photodegradation method.Utilizing metal nano material is the effective ways of photodegradation pollutent as catalyzer; But nanoparticle is conventionally synthetic comparatively complicated as photoresponse catalyzer, the nanoparticle being synthesized may have sizes simultaneously, and the recycle of metal nanoparticle has difficulties, thereby this method is restricted in application.Metal complexes has higher light stability and chemical stability, nontoxic, and synthetic method is conventionally fairly simple, so metal complexes is a kind of desirable photoresponse catalyzer.
Open the strong two kinds of two-dimentional cupprous ligand polymer of openly having reported, they are isomerss and Methylene blue, rhodamine B and tropeolin-D are all had to good catalysis photodegradation reactivity worth, two kinds of ligand polymer to three kinds of dyestuffs can recycle (referring to Tian Wen, De Xiang Zhang, Jian Zhang, Inorg. Chem. 2013,52,12 14); But its cyclic utilization rate in the reaction of photocatalytic degradation rhodamine B is low.
Summary of the invention
The object of the invention is openly a kind of preparation method of zinc coordination polymer of ZnO thin film.
To achieve the above object of the invention, the technical solution used in the present invention is:
A preparation method for the zinc coordination polymer of ZnO thin film, comprises the following steps:
(1) mixed solvent of zinc nitrate hexahydrate, m-phthalic acid, four [4-(1-imidazolyl) phenyl] methane and acetonitrile/water is put into reactor, after sealing, in 150 DEG C of reactions 2 days; After reaction finishes, be cooled to room temperature, obtain product 1;
In molar ratio, zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=(2～2.5): 1: 2;
(2) above-mentioned product 1 is placed in to the acetonitrile/water mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, after sealing, in 80 DEG C of reactions 24 hours, obtains the zinc coordination polymer of ZnO thin film, its molecular formula is C 53h 36n 8o 8zn 1.952co 0.048.
In technique scheme, the molecular formula of product 1 is C 53h 36n 8o 8zn 2.
In technique scheme, in the mixed solvent of acetonitrile/water, the volume ratio of acetonitrile and water is 1: 1.
In technique scheme, in step (1), rate of temperature fall is 5 DEG C/h.
Preferred technical scheme, in step (1), according to mol ratio, zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=2: 1: 2.
In technique scheme, in step (2), according to mol ratio, product 1: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES=1: 5.
The present invention also asks to protect a kind of preparation method of zinc coordination polymer, comprise the following steps, the mixed solvent of zinc nitrate hexahydrate, m-phthalic acid, four [4-(1-imidazolyl) phenyl] methane and acetonitrile/water is put into reactor, after sealing, in 150 DEG C of reactions 2 days; After reaction finishes, be cooled to room temperature, obtain zinc coordination polymer, molecular formula is C 53h 36n 8o 8zn 2; In molar ratio, zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=(2～2.5): 1: 2.
In technique scheme, in the mixed solvent of acetonitrile/water, the volume ratio of acetonitrile and water is 1: 1.
In technique scheme, rate of temperature fall is 5 DEG C/h.
Preferred technical scheme, according to mol ratio, zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=2: 1: 2.
The present invention also asks the zinc coordination polymer of protecting above-mentioned preparation method to prepare.Described zinc coordination polymer is C 53h 36n 8o 8zn 1.952co 0.048or C 53h 36n 8o 8zn 2.
By above-mentioned zinc coordination polymer C 53h 36n 8o 8zn 2or the zinc coordination polymer C of ZnO thin film 53h 36n 8o 8zn 1.952co 0.048add in the rhodamine B aqueous solution, under ultraviolet lamp, can carry out catalysis photodegradation rhodamine B; So the present invention also asks to protect the application of above-mentioned zinc coordination polymer in catalysis photodegradation rhodamine B.
In technique scheme, rhodamine B carries out under 400W ultraviolet ray in catalysis photodegradation.
In the present invention, the structural formula of four [4-(1-imidazolyl) phenyl] methane is:
The structural formula of rhodamine B is:
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention, first under solvent thermal condition, prepares zinc coordination polymer, then by a small amount of cobalt ion of doping, obtains a kind of zinc coordination polymer of ZnO thin film; Products therefrom Stability Analysis of Structures, superior performance, and can reuse, after recycling for 5 times, catalytic efficiency and structure all do not change;
2. the zinc coordination polymer that the inventive method prepares has the performance of good catalysis photodegradation rhodamine B, the degradation rate of rhodamine B is reached to 70% in 2 hours; And improved its catalytic performance by a small amount of cobalt ion that adulterates, degradation time reduces half, 2 hours to the degradation rate of rhodamine B up to 96%;
3. preparation method disclosed by the invention is simple, is conducive to high, the easy recycling of purifying, product yield of product, is applicable to industrialization operation.
Brief description of the drawings
Fig. 1 is C in embodiment mono- 53h 36n 8o 8zn 2solid UV Diffuse Reflectance Spectroscopy figure;
Fig. 2 is C in embodiment bis- 53h 36n 8o 8zn 1.952co 0.048solid UV Diffuse Reflectance Spectroscopy figure;
Fig. 3 is C in embodiment tri- 53h 36n 8o 8zn 2the uv absorption spectra of catalysis photodegradation RhB;
Fig. 4 is C in embodiment tri- 53h 36n 8o 8zn 2the change in concentration figure of catalysis photodegradation RhB five times circulation;
Fig. 5 is C in embodiment tri- 53h 36n 8o 8zn 2powder x-ray diffraction (PXRD) figure;
Fig. 6 is C in embodiment tetra- 53h 36n 8o 8zn 1.952co 0.048the uv absorption spectra of catalysis photodegradation RhB;
Fig. 7 is C in embodiment tetra- 53h 36n 8o 8zn 1.952co 0.048the change in concentration figure of catalysis photodegradation RhB five times circulation;
Fig. 8 is C in embodiment tetra- 53h 36n 8o 8zn 1.952co 0.048pXRD figure;
Fig. 9 is C in embodiment tri-and four 53h 36n 8o 8zn 2and C 53h 36n 8o 8zn 1.952co 0.048the change in concentration rate diagram of catalyzed degradation RhB.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described:
Embodiment mono-: zinc coordination polymer synthetic
Get zinc nitrate hexahydrate Zn (NO 3) 26H 2o(0.030g, 0.1mmol), m-phthalic acid 1,3-H 2bDC(0.016g, 0.1mmol) and four [4-(1-imidazolyl) phenyl] methane (0.029g, 0.05mmol) put into the heat-resistant glass tube of 8mL, add the 3mL volume ratio mixed solvent acetonitrile/water rear enclosed of 1: 1.In baking oven, 150 DEG C of isothermal reactions 2 days, are slowly down to room temperature with 5 DEG C/h of speed, and obtaining yellow crystals through filtration, distilled water wash, oven dry is product 1, i.e. zinc coordination polymer, and molecular formula is C 53h 36n 8o 8zn 2.
To product 1carry out infrared analysis, result is as follows:
IR:?v(KBr)/cm -1?3447m,?3136w,?1613s,?1561w,?1523s,?1373s,?1313w,?1270w,?1126w,?1068m,?966m,?827m,?762s,?656m,?561m。
Utilize X-ray single crystal diffraction to analyze product 1 structure, the results are shown in Table 1, confirmed the single crystal structure of product by table 1.
Accompanying drawing 1 is zinc coordination polymer C 53h 36n 8o 8zn 2solid UV Diffuse Reflectance Spectroscopy K-M equation, known from accompanying drawing 1, the band gap value of zinc coordination polymer is 2.27eV, illustrates that it excites required energy size, general edge energy Eg is less than 3.40eV, just can utilize the UV-light of 365nm to carry out light-catalyzed reaction.
The crystallographic parameter of table 1 zinc coordination polymer
Embodiment bis-: the zinc coordination polymer of Co ion doping synthetic
Get zinc coordination polymer C 53h 36n 8o 8zn 2be placed in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES Co (NO 3) 26H 2in the acetonitrile/water mixing solutions of O, and be sealed in heat-resistant glass tube, 80 DEG C of constant temperature 24 hours in baking oven, through filtration, distilled water wash, oven dry, obtains orange compound ,for the zinc coordination polymer of ZnO thin film, molecular formula is C 53h 36n 8o 8zn 1.952co 0.048.ICP analyzes discovery, contains 97.60% Zn in the zinc coordination polymer of ZnO thin film 2+with 2.40% Co 2+.To the zinc coordination polymer C of ZnO thin film 53h 36n 8o 8zn 1.952co 0.048carry out infrared analysis, result is as follows:
IR:?v(KBr)/cm -1?3445m,?3133w,?1615s,?1562w,?1523s,?1373s,?1314w,?1270w,?1126w,?1068m,?966m,?826m,?762s,?656m,?561m。
Utilize the zinc coordination polymer C of X-ray single crystal diffraction to ZnO thin film 53h 36n 8o 8zn 1.952co 0.048structure is analyzed, and the results are shown in Table 2, and the crystalline structure of the zinc coordination polymer of ZnO thin film is identical with zinc coordination polymer as shown in Table 2.
The zinc coordination polymer C that accompanying drawing 2 is ZnO thin film 53h 36n 8o 8zn 1.952co 0.048solid UV Diffuse Reflectance Spectroscopy K-M equation, known from accompanying drawing 2, C 53h 36n 8o 8zn 1.952co 0.048band gap value be 2.13eV.
The crystallographic parameter of the zinc coordination polymer of table 2 ZnO thin film
Embodiment tri-: zinc coordination polymer catalysis photodegradation rhodamine B
Get the zinc coordination polymer C of 10mg 53h 36n 8o 8zn 2be 3 × 10 in 50mL concentration -4mol .l -1the rhodamine B aqueous solution in, under 400W ultraviolet lamp, carry out catalysis photodegradation reaction, every 30min sampling 1mL, survey uv-absorbing with distilled water diluting to 10mL.Accompanying drawing 3 is the uv absorption spectra of the rhodamine B aqueous solution, can find out, zinc coordination polymer catalysis photodegradation rhodamine B needs 240min.
After having degraded, by the filtration of zinc coordination polymer process, washing, dried recovered, again carry out the experiment of catalysis photodegradation rhodamine B.Accompanying drawing 4 is the change in concentration figure of cycle index and rhodamine B, and in figure, ordinate zou refers to the changing value of the concentration of rhodamine B; Time is longer, and the variable quantity of the concentration of rhodamine B solution is larger, and rhodamine B degradation amount is higher, and the concentration of its aqueous solution is lower; Can find out and circulate after 5 times, catalytic efficiency is substantially constant.After 5 times recycle, zinc coordination polymer confirms through powder x-ray diffraction, and structure does not change, and sees accompanying drawing 5, in figure, a bottom simulation curve refers to the theoretical diagram obtaining according to crystal monocrystalline data fitting, and a middle actual measurement refers to zinc coordination polymer C 53h 36n 8o 8zn 2do recording before catalysis experiment, after a catalysis topmost, refer to zinc coordination polymer C 53h 36n 8o 8zn 2after 5 circulation catalysis, record; Article three, curve is basically identical shows that crystal structure after catalysis does not have destroyed.
Embodiment tetra-: the zinc coordination polymer catalysis photodegradation rhodamine B of ZnO thin film
Get the zinc coordination polymer C of the ZnO thin film of 10mg 53h 36n 8o 8zn 1.952co 0.048be 3 × 10 in 50mL concentration -4mol .l -1the rhodamine B aqueous solution in, under 400W ultraviolet lamp, carry out catalysis photodegradation reaction, every 30min sampling 1mL, survey uv-absorbing with distilled water diluting to 10mL.Accompanying drawing 6 is the uv absorption spectra of the rhodamine B aqueous solution, can find out, the zinc coordination polymer catalysis photodegradation rhodamine B of ZnO thin film only needs 120min.After having degraded, by the filtration of zinc coordination polymer process, washing, the dried recovered of catalyst cobalt ion doping, again carry out the experiment of catalysis photodegradation rhodamine B.Accompanying drawing 7 is the change in concentration figure of cycle index and rhodamine B, can find out that catalytic efficiency is substantially constant.After 5 times recycle, the zinc coordination polymer of ZnO thin film confirms through powder x-ray diffraction, and structure does not change, and sees accompanying drawing 8.
Accompanying drawing 9 is C in embodiment tri-and four 53h 36n 8o 8zn 2and C 53h 36n 8o 8zn 1.952co 0.048the change in concentration rate diagram of catalyzed degradation RhB, as can be seen from Fig., C 53h 36n 8o 8zn 2rhodamine B is degraded to 4% with 4 hours, and C 53h 36n 8o 8zn 1.952co 0.048only just rhodamine B was degraded to 4% with 2 hours.
Result shows, zinc coordination polymer is catalysis photodegradation rhodamine B effectively, and through a small amount of Co 2+doping, the catalytic effect of the ligand polymer of Zn is significantly improved.

Claims (10)

1. a preparation method for the zinc coordination polymer of ZnO thin film, is characterized in that, comprises the following steps:
(1) mixed solvent of zinc nitrate hexahydrate, m-phthalic acid, four [4-(1-imidazolyl) phenyl] methane and acetonitrile/water is put into reactor, after sealing, in 150 DEG C of reactions 2 days; After reaction finishes, be cooled to room temperature, obtain product 1;
In molar ratio, zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=(2～2.5): 1: 2;
(2) above-mentioned product 1 is placed in to the acetonitrile/water mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, after sealing, in 80 DEG C of reactions 24 hours, obtains the zinc coordination polymer of ZnO thin film, its molecular formula is C 53h 36n 8o 8zn 1.952co 0.048.
2. the preparation method of the zinc coordination polymer of ZnO thin film according to claim 1, is characterized in that: in step (1), in molar ratio, zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=2: 1: 2.
3. the preparation method of the zinc coordination polymer of ZnO thin film according to claim 1, is characterized in that: in the mixed solvent of acetonitrile/water, the volume ratio of acetonitrile and water is 1: 1.
4. the preparation method of the zinc coordination polymer of ZnO thin film according to claim 1, is characterized in that: in step (1), rate of temperature fall is 5 DEG C/h.
5. the preparation method of the zinc coordination polymer of ZnO thin film according to claim 1, is characterized in that: in step (2), in molar ratio, the ratio of product 1 and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 1: 5.
6. the preparation method of a zinc coordination polymer, it is characterized in that, comprise the following steps, the mixed solvent of zinc nitrate hexahydrate, m-phthalic acid, four [4-(1-imidazolyl) phenyl] methane and acetonitrile/water is put into reactor, after sealing, in 150 DEG C of reactions 2 days; After reaction finishes, be cooled to room temperature, obtain zinc coordination polymer, molecular formula is C 53h 36n 8o 8zn 2; In molar ratio, zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=(2～2.5): 1: 2.
7. the preparation method of zinc coordination polymer according to claim 6, is characterized in that: in molar ratio, and zinc nitrate hexahydrate: m-phthalic acid: four [4-(1-imidazolyl) phenyl] methane=2: 1: 2; In the mixed solvent of acetonitrile/water, the volume ratio of acetonitrile and water is 1: 1.
8. the preparation method of the zinc coordination polymer of ZnO thin film according to claim 6, is characterized in that: rate of temperature fall is 5 DEG C/h.
9. the zinc coordination polymer that described in employing claim 1～8, any one preparation method prepares.
10. the application of zinc coordination polymer claimed in claim 9 in catalysis photodegradation rhodamine B.
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CN111393663A (en) * 2020-04-07 2020-07-10 曲靖师范学院 Perylene bisimide base coordination polymer, preparation method and application thereof
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CN104402914A (en) * 2014-10-16 2015-03-11 东北师范大学 Zinc metal organic framework material for catalysis degradation of organic dye under visible light
CN104693224A (en) * 2014-10-31 2015-06-10 安阳师范学院 Cadmium metal complex with dye catalytic light degradation property and preparation method of cadmium metal complex
CN104693224B (en) * 2014-10-31 2016-07-20 安阳师范学院 There is cadmium metal complex of catalysis light degradation dye property and preparation method thereof
CN104530140A (en) * 2014-12-15 2015-04-22 常熟市新腾化工有限公司 Preparation method of copper and zinc bi-coordination polymer
CN104528873A (en) * 2014-12-15 2015-04-22 常熟市新腾化工有限公司 Application of copper and zinc bi-coordination polymer
CN104558059A (en) * 2014-12-15 2015-04-29 常熟市新腾化工有限公司 Copper-zinc double coordination polymer
CN105669773A (en) * 2015-12-31 2016-06-15 郑州大学 Co-MOF material, preparation method and application thereof
CN105669773B (en) * 2015-12-31 2018-01-26 郑州大学 A kind of Co MOF materials and preparation method thereof, purposes
CN106732481B (en) * 2017-01-10 2019-04-05 苏州大学 A kind of pertechnetate adsorbent and its synthetic method and the application in processing radioactive wastewater
CN106732481A (en) * 2017-01-10 2017-05-31 苏州大学 A kind of pertechnetate adsorbent and its synthetic method and the application in radioactive wastewater is processed
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CN109762178A (en) * 2019-02-11 2019-05-17 洛阳师范学院 A kind of metal-organic framework materials, metal-organic framework materials of rhodamine B-sensitized and its preparation method and application
CN110330515A (en) * 2019-07-31 2019-10-15 商丘师范学院 A kind of nitrogen oxygen mixed ligand Zn complex and preparation method thereof
CN110330515B (en) * 2019-07-31 2021-06-25 商丘师范学院 Nitrogen-oxygen mixed ligand zinc complex and preparation method thereof
CN111393663A (en) * 2020-04-07 2020-07-10 曲靖师范学院 Perylene bisimide base coordination polymer, preparation method and application thereof
CN113336956A (en) * 2021-04-12 2021-09-03 皖西学院 Metal-organic pore cobalt compound, preparation method and application thereof
CN113336956B (en) * 2021-04-12 2022-05-31 皖西学院 Metal-organic pore cobalt compound, preparation method and application thereof

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