CN103626788A - Hybrid material with function of adsorbing and desorbing iodine and synthetic methods thereof - Google Patents

Hybrid material with function of adsorbing and desorbing iodine and synthetic methods thereof Download PDF

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Publication number
CN103626788A
CN103626788A CN201310437621.1A CN201310437621A CN103626788A CN 103626788 A CN103626788 A CN 103626788A CN 201310437621 A CN201310437621 A CN 201310437621A CN 103626788 A CN103626788 A CN 103626788A
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hybrid material
iodine
adsorption desorption
tetramethyl
acetonitrile
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何军
段晶晶
曹鹏
陈嘉华
孙明
余林
成晓玲
吴雪彬
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Guangdong University of Technology
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Guangdong University of Technology
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Abstract

The invention relates to a hybrid material with a function of adsorbing and desorbing iodine and synthetic methods thereof. The chemical formula of the hybrid material is C12H17CuIN5, wherein the crystals belong to an orthorhombic system, the space group is Ima2, and the lattice parameters are as follows: a=17.670(6) angstrom, b=12.348(4) angstrom, c=7.295(3) angstrom, alpha=beta=gamma=90 degrees; v=1591.6(9) angstrom<3>. Two synthetic methods are provided. One of the synthetic methods comprises the following steps: dissolving a mixture of an organic ligand 3, 5, 3', 5'-tetramethyl bipyrazol and metal salt CuI in an acetonitrile solvent; heating and reacting for 24-72 hours under a solvothermal condition to obtain red butterfly crystals; and washing by acetonitrile and drying. The other one of the synthetic methods comprises the following steps: mixing the organic ligand 3, 5, 3', 5'-tetramethyl bipyrazol and metal salt CuI in a molar ratio of 0.5:(1.0-2.0):1.0, and dissolving in acetonitrile liquor; heating flux to react; then filtering the liquor; collecting powder; and drying. The hybrid material synthesized by the invention is high in crystallinity, stable in main body frame, free from remarkable weightlessness below 265 DEG C and high in porosity, has the adsorbing and desorbing function to iodine simple substance, and can be recycled. The synthetic methods are simple, high in yield, low in cost and suitable for industrialized production on a large scale.

Description

A kind of hybrid material and synthetic method thereof with adsorption desorption iodine
Technical field
The present invention relates to a kind of hole metal complexes material, be specifically related to a kind of hybrid material and synthetic method thereof with adsorption desorption iodine, belong to transition metal complex material technology field.
Background technology
Hybrid inorganic-organic materials is one dimension, two dimension or the three-dimensional network skeleton being formed by connecting by coordinate bond by metal ion or metal cluster and organic ligand, also can be described as metal-organic framework materials.The method of preparing hybrid inorganic-organic materials is varied, generally includes hydro-thermal (solvent thermal) synthesis method, natural volatilization method, diffusion process, microwave assisting method, sol-gel method and circumfluence method etc.At present, it is hydro-thermal (solvent thermal) synthesis method that people adopt maximum, and it is that reactant is mixed and put in the reactor of tetrafluoroethylene, puts into stainless steel outer lining, and under High Temperature High Pressure, reaction obtains product.This method reaction times is short, has solved reactant undissolvable problem at normal temperatures and pressures, and still, with respect to other method, hydrothermal synthesis method requires high to equipment corrosion, need high temperature high voltage resistant, and reaction conditions is harsher.Circumfluence method is to adopt reflux by reactant reacting by heating under normal pressure, although use range is limited, reaction conditions is gentle, and easily operation, is applicable to scale operation.The present invention not only can adopt hydrothermal synthesis method to obtain, and can adopt circumfluence method to obtain product.
In recent years, because the potential application examples of the extremely unique structure of hybrid inorganic-organic materials and each field makes them particularly noticeable as aspects such as gas storage, gas adsorption and separated, heterogeneous catalyst, medicine storage and transportation, molecular recognition, photoluminescence and chiral separation.At present, the research that hybrid inorganic-organic materials is applied to gas storage and absorption aspect is the most deep, have a large amount of bibliographical informations by hybrid inorganic-organic materials for absorption with store H 2, CH 4, CO 2deng gas, yet, recently, the research that hybrid inorganic-organic materials is applied to adsorb iodine that also had a small amount of bibliographical information, as document 1(Ming-Hua Zeng, Mohamedally Kurmoo, j. Am. Chem. Soc.2010,132,2561-2563), document 2(Zheng Yin, and Qiang-Xin Wang, and Ming-Hua Zeng, j. Am. Chem. Soc. 2012,134, report 4857-4863) makes us fresh and new, has expanded the application potential of hybrid inorganic-organic materials.
Yet the application of hybrid inorganic-organic materials is at present subject to a lot of restrictions, wherein, maximum limitation is that hybrid inorganic-organic materials lacks good stability, and their skeleton structure is easy to cave in, and is impatient at high temperature, thereby has limited its application.Hybrid inorganic-organic materials thermostability prepared by the present invention can reach 265 ℃, we not only can use the iodide ion in this material adsorbent solution, and the iodine molecule in adsorbable gas, and the iodine of absorption can be discharged, structure remains unchanged, and can realize recycle.This material has broad application prospects for the area containing iodine sewage, high iodine water source area, high iodine steam and radioiodine radiation.
Summary of the invention
The object of the present invention is to provide a kind of hybrid material with adsorption and desorption iodine function.
Another object of the present invention is to provide a kind of synthetic method with the hybrid material of adsorption desorption iodine.
In order to address the above problem, the technical solution adopted in the present invention is:
A hybrid material with adsorption desorption iodine, chemical formula is C 12h 17cuIN 5, structural representation is shown in accompanying drawing 2.
The described hybrid material with adsorption desorption iodine, main infrared absorption peak is as follows:
3309.6(s),2919.8(m),1670.6(w),1631.6(m),1459.1(w),1419.4(m),1384.5(w),1281.2(w),1028.3(s),659.5(m),556.9(m)。
The described crystal with the hybrid material of adsorption desorption iodine function belongs to rhombic system, and spacer is: ima2, unit cell parameters is: a=17.670 (6); B=12.348 (4); C=7.295 (3); a= b= g=90 °; V=1591.6 (9) 3; Wherein, Cu (I) metal center angle is 97.46 (9) ~ 126.68 (19) °, adopt the tetrahedral coordination of distortion, wherein, Cu atom respectively with two 3,5, N coordination (Cu N bond distance is 1.999 (3)) in 3 ', 5 '-tetramethyl-connection pyrazoles, (Cu I bond distance is respectively 2.6487 (9) in two I coordinations, 2.8410 (7)), formed the three-dimensional diamond network that porosity is 55.8%.
A synthetic method with the hybrid material of adsorption desorption iodine, comprises the steps:
Organic ligand 3,5, the mixture of 3 ', 5 '-tetramethyl-connection pyrazoles and metal-salt CuI is dissolved in acetonitrile solvent, after reacting by heating, collects crystal, with acetonitrile washing, dry.
Described 3,5,3 ', 5 '-tetramethyl-connection pyrazoles is 0.5:1.0 ~ 2.0:1.0 with the mol ratio of metal-salt CuI, preferred 1.0:1.0.
Described Heating temperature is 120 ~ 160 ° of C, preferably 140 ° of C.
The described reaction times is 24 ~ 72h, preferably 48h.
Another kind has the synthetic method of the hybrid material of adsorption desorption iodine, comprises the steps:
Organic ligand 3,5, the mixture of 3 ', 5 '-tetramethyl-connection pyrazoles and metal-salt CuI is dissolved in acetonitrile solvent, under reflux, reacts, and subsequent filtration solution, collects powder, with acetonitrile washing, dry.
Described 3,5,3 ', 5 '-tetramethyl-connection pyrazoles is 0.5:1.0 ~ 2.0:1.0 with the mol ratio of metal-salt CuI, preferred 1.0:1.0.
Described Heating temperature is 82 ~ 160 ° of C.
The described reaction times is 1 ~ 5h.
The invention has the beneficial effects as follows:
(1) this material not only useable solvents thermal synthesis method obtain, and can under normal pressure, adopt circumfluence method to prepare, reaction conditions is gentle, preparation method is simple, and product purity is high, and aftertreatment is easy and productive rate is higher, cost is low, is applicable to carrying out large-scale industrial production.
(2) material of synthesized has the crystallinity of height, structure easily characterizes, better heat stability, can reach 265 ℃, and porosity is up to 55.8%, iodine molecule is had to adsorption and desorption function, the iodine molecule in adsorbable solution not only, and can adsorb the iodine molecule in steam, and the iodine of absorption can be discharged, but its structure does not change, can recycle.
Accompanying drawing explanation
Fig. 1 hybrid material C of the present invention 12h 17cuIN 5thermogram;
Fig. 2 hybrid material C of the present invention 12h 17cuIN 5single crystal structure figure;
Fig. 3 hybrid material C of the present invention 12h 17cuIN 5tomograph;
Fig. 4 hybrid material C of the present invention 12h 17cuIN 5x-ray powder diffraction figure;
Fig. 5 hybrid material C of the present invention 12h 17cuIN 5suction iodine colour-change figure;
Fig. 6 hybrid material C of the present invention 12h 17cuIN 5de-iodine ultraviolet-visible pectrophotometer figure.
Embodiment
Below by embodiment, the present invention is described in further details, these embodiment are only used for illustrating the present invention, do not limit the scope of the invention.
hybrid material synthetic with adsorption desorption iodine:
embodiment 1
By 3 of 0.1mmol, 5,3 ', 5 '-tetramethyl-connection pyrazoles and 0.1 mmol cuprous iodide are dissolved in 8 mL acetonitrile solutions, stirring at normal temperature 10 min, transfer in tetrafluoroethylene autoclave subsequently, place it in 140 ℃ of baking ovens and react 48h, naturally cooling filters and obtains target product, productive rate 52.6% afterwards.
embodiment 2
By 3 of 0.05mmol, 5,3 ', 5 '-tetramethyl-connection pyrazoles and 0.2 mmol cuprous iodide are dissolved in 8 mL acetonitrile solutions, stirring at normal temperature 10min, transfers in tetrafluoroethylene autoclave subsequently, places it in 120 ℃ of baking ovens and reacts 48h, naturally cooling filters and obtains target product, productive rate 32.6% afterwards.
embodiment 3
By 3 of 0.1mmol, 5,3 ', 5 '-tetramethyl-connection pyrazoles and 0.2 mmol cuprous iodide are dissolved in 8 mL acetonitrile solutions, stirring at normal temperature 10min, transfers in tetrafluoroethylene autoclave subsequently, places it in 160 ℃ of baking ovens and reacts 48h, naturally cooling filters and obtains target product, productive rate 45.7% afterwards.
embodiment 4
By 3,5 of 0.3 mmol, 3 ' 5 '-tetramethyl-connection pyrazoles and 0.3 mmol cuprous iodide are dissolved in 15mL acetonitrile solution, be heated 82 ℃ and the 1h that refluxes, naturally cooling filters afterwards, collects powder, with acetonitrile washing, be dried to obtain target product, productive rate is 94.6%.
embodiment 5
By 3,5 of 0.3 mmol, 3 ' 5 '-tetramethyl-connection pyrazoles and 0.6 mmol cuprous iodide are dissolved in 15mL acetonitrile solution, be heated 82 ℃ and the 1h that refluxes, naturally cooling filters afterwards, collects powder, with acetonitrile washing, be dried to obtain target product, productive rate is 64.8%.
embodiment 6
By 3,5 of 0.4 mmol, 3 ' 5 '-tetramethyl-connection pyrazoles and 0.6 mmol cuprous iodide are dissolved in 15mL acetonitrile solution, be heated 160 ℃ and the 5h that refluxes, naturally cooling filters afterwards, collects powder, with acetonitrile washing, be dried to obtain target product, productive rate is 84.7%.
embodiment 7
(1) X-ray powder diffraction characterizes purity, and accompanying drawing 4 is hybrid material C of the present invention 12h 17cuIN 5x-ray powder diffraction pattern.Powder diffraction data is collected on Bruker D8 advance diffractometer and completes, the operating voltage of instrument is 40 KV, and electric current is 40 mA, uses copper target X-ray (the Cu Ka of graphite monochromatization, λ=1.5418), within the scope of 5 ° to 30 °, continuous sweep completes.Single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury software.
(2) mensuration of crystalline structure
Choose under the microscope on the Gmini A diffractometer of monocrystalline ， Agilent company of suitable size (Cu Ka, λ=1.5418), ray is monochromatic by graphite monochromator.Data processing is used the program CrysAlis of diffractometer pro.1; Structure is used direct method to solve initial model, then use based on f 2method of least squares refined structure.All non-hydrogen atoms all carry out anisotropic refine, determine the position of hydrogen atom by the method for theoretical hydrogenation.Accompanying drawing 3 is hybrid material C of the present invention 12h 17cuIN 5crystalline structure figure.The partial parameters of the data gathering of crystallography point diffraction and structure refinement is listed in table 1.
the hybrid material adsorption and desorption iodine with adsorption desorption iodine:
embodiment 8
Get 50mg hybrid material C 12h 17cuIN 5powder is placed in the cyclohexane solution that 5mL is dissolved with 5mg iodine, observes it and inhales iodine colour-change.Just start, solution is intense violet color clear solution, and powder is light yellow, and along with the prolongation of time, deep purple solution shoals gradually, powder color burn, and after 2.5h, solution becomes light red, approaches water white transparency, and powder becomes brown, sees Fig. 5.
embodiment 9
Get 100mg hybrid material C 12h 17cuIN 5be placed in plastic containers and put into the vial with cover that 0.5g iodine is housed, standing a couple of days, take out powder and rinse with ether, dry, weigh to obtain 118mg.Get 5 suction iodine crystal and be placed in 2mL methanol solution, with ultraviolet-visible pectrophotometer, measure its de-iodine speed, see Fig. 6.
The crystallographic data of table 1 hybrid material
Figure 21019DEST_PATH_IMAGE001
。

Claims (10)

1. a hybrid material with adsorption desorption iodine, is characterized in that: chemical formula is C 12h 17cuIN 5, its structural formula is:
Figure RE-370855DEST_PATH_IMAGE001
。
2. a kind of hybrid material with adsorption desorption iodine according to claim 1, is characterized in that: crystal belongs to rhombic system, and spacer is: ima2; Unit cell parameters is: a=17.670 (6), b=12.348 (4), c=7.295 (3);
Figure 53991DEST_PATH_IMAGE002
; V=1591.6 (9) 3.
3. a kind of hybrid material with adsorption desorption iodine according to claim 2, is characterized in that: copper atom is taked four-coordination tetrahedral configuration, and with two iodine Atomic coordinates, Cu I bond distance is respectively 2.6487 (9) respectively, 2.8410 (7); Two connection nitrogen coordination Cu N bond distances on pyrazoles are 1.999 (3), the three-dimensional diamond network that to have formed porosity be 55.8%.
4. for the synthesis of a method with the hybrid material of adsorption desorption iodine claimed in claim 1, it is characterized in that: comprise the steps:
Organic ligand 3,5, the mixture of 3 ', 5 '-tetramethyl-connection pyrazoles and metal-salt CuI is dissolved in acetonitrile solvent, and reacting by heating under solvent thermal condition, obtains red butterfly-like crystal, with acetonitrile washing, dry.
5. a kind of synthetic method with the hybrid material of adsorption desorption iodine according to claim 4, is characterized in that: the described reacting by heating time is 24 ~ 72h.
6. a kind of synthetic method with the hybrid material of adsorption desorption iodine according to claim 4, is characterized in that: described 3,5, the mol ratio of 3 ', 5 '-tetramethyl-connection pyrazoles and metal-salt CuI is 0.5:1.0 ~ 2.0:1.0.
7. a kind of synthetic method with the hybrid material of adsorption desorption iodine according to claim 4, is characterized in that: described 3,5, the mol ratio of 3 ', 5 '-tetramethyl-connection pyrazoles and metal-salt CuI is 1.0:1.0.
8. a kind of synthetic method with the hybrid material of adsorption desorption iodine according to claim 4, is characterized in that: described Heating temperature is 120 ~ 160 ° of C.
9. for the synthesis of a method with the hybrid material of adsorption desorption iodine claimed in claim 1, it is characterized in that: comprise the steps:
Organic ligand 3,5,3 ', 5 '-tetramethyl-connection pyrazoles is after 0.5:1.0 ~ 2.0:1.0 mixes with metal-salt mol ratio, is dissolved in acetonitrile solution, heating reflux reaction, subsequent filtration solution, collects powder, with acetonitrile washing, dry.
10. a kind of synthetic method with the hybrid material of adsorption desorption iodine according to claim 9, is characterized in that: described reflux time is 1h ~ 5h; Reacting by heating temperature is 82 ~ 160 ° of C.
CN201310437621.1A 2013-09-24 2013-09-24 Hybrid material with function of adsorbing and desorbing iodine and synthetic methods thereof Pending CN103626788A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744495A (en) * 2014-07-04 2015-07-01 广东工业大学 Chiral double-helix coordination polymer and preparation method thereof
CN105153432A (en) * 2014-11-22 2015-12-16 广东工业大学 Coordination polymer based on flexible dual ligand containing nitrogen and carboxylic acid and preparation method of coordination polymer
CN106698457A (en) * 2017-03-13 2017-05-24 青岛大学 Three-dimensional expansion skeleton copper iodide material having 27-MR oversized pore passages and preparation method thereof
CN108640934A (en) * 2018-05-30 2018-10-12 山西大学 A kind of cadmium metal organic framework material and its preparation method and application
CN112892565A (en) * 2021-01-26 2021-06-04 华侨大学 Polyacid-based copper metal organic-inorganic hybrid material and preparation method and application thereof
CN113201142A (en) * 2021-04-27 2021-08-03 北京工业大学 Hydrogen bond organic grid material based on aromatic tetrapyrazole and preparation method and application thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
AUREL TĂBĂCARU ET AL.: ""Enlarging an Isoreticular Family: 3,3′,5,5′-Tetramethyl-4,4′- bipyrazolato-Based Porous Coordination Polymers"", 《CRYST. GROWTH DES.》 *
ISHTVAN BOLDOG,ET AL.: ""Acentric Extended Solids by Self Assembly of 4,4＇-Bipyrazolyls"", 《ANGEW. CHEM. INT. ED.》 *
JIE-PENG ZHANG ET AL.: ""Supramolecular Isomerism, Framework Flexibility, Unsaturated Metal Center, and Porous Property of Ag(I)/Cu(I) 3,3’,5,5’-Tetrametyl-4,4’-Bipyrazolate"", 《J. AM. CHEM. SOC.》 *
JING-XIANG ZHANG ET AL.: ""Novel Thermochromism Relating to Supramolecular Cuprophilic Interaction: Design, Synthesis, and Luminescence of Copper(I) Pyrazolate Trimer and Polymer"", 《INORGANIC CHEMISTRY》 *
何军: ""吡唑类配体的Cu-Ⅰ/Zn-Ⅱ金属配位聚合物合成、结构、荧光和热性质研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744495A (en) * 2014-07-04 2015-07-01 广东工业大学 Chiral double-helix coordination polymer and preparation method thereof
CN105153432A (en) * 2014-11-22 2015-12-16 广东工业大学 Coordination polymer based on flexible dual ligand containing nitrogen and carboxylic acid and preparation method of coordination polymer
CN106698457A (en) * 2017-03-13 2017-05-24 青岛大学 Three-dimensional expansion skeleton copper iodide material having 27-MR oversized pore passages and preparation method thereof
CN108640934A (en) * 2018-05-30 2018-10-12 山西大学 A kind of cadmium metal organic framework material and its preparation method and application
CN108640934B (en) * 2018-05-30 2020-07-10 山西大学 Metal cadmium organic framework material and preparation method and application thereof
CN112892565A (en) * 2021-01-26 2021-06-04 华侨大学 Polyacid-based copper metal organic-inorganic hybrid material and preparation method and application thereof
CN112892565B (en) * 2021-01-26 2023-06-20 华侨大学 Polyacid-based copper metal organic-inorganic hybrid material, and preparation method and application thereof
CN113201142A (en) * 2021-04-27 2021-08-03 北京工业大学 Hydrogen bond organic grid material based on aromatic tetrapyrazole and preparation method and application thereof

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