CN104530140A - Preparation method of copper and zinc bi-coordination polymer - Google Patents
Preparation method of copper and zinc bi-coordination polymer Download PDFInfo
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- CN104530140A CN104530140A CN201410770324.3A CN201410770324A CN104530140A CN 104530140 A CN104530140 A CN 104530140A CN 201410770324 A CN201410770324 A CN 201410770324A CN 104530140 A CN104530140 A CN 104530140A
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Abstract
The invention discloses a preparation method of a copper and zinc bi-coordination polymer. The preparation method comprises the steps of firstly, preparing a zinc complex under a solvothermal condition; and then, doping a small amount of copper ions to obtain the copper and zinc bi-coordination polymer. Compared with the existing method, the preparation method disclosed by the invention has the advantages that the reaction effect for catalyzing light degradation of rhodamine B by using a zinc complex catalyst doped with a small amount of the copper ions is better, recycling can be realized, and relatively high catalysis efficiency is kept.
Description
Technical field
The present invention relates to the preparation method of ligand polymer, be specifically related to the preparation method of the two ligand polymer of a kind of copper zinc.
Background technology
In recent years along with the reinforcement of people's environmental protection consciousness, catalysis photodegradation pollutent has become a very active research direction of photochemistry field.Wherein rhodamine B is a kind of dyestuff with fresh pinkish synthetic, and can cause subcutis raw meat knurl, be carcinogenic substance.Rhodamine B has application at fluorescent dye, tinted shade, characteristic fireworks and firecrackers, foodstuff additive.Therefore the organic dye pollutant in degraded 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 process capacity is large, the redox medicament that by force, do not need to introduce other to the tolerance of environment.
Design and synthesis is eco-friendly, and the simple photoresponse catalyzer of synthetic method is the gordian technique of catalysis photodegradation method.But conventional nanoparticle synthesizes comparatively complicated usually as photoresponse catalyzer, the nanoparticle be synthesized may have sizes, and the recycle of metal nanoparticle has difficulties, thus makes this method be restricted in the application simultaneously.Metal complexes has higher light stability and chemical stability, nontoxic, and synthetic method is usually fairly simple, so metal complexes is a kind of desirable photoresponse catalyzer.
Summary of the invention
The object of the invention is the preparation method of the two ligand polymer of openly a kind of copper zinc.
To achieve the above object of the invention, the technical solution used in the present invention is:
A preparation method for the two ligand polymer of copper zinc, comprises the following steps:
(1) in nitrogen, zinc nitrate hexahydrate, oxalic acid, four [4-(1-imidazolyl) phenyl] methane and toluene are put into reactor, back flow reaction 51-55 hour, cooling obtains product 1;
In molar ratio, zinc nitrate hexahydrate: oxalic acid: four [4-(1-imidazolyl) phenyl] methane=2.3: 1: 2;
(2) above-mentioned product 1 is placed in the acetonitrile solution of cupric nitrate, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc, its molecular formula is C
53h
36n
8o
8zn
1.1cu
0.9.
Preferably, step (1) back flow reaction 52 hours.
In technique scheme, in step (1), rate of temperature fall is 2 DEG C/h.
In technique scheme, in step (2), in molar ratio, the ratio 1: 3 of product 1 and cupric nitrate.
Two for above-mentioned copper zinc ligand polymer is added in the rhodamine B aqueous solution, catalysis photodegradation rhodamine B can be carried out under ultraviolet lamp; Rhodamine B carries out under 400W ultraviolet in catalysis photodegradation.
In technique scheme, rhodamine B carries out under 400W ultraviolet in catalysis photodegradation.
Because technique scheme is used, the present invention compared with prior art has following advantages:
The present invention under solvent thermal condition, prepares zinc coordination polymer first, then by a small amount of cupric ion of doping, obtains a kind of copper ion doped zinc coordination polymer; Products therefrom Stability Analysis of Structures, superior performance, and can reuse, can be recycled 8 times; And preparation method disclosed by the invention is simple, is conducive to high, the easy recycling of purifying, product yield of product, be applicable to industrial operation.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment one: the synthesis of copper zinc coordination polymer
(1) in nitrogen, 0.23mmol zinc nitrate hexahydrate, 0.23mmol oxalic acid, 0.2mmol tetra-[4-(1-imidazolyl) phenyl] methane and 3mL toluene are put into the heat-resistant glass tube of 20mL, back flow reaction 51 hours, slowly be down to room temperature with 2 DEG C/h of speed, obtain product 1 through filtration, distilled water wash, oven dry;
Carry out infrared analysis to product 1, result is as follows:
IR:v(KBr)/cm
-13447m,3136w,1613s,1561w,1523s,1373s,1313w,1270w,1126w,1068m,966m,827m,762s,656m,561m；
(2) 0.1mmol product 1 is placed in the acetonitrile solution of 0.3mmol cupric nitrate, and is sealed in heat-resistant glass tube, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc through filtration, distilled water wash, oven dry, its molecular formula is C
53h
36n
8o
8zn
1.1cu
0.9.Carry out infrared analysis to the two ligand polymer of copper zinc, result is as follows:
IR:v(KBr)/cm
-13445m,3133w,1615s,1562w,1523s,1373s,1314w,1270w,1126w,1068m,966m,826m,762s,656m,561m。
Embodiment two: the synthesis of copper zinc coordination polymer
(1) in nitrogen, 0.23mmol zinc nitrate hexahydrate, 0.23mmol oxalic acid, 0.2mmol tetra-[4-(1-imidazolyl) phenyl] methane and 3mL toluene are put into the heat-resistant glass tube of 20mL, back flow reaction 55 hours, slowly be down to room temperature with 2 DEG C/h of speed, obtain product 1 through filtration, distilled water wash, oven dry;
(2) 0.1mmol product 1 is placed in the acetonitrile solution of 0.3mmol cupric nitrate, and is sealed in heat-resistant glass tube, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc through filtration, distilled water wash, oven dry.
Embodiment three: the synthesis of copper zinc coordination polymer
(1) in nitrogen, 0.23mmol zinc nitrate hexahydrate, 0.23mmol oxalic acid, 0.2mmol tetra-[4-(1-imidazolyl) phenyl] methane and 3mL toluene are put into the heat-resistant glass tube of 20mL, back flow reaction 52 hours, slowly be down to room temperature with 2 DEG C/h of speed, obtain product 1 through filtration, distilled water wash, oven dry;
(2) 0.1mmol product 1 is placed in the acetonitrile solution of 0.3mmol cupric nitrate, and is sealed in heat-resistant glass tube, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc through filtration, distilled water wash, oven dry.
Embodiment four: the synthesis of copper zinc coordination polymer
(1) in nitrogen, 0.23mmol zinc nitrate hexahydrate, 0.23mmol oxalic acid, 0.2mmol tetra-[4-(1-imidazolyl) phenyl] methane and 3mL toluene are put into the heat-resistant glass tube of 20mL, back flow reaction 53 hours, slowly be down to room temperature with 2 DEG C/h of speed, obtain product 1 through filtration, distilled water wash, oven dry;
(2) 0.1mmol product 1 is placed in the acetonitrile solution of 0.3mmol cupric nitrate, and is sealed in heat-resistant glass tube, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc through filtration, distilled water wash, oven dry.
Embodiment five: the synthesis of copper zinc coordination polymer
(1) in nitrogen, 0.23mmol zinc nitrate hexahydrate, 0.23mmol oxalic acid, 0.2mmol tetra-[4-(1-imidazolyl) phenyl] methane and 3mL toluene are put into the heat-resistant glass tube of 20mL, back flow reaction 54 hours, slowly be down to room temperature with 2 DEG C/h of speed, obtain product 1 through filtration, distilled water wash, oven dry;
(2) 0.1mmol product 1 is placed in the acetonitrile solution of 0.3mmol cupric nitrate, and is sealed in heat-resistant glass tube, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc through filtration, distilled water wash, oven dry.
Embodiment six: the synthesis of copper zinc coordination polymer
(1) in nitrogen, 0.23mmol zinc nitrate hexahydrate, 0.23mmol oxalic acid, 0.2mmol tetra-[4-(1-imidazolyl) phenyl] methane and 3mL toluene are put into the heat-resistant glass tube of 20mL, back flow reaction 52 hours, naturally be down to room temperature, obtain product 1 through filtration, distilled water wash, oven dry;
(2) 0.1mmol product 1 is placed in the acetonitrile solution of 0.3mmol cupric nitrate, and is sealed in heat-resistant glass tube, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc through filtration, distilled water wash, oven dry.
Embodiment seven: the two ligand polymer catalysis photodegradation rhodamine B of copper zinc
The two ligand polymer of copper zinc of getting 1mg in 10mL concentration be 2 × 10
-4molL
-1the rhodamine B aqueous solution in, under 400W ultraviolet lamp, carry out catalysis photodegradation reaction, every 30min sample 1mL, survey uv-absorbing with distilled water diluting to 10mL.The two ligand polymer catalysis photodegradation rhodamine B of copper zinc needs 4 hours.
After having degraded, two for copper zinc ligand polymer is passed through filtration, washing, dried recovered, again carry out the experiment of catalysis photodegradation rhodamine B.After 8 times recycle, the two ligand polymer catalysis photodegradation rhodamine B of copper zinc is 4.2 hours.
Claims (4)
1. a preparation method for the two ligand polymer of copper zinc, is characterized in that, comprise the following steps:
(1) in nitrogen, zinc nitrate hexahydrate, oxalic acid, four [4-(1-imidazolyl) phenyl] methane and toluene are put into reactor, back flow reaction 51-55 hour, cooling obtains product 1;
In molar ratio, zinc nitrate hexahydrate: oxalic acid: four [4-(1-imidazolyl) phenyl] methane=2.3: 1: 2;
(2) above-mentioned product 1 is placed in the acetonitrile solution of cupric nitrate, back flow reaction 15 hours, obtain the two ligand polymer of copper zinc, its molecular formula is C
53h
36n
8o
8zn
1.1cu
0.9.
2. the preparation method of the two ligand polymer of copper zinc according to claim 1, is characterized in that: step (1) back flow reaction 52 hours.
3. the preparation method of the two ligand polymer of copper zinc according to claim 1, it is characterized in that: in step (1), rate of temperature fall is 2 DEG C/h.
4. the preparation method of the two ligand polymer of copper zinc according to claim 1, is characterized in that: in step (2), in molar ratio, the ratio 1: 3 of product 1 and cupric nitrate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107501535A (en) * | 2017-08-14 | 2017-12-22 | 常州大学 | Zn complex catalyst of PLA and preparation method thereof is prepared for ring-opening polymerisation |
| CN110734554A (en) * | 2019-11-23 | 2020-01-31 | 南京科技职业学院 | Zn (II) three-dimensional blending coordination polymer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104098614A (en) * | 2014-07-23 | 2014-10-15 | 苏州大学 | Zinc coordination polymer as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098614A (en) * | 2014-07-23 | 2014-10-15 | 苏州大学 | Zinc coordination polymer as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| HUI YANG等,: "Doping copper into ZIF-67 for enhancing gas uptake capacity and visible-light-driven photocatalytic degradation of organic dye", 《J. MATER. CHEM.》 * |
| XIN-XIN XU等,: "Photocatalytic activity of transition-metal-ion doped coordination polymer (CP): photoresponse region extension and quantum yields enhancement via doping of transition metal ions into the framework of CPs", 《DALTON TRANSACTIONS》 * |
| 王艳: "羧酸类配位聚合物的研究进展", 《应用化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN107501535A (en) * | 2017-08-14 | 2017-12-22 | 常州大学 | Zn complex catalyst of PLA and preparation method thereof is prepared for ring-opening polymerisation |
| CN110734554A (en) * | 2019-11-23 | 2020-01-31 | 南京科技职业学院 | Zn (II) three-dimensional blending coordination polymer and preparation method thereof |
| CN110734554B (en) * | 2019-11-23 | 2021-07-27 | 南京科技职业学院 | Zn (II) three-dimensional mixed coordination polymer and preparation method thereof |
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Application publication date: 20150422 |