CN105884805B - A kind of Cd (II) mixture coordination polymer and preparation method thereof - Google Patents
A kind of Cd (II) mixture coordination polymer and preparation method thereof Download PDFInfo
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- CN105884805B CN105884805B CN201610297015.8A CN201610297015A CN105884805B CN 105884805 B CN105884805 B CN 105884805B CN 201610297015 A CN201610297015 A CN 201610297015A CN 105884805 B CN105884805 B CN 105884805B
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 58
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 239000012153 distilled water Substances 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 235000019441 ethanol Nutrition 0.000 claims description 29
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- 229910001220 stainless steel Inorganic materials 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims description 18
- 230000004044 response Effects 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 12
- 150000001661 cadmium Chemical class 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 3
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- PSIBWKDABMPMJN-UHFFFAOYSA-L cadmium(2+);diperchlorate Chemical compound [Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PSIBWKDABMPMJN-UHFFFAOYSA-L 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000013140 multifunctional metal-organic framework Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/08—Cadmium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention relates to a kind of Cd (II) mixture coordination polymers and preparation method thereof.Mixture coordination polymer is constructed by metal Cd ions and two organic molecular species ligands, and Cd (II) mixture coordination polymer stability of the present invention is good, has photoluminescent property, is expected to be used as fluorescent material.The preparation method of Cd (II) mixture coordination polymer of the present invention is simple, easy to operate, and yield is high, and reproducibility is good.
Description
Technical field
The present invention relates to coordination polymer technical fields, more particularly to a kind of cadmium (II) mixture coordination polymer and its preparation
Method.
Background technology
Coordination polymer is with organic ligand and metal ion (or metal cluster) for construction unit, by between them
Metal organic framework crystalline material (the Metal-Organic with periodic network structure that interaction force is self-assembly of
Frameworks, MOFs).Compared with traditional inorganic material and organic supermolecular material, such compound is due to metal ion
It is wider with the range of choice of organic ligand, therefore can design and synthesize with rich and varied skeleton structure and show excellent
Physical and chemical performance material.Since such compound not only possesses aesthetic value and in itself in gas storage, separation, gas
Many necks such as body storage, separation, trapping, selective catalysis, chiral resolution, drug conveying, light, electricity, magnetics and molecular recognition
Domain suffers from potential actual application value.
Nitrogenous heterocyclic ligand includes pyridine, imidazoles, triazole, tetrazolium, pyrazoles, pyrazine and its various derivatives etc., due to
Such ligand has been widely used for constructing new function coordination polymer to nitrogen-atoms coordination ability by force, but only azacyclo- is matched
Body has coordination mode relatively simple.
The carboxyl oxygen atom of organic carboxyl acid class ligand has abundant coordination mode, can be with transition, rare earth ion, metal
The features such as complex skeleton structure that the coordinations such as cluster are formed, such thermal analysis is high, Scalability.Especially aromatics
Carboxylic acid ligand can effectively be prevented the generation through structure, be established to construct Porous materials due to the rigidity characteristic of itself skeleton
Basis is determined.
Based on the design controllability to object construction, it is to make full use of this two classes ligand respective that chemists, which commonly use strategy,
Advantage constructs mixture coordination polymer.
For containing d10For the complex of metal ion, photoluminescent property is an important performance of such cooperation polymer.
Currently, the research work about fluorescence MOFs materials is concentrated mainly on：Creating has the MOFs materials of adjustable photoluminescent property, opens
Send out its application in terms of luminescent device；Using fluorescence MOFs materials as probe in detecting environment, it is studied in terms of chemical sensor
Application；The multi-functional MOFs materials in conjunction with fluorescence, magnetism and biocompatibility are created, its answering in biomedical aspect is developed
With, such as cell biological imaging of tissue and drug conveying monitoring and treatment.
Invention content
Technical problem to be solved by the invention is to provide a kind of cadmium (II) mixture coordination polymer coordination polymers.
In order to solve the above technical problems, technical solution provided by the invention is：Using Formulas I as the coordination polymerization of skeleton unit
Object,
Formulas I：
Wherein, Cd (II) be hexa-coordinate, distortion octahedral coordination configuration.
Preferably, Cd (II) the mixture coordination polymer belongs to rhombic system, Pbcn space groups, cell parameter a=
13.201 (3) nm, b=10.104 (2) nm, c=19.943 (4) nm, α=β=γ=90.00 °, V=2660.1 (9) nm3。
In the present invention, the chemical formula of Cd (II) the mixture coordination polymer is Cd (C10H8N2)2(C10H4O8), wherein
C10H8N2It is 2,2 '-bipyridyls, structural formula is as follows：
C10H4O8For Pyromellitic Acid dianion, structural formula is as follows：
The basic construction unit of Cd (II) mixture coordination polymer is one-dimentional structure, and wherein Cd (II) is hexa-coordinate, respectively
4 N atoms of the 2,2 '-bipyridine ligands different from coming from two and 2 O originals for coming from two equal benzene tetramethyl radical ions
Son coordination, what cadmium central ion was taken is the octahedral coordination configuration of distortion.Equal benzene tetramethyl radical ion plays bridge linking effect, even
Adjacent metal Cd ion centers are tied, one-dimensional chain structure is formed, adjacent one-dimensional chain passes through the carboxylic acid on Pyromellitic Acid
Group forms intermolecular H-OH hydrogen bond actions and is further built into two-dimensional layered structure.
Another technical problem to be solved by the present invention is that providing a kind of side preparing above-mentioned Cd (II) mixture coordination polymer
Method.
In order to solve the above technical problems, technical solution provided by the invention is：The preparation of Cd (II) mixture coordination polymer
Method includes the following steps：By cadmium salt, 2,2 '-bipyridyls and Pyromellitic Acid are added in the mixed solution of ethyl alcohol and distilled water,
Regulation system is subsequently placed in autoclave in acidity and carries out water after stirring（Solvent）Thermal response, cooling after reaction, mistake
Filter obtains the Cd (II) mixture coordination polymer.
Preferably, the cadmium salt is one or more of caddy, cadmium nitrate, cadmium perchlorate, cadmium acetate, cadmium sulfate
Mixture.
Preferably, the ratio between molal quantity of the molal quantity of cadmium and 2 in cadmium salt, 2 '-bipyridyls and Pyromellitic Acid is 1:
1.8-3 : 1-2；Preferably, the ratio between molal quantity of the molal quantity of cadmium and 2 in cadmium salt, 2 '-bipyridyls and Pyromellitic Acid is 1:
2.2-2.6 : 1.2-1.8；Preferably, the molal quantity of the molal quantity of cadmium and 2 in cadmium salt, 2 '-bipyridyls and Pyromellitic Acid it
Than being 1: 2.5 : 1.5
Preferably, cadmium salt and 2,2 '-bipyridyls and Pyromellitic Acid are added in the mixed solution of ethyl alcohol and distilled water, are stirred
The pH values for mixing rear regulation system are 2-6；Preferably, ethyl alcohol and steaming is added in cadmium salt and 2,2 '-bipyridyls and Pyromellitic Acid
In the mixed solution of distilled water, the pH values of regulation system are 3-5 after stirring；Preferably, by cadmium salt and 2,2 '-bipyridyls and equal benzene
Tetracarboxylic acid is added in the mixed solution of ethyl alcohol and distilled water, and the pH values of regulation system are 4 after stirring.
Preferably, the temperature of water (solvent) thermal response is 120-160 DEG C, and the time of water (solvent) thermal response is 24-
72h ；Preferably, the temperature of water (solvent) thermal response is 130-150 DEG C, and the time of hydro-thermal reaction is 36-60h；It is preferred that
The temperature on ground, water (solvent) thermal response is 140 DEG C, and the time of water (solvent) thermal response is 48h.
Preferably, ethyl alcohol and distilled water volume ratio are 1 in the mixed solution of the ethyl alcohol and distilled water: 4；Preferably,
Ethyl alcohol and distilled water volume ratio are 2 in the mixed solution of the ethyl alcohol and distilled water: 3；Preferably, the ethyl alcohol and distilled water
Mixed solution in ethyl alcohol and distilled water volume ratio be 1: 1.
Beneficial effects of the present invention：In the present invention, as shown in Fig. 4, Cd (II) the mixture coordination polymer, which has, to be stablized
Fluorescence, can be used as potential fluorescent material, as shown in Fig. 5, Cd (II) the mixture coordination polymers are on 185 DEG C of left sides
It is right to start to decompose, and it is placed to it at room temperature can stablize the several months, therefore its stability is good, to be carried as potential fluorescent material
Basis is supplied；The preparation method of Cd (II) mixture coordination polymer of the present invention, it is simple, convenient, it is prepared by adjusting
Parameters in method keep the preparation method yield of the Cd (II) mixture coordination polymer high, favorable reproducibility.
Description of the drawings
The coordination context diagram of Cd (II) in Fig. 1 Cd of the present invention (II) coordination polymer；
One-dimensional catenary structure figure in Fig. 2 Cd of the present invention (II) coordination polymer；
The two-dimensional layered structure figure formed in Fig. 3 Cd of the present invention (II) coordination polymer；
The solid state fluorescence figure of Fig. 4 Cd of the present invention (II) coordination polymers and 2,2 '-bipyridyls and Pyromellitic Acid
Spectrum；
The thermogravimetric collection of illustrative plates of Fig. 5 Cd of the present invention (II) position polymer；
The infrared light collection of illustrative plates of Fig. 6 Cd of the present invention (II) position polymer.
Specific implementation mode
Embodiment 1：
0.1mmol cadmium nitrates, 0.25mmol 2,2 '-bipyridyls and 0.15mmol Pyromellitic Acids are dissolved in 20mL
Ethyl alcohol/distilled water (V:V=1:1) in, the pH of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
Value is 4, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), will
It is put into baking oven after stainless steel cauldron sealing, water (solvent) thermal response 48h, cooled to room temperature, after filtering at 140 DEG C
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 63.6% (being based on Cd).
Embodiment 2：
0.1mmol cadmium sulfates, 0.22mmol 2,2 '-bipyridyls and 0.15mmol Pyromellitic Acids are dissolved in 20mL
Ethyl alcohol/distilled water (V:V=1:4) in, the pH of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
Value is 5, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), will
Stainless steel cauldron sealing after be put into baking oven, at 160 DEG C water (solvent) thermal response for 24 hours, cooled to room temperature, after filtering
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 62.8% (being based on Cd).
Embodiment 3：
0.1mmol cadmium acetates, 0.2mmol 2,2 '-bipyridyls and 0.15mmol Pyromellitic Acids are dissolved in 20mL second
Alcohol/distilled water (V:V=2:3) in, the pH value of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
It is 4, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), it will not
It is put into baking oven after rust steel reaction kettle sealing, water (solvent) thermal response 72h, cooled to room temperature, after filtering at 140 DEG C
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 61.5% (being based on Cd).
Embodiment 4：
0.1mmol caddies, 0.22mmol 2,2 '-bipyridyls and 0.12mmol Pyromellitic Acids are dissolved in 20mL second
Alcohol/distilled water (V:V=1:1) in, the pH value of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
It is 3, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), it will not
It is put into baking oven after rust steel reaction kettle sealing, water (solvent) thermal response 36h, cooled to room temperature, after filtering at 130 DEG C
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 62.1% (being based on Cd).
Embodiment 5：
0.1mmol cadmium perchlorates, 0.26mmol 2,2 '-bipyridyls and 0.13mmol Pyromellitic Acids are dissolved in 20mL
Ethyl alcohol/distilled water (V:V=1:1) in, the pH of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
Value is 3, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), will
Stainless steel cauldron sealing after be put into baking oven, at 140 DEG C water (solvent) thermal response for 24 hours, cooled to room temperature, after filtering
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 62.6% (being based on Cd).
Embodiment 6：
0.1mmol cadmium sulfates, 0.25mmol 2,2 '-bipyridyls and 0.15mmol Pyromellitic Acids are dissolved in 20mL second
Alcohol/distilled water (V:V=1:1) in, the pH value of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
It is 4, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), it will not
It is put into baking oven after rust steel reaction kettle sealing, water (solvent) thermal response 48h, cooled to room temperature, after filtering at 140 DEG C
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 63.5% (being based on Cd).
Embodiment 7：
0.1mmol cadmium sulfates, 0.25mmol 2,2 '-bipyridyls and 0.12mmol Pyromellitic Acids are dissolved in 20mL second
Alcohol/distilled water (V:V=1:1) in, the pH value of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
It is 4, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), it will not
It is put into baking oven after rust steel reaction kettle sealing, water (solvent) thermal response 48h, cooled to room temperature, after filtering at 140 DEG C
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 62.5% (being based on Cd).
Embodiment 8：
0.1mmol cadmium sulfates, 0.25mmol 2,2 '-bipyridyls and 0.15mmol Pyromellitic Acids are dissolved in 20mL second
Alcohol/distilled water (V:V=1:4) in, the pH of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
Value is 4, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), will
It is put into baking oven after stainless steel cauldron sealing, water (solvent) thermal response 48h, cooled to room temperature, after filtering at 140 DEG C
A large amount of colourless bulk crystals are obtained, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water, are produced
Rate is 62.8% (being based on Cd).
Embodiment 9：
0.1mmol cadmium sulfates, 0.25mmol 2,2 '-bipyridyls and 0.12mmol Pyromellitic Acids are dissolved in 20mL second
Alcohol/distilled water (V:V=1:1) in, the pH of the sodium hydroxide solution regulation system of 0.2mol/L is utilized after stirring at normal temperature 15min
Value is 4, is filtered after stirring 15min at room temperature, filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), will
It is put into baking oven after stainless steel cauldron sealing, water (solvent) the thermal response 48h at 130 DEG C, cooled to room temperature, filtering
After obtain a large amount of colourless bulk crystals, the Cd (II) coordination polymer is obtained after colourless bulk crystals are washed with distilled water,
Yield is 63.3% (being based on Cd).
The chemical formula of Cd (II) the mixture coordination polymer prepared in Example 1 is C30H20N4O8Cd carries out member to it
Element analysis, it is as a result as follows：Theoretical value (%)：C, 53.25；H, 2.96；N, 8.28.Measured value (%)：C, 53.31; H,
2.91; N, 8.32。
Cd (II) the mixture coordination polymer prepared in Example 1 carries out examination of infrared spectrum, spectrogram such as Fig. 6 institutes
Show.
Cd (II) the mixture coordination polymer prepared in Example 1 carries out crystal structure test, predominant crystal data
As shown in table 1.
The predominant crystal data of Cd (II) the mixture coordination polymer prepared in 1 embodiment 1 of table
| Compound | 1 |
| Empirical formula | C30 H20 N4 O8 Cd |
| Formular weight | 676.90 |
| Crystal size / mm | 0.30×0.25×0.20 |
| Crystal system | Orthorhombic |
| Space group | Pbcn |
| a / nm | 13.201(3) |
| b / nm | 13.201(3) |
| c/ nm | 19.943(4) |
| α / (º) | 90.00 |
| β / (º) | 90.00 |
| γ / (º) | 90.00 |
| V / nm3 | 2660.1(9) |
| Z | 4 |
| D c / (g·cm-3) | 1.690 |
| λ / nm | 0.071073 |
| Temperature / K | 223.15 |
| θ range / (º) | 1.54~27.47 |
| Collected reflections | 10560 |
| Unique reflections | 3027 |
| Observed reflection | 2727 |
| R int | 0.0204 |
| F(000) | 1360 |
| μ / mm-1 | 0.884 |
| R 1 | 0.0323 |
| wR 2 | 0.1149 |
Cd (II) mixture coordination polymer of the present invention, chemical formula are Cd (C10H8N2)2(C10H4O8), wherein
C10H8N2It is 2,2 '-bipyridyls, C10H4O8For Pyromellitic Acid root dianion.The coordination polymer belongs to rhombic system,
Pbcn space groups, cell parameter are:A=13.201 (3) nm, b=10.104 (2) nm, c=19.943 (4) nm, α=β=γ
=90.00 °, V=2660.1 (9) nm3.It is one-dimentional structure that Cd (II) the mixture coordination polymers construct primitive substantially, therein
Cd (II) is hexa-coordinate, and what is taken is the octahedral coordination configuration of distortion, comes from two with 4 coordination N atoms of Cd coordinations
A 2,2 '-different bipyridine ligands, 2 O atoms are respectively from the carboxylic acid group on two equal benzene tetramethyl radical ions, such as scheme
1, shown in Fig. 2.Equal benzene tetramethyl radical ion plays bridge linking effect, links adjacent metal center Cd ions, forms one-dimensional chain
Structure, adjacent one-dimensional chain form intermolecular H-OH hydrogen bond actions into one by the carboxylic acid group on Pyromellitic Acid
Step is built into two-dimensional layered structure, as shown in Figure 3.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (8)
1. a kind of Cd (II) mixture coordination polymer, chemical formula is Cd (C10H8N2)2(C10H4O8), wherein C10H8N2It is 2,
2 '-bipyridyls, C10H4O8For Pyromellitic Acid root dianion；
It is characterized in that, the coordination polymer belongs to rhombic system, Pbcn space groups, cell parameter is a=13.201 (3)
Nm, b=10.104 (2) nm, c=19.943 (4) nm, α=β=γ=90.00 °, V=2660.1 (9) nm3；
The coordination polymer using Formulas I as the coordination polymer of skeleton unit,
Formulas I：
Wherein, Cd (II) be hexa-coordinate, distortion octahedral coordination configuration.
2. the preparation method of Cd (II) mixture coordination polymer according to claim 1, includes the following steps：By cadmium salt, 2,
2 '-bipyridyls and Pyromellitic Acid are added in the mixed solution of ethyl alcohol and distilled water, and after stirring then regulation system is set in acidity
Hydro-thermal reaction is carried out in autoclave, cools down after reaction, the Cd (II) coordination polymer is obtained by filtration.
3. the preparation method of Cd (II) mixture coordination polymer according to claim 2, which is characterized in that the cadmium salt is chlorine
The mixture of one or more of cadmium, cadmium nitrate, cadmium perchlorate, cadmium acetate, cadmium sulfate.
4. the preparation method of Cd (II) mixture coordination polymer according to claim 2, which is characterized in that cadmium rubs in cadmium salt
Your the ratio between number and the molal quantity of 2,2 '-bipyridyls and Pyromellitic Acid are 1: 2.5 : 1.5.
5. the preparation method of Cd (II) mixture coordination polymer according to claim 2, which is characterized in that by cadmium salt and 2,
2 '-bipyridyls and Pyromellitic Acid are added in the mixed solution of ethyl alcohol and distilled water, and the pH value of regulation system is 4 after stirring.
6. the preparation method of Cd (II) mixture coordination polymer according to claim 2, which is characterized in that the ethyl alcohol and steaming
Ethyl alcohol and distilled water volume ratio are 1 in the mixed solution of distilled water:1.
7. the preparation method of Cd (II) mixture coordination polymer according to claim 2, which is characterized in that the hydro-thermal reaction
Temperature be 140 DEG C, time of water (solvent) thermal response is 48h.
8. the preparation method of Cd (II) mixture coordination polymer according to claim 2, which is characterized in that including following step
Suddenly：0.1mmol cadmium nitrates, 0.25mmol 2,2 '-bipyridyls and 0.15mmol Pyromellitic Acids are dissolved in 20mL ethyl alcohol and steaming
In distilled water, the volume ratio of the ethyl alcohol and distilled water is 1：It is molten using the sodium hydroxide of 0.2mol/L after 1, stirring at normal temperature 15min
The pH value of liquid regulation system is 4, and filtrate is transferred to and is made in the stainless steel cauldron of lining with polytetrafluoroethylene (PTFE), by stainless steel
It is put into baking oven after reaction kettle sealing, the hydro-thermal reaction 48h at 140 DEG C, cooled to room temperature obtains the Cd after filtering
(II) mixture coordination polymer；
Or by 0.1mmol cadmium sulfates, 0.22mmol2,2 '-bipyridyls and 0.15mmol Pyromellitic Acids be dissolved in 20m ethyl alcohol and
In distilled water, the volume ratio of the ethyl alcohol and distilled water is 1：The sodium hydroxide of 0.2mol/L is utilized after 4, stirring at normal temperature 15min
The pH value of solution regulation system is 5, is filtered after stirring 15min at room temperature, filtrate is transferred to and makees lining with polytetrafluoroethylene (PTFE)
It in stainless steel cauldron, is put into baking oven after stainless steel cauldron is sealed, hydro-thermal reaction for 24 hours, naturally cools at 160 DEG C
Room temperature obtains the Cd (II) mixture coordination polymer after filtering；
Or 0.1mmol caddies, 0.22mmol 2,2 '-bipyridyls and 0.12mmol Pyromellitic Acids are dissolved in 20mL ethyl alcohol
In distilled water, the volume ratio of the ethyl alcohol and distilled water is 1：The hydroxide of 0.2mol/L is utilized after 1, stirring at normal temperature 15min
The pH value of sodium solution regulation system is 3, is filtered after stirring 15min at room temperature, filtrate is transferred to and makees lining with polytetrafluoroethylene (PTFE)
Stainless steel cauldron in, be put into baking oven after stainless steel cauldron is sealed, in 130 DEG C of hydro-thermal reaction 36h, naturally cool to
Room temperature obtains the Cd (II) mixture coordination polymer after filtering.
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