CN108084454A - A kind of sodium（I）Coordination polymer and preparation method and application - Google Patents
A kind of sodium（I）Coordination polymer and preparation method and application Download PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 49
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 48
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229930002839 ionone Natural products 0.000 claims abstract description 3
- 150000002499 ionone derivatives Chemical class 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 36
- 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 description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- SXSLRMSHMPMPHK-UHFFFAOYSA-N 4-[3-(4-carboxyphenyl)-1h-1,2,4-triazol-5-yl]benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=NNC(C=2C=CC(=CC=2)C(O)=O)=N1 SXSLRMSHMPMPHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002500 ions Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000000975 dye Substances 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract 1
- 229940043267 rhodamine b Drugs 0.000 description 13
- 239000000843 powder Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003292 diminished effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/12—Sodium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Hydrology & Water Resources (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of sodium（I）Coordination polymer and preparation method and application, the coordination polymer is by by sodium hydroxide, 3, and 5 two（4 ' carboxyl phenyls）1,2,4 triazole, N, N ' dimethylformamides and water mixing carried out solvent thermal reaction after 3 ~ 5 days, were obtained after cooling crystallization, washed drying, which is { [Na4（µ2‑H2O）（DMF）2（BCT）2]·DMF}n, the coordination polymer is with sodium（I）Centered on ion one one-dimensional sodium ion chain is constituted by hydrone and DMF molecule bridgings, by BCT2‑Ligand constitutes the skeleton structure in a three-dimensional porous road.Coordination polymer of the present invention has good thermal stability, and the degradation rate of 60 min interior focusing rhodamine Bs reaches 78% under visible light conditions, which can use as special light degradation organic dyestuff catalyst.
Description
Technical field
The invention belongs to organic pollution photocatalytic degradation field more particularly to a kind of sodium with Photocatalytic Degradation Property
（I）Coordination polymer and preparation method and application.
Background technology
Water is lifespring, how it is effective and reasonable processing water pollution be related to be human survival major issue.It is existing
Make for industrial expansion increasing in the industrial wastewater containing Recalcitrant chemicals.Rhodamine B（Rhodamine B）Also known as rose
Rare red or basic rhodamine, is commonly called as that pollen is red, is a kind of artificial synthesized dyestuff with fresh pink.It belongs to triphen first
Alkanes dyestuff is widely used in weaving, print, in foods and cosmetics industry.The colourity of rhodamine waste water is high, can give birth to
The property changed is poor, if directly discharged without processing, can cause the lasting deterioration of water body environment.People are with a variety of methods to above-mentioned useless
Water is handled, such as absorption method, ion-exchange, biologic treating technique and advanced chemical oxidation etc..Wherein, photocatalysis is
One kind in advanced chemical oxidation, the main photocatalysis property for utilizing semiconductor, degradation speed is fast, does not generate secondary dirt
Dye, reaction condition is mild, is the research hotspot of environmental area.
In recent years, metal organic coordination polymer is due to its abundant topological structure, various accumulation mode, make its
Light, electricity, magnetic, photocatalytic degradation and gas storage etc. show huge application potential.At present, the metal reported for work is organic
The coordination polymer overwhelming majority is the ion centered on d p-block element ps, and ion is less centered on s p-block element ps.Further, since 3,
5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles（H2BCT）Coordination mode is versatile and flexible, and coordination site enriches, and is also used extensively
In the synthesis of metal coordinating polymer material.
The content of the invention
It is an object of the invention to provide a kind of sodium with Photocatalytic Degradation Property（I）Coordination polymer.
It is still another object of the present invention to provide above-mentioned sodium（I）The preparation method of coordination polymer.
Another object of the present invention is to provide above-mentioned sodium（I）Coordination polymer is in terms of photocatalysis degradation organic contaminant
Application.
The present invention is achieved in that a kind of sodium（I）Coordination polymer, the chemical expression of the coordination polymer are：
{[Na4（µ2-H2O）（DMF）2（BCT）2]·DMF}n；Wherein, n is the natural number not including 0（It is infinitely great）；
DMF is organic solvent molecule N, and N '-dimethyl formamide, structure is as shown in following formula 1：
Formula 1
H2BCT is 3,5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles, structure is as shown in following formula 2：
Formula 2
The coordination polymer is with sodium（I）Centered on ion one one-dimensional sodium is constituted by hydrone and DMF molecule bridgings
Ion chain, by BCT2-Ligand constitutes the skeleton structure in a three-dimensional porous road.
The complex crystal belongs to orthorhombic system, space group Pbcn, and cell parameter is a=33.2423（15）, b=
11.7066（6）, c=14.1136（15）, the ゜ of α=β=γ=90.00, V=5492.4（7） Å3。
The present invention further discloses above-mentioned sodium（I）The preparation method of coordination polymer, this method comprise the following steps：
（1）By sodium hydroxide, 3,5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles, N, N '-dimethyl formamide and water mix
It closes, mixture carries out solvent thermal reaction 3 ~ 5 days at 120 ~ 160 DEG C；Wherein, it is described by sodium hydroxide, 3,5- bis-（4 '-carboxyl-
Phenyl）The molar ratio of -1,2,4- triazoles, N, N '-dimethyl formamide and water is（0.2~1）：（0.1~0.5）：（13~52）：
（0~220）；
（2）By reaction product natural cooling crystallization, sodium is obtained after the washed drying of crystal（I）Coordination polymer.
Preferably, in step（1）In, the mixture, which is placed in, to be sealed in autoclave with 5 ~ 10 DEG C per hour of liter
Warm rate is warming up to 120 ~ 160 DEG C.
Preferably, in step（1）In, the solvent thermal reaction time is 3 ~ 4 days.
The present invention further discloses above-mentioned sodium（I）Coordination polymer answering in terms of photocatalysis degradation organic contaminant
With.
Compared with the prior art the shortcomings that and deficiency, the invention has the advantages that：
（1）Coordination polymer of the present invention has good thermal stability, the 60 min interior focusing rhodamine Bs under visible light conditions
Degradation rate reaches 78%, which can use as special light degradation organic dyestuff catalyst；
（2）The present invention can prepare the sodium with Photocatalytic Degradation Property using one pot of solvent thermal reaction（I）Coordination polymerization
Object, the preparation method have the advantages that process is simple, easy to operate, yield is high and reproducibility is good.
Description of the drawings
Fig. 1 is sodium prepared by the embodiment of the present invention（I）The coordination context diagram of sodium in coordination polymer；
Fig. 2 is sodium prepared by the embodiment of the present invention（I）Sodium and H in coordination polymer2The one-dimensional zigzag chain that O and DMF is formed；
Fig. 3 is sodium prepared by the embodiment of the present invention（I）Coordination polymer three-dimensional pore space structure；
Fig. 4 is sodium prepared by the embodiment of the present invention（I）The powder x-ray diffraction figure of coordination polymer；
Fig. 5 is sodium prepared by the embodiment of the present invention（I）Coordination polymer thermogravimetric curve figure；
Fig. 6 is sodium prepared by the embodiment of the present invention（I）The uv absorption spectra that coordination polymer degrades to rhodamine B；
Fig. 7 is sodium prepared by the embodiment of the present invention（I）Coordination polymer is to the degradation rate of rhodamine B with degrading during no catalyst
Rate comparison.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment 1
（1）By 0.2mmol sodium hydroxides, 0.5mmol 3,5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles（H2BCT）、
13mmol N, N '-dimethyl formamide（DMF）It is mixed with 220mmol water, mixture carries out solvent thermal reaction 5 at 120 DEG C
My god；
（2）By reaction product natural cooling crystallization, crystal is rinsed with absolute ethyl alcohol, is filtered under diminished pressure to obtain white crystalline powder, put
Constant temperature obtains sodium after 3 hours in 60 DEG C of baking oven（I）Coordination polymer 1.
Embodiment 2
（1）By 1mmol sodium hydroxides, 0.1mmol3,5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles（H2BCT）、52mmol
N, N '-dimethyl formamide（DMF）Mixing, mixture, which is placed in, to be sealed in autoclave with 10 DEG C per hour of heating rate
Solvent thermal reaction is carried out after being warming up to 160 DEG C 3 days；
（2）By reaction product natural cooling crystallization, crystal is rinsed with absolute ethyl alcohol, is filtered under diminished pressure to obtain white crystalline powder, put
Constant temperature obtains sodium after 3 hours in 60 DEG C of baking oven（I）Coordination polymer 2.
Embodiment 3
（1）By 0.3mmol sodium hydroxides, 0.1mmol 3,5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles（H2BCT）、
25.8 mmol N, N '-dimethyl formamide（DMF）It is mixed with 111mmol water, mixture, which is placed in, to be sealed in autoclave
Solvent thermal reaction is carried out after being warming up to 120 ~ 160 DEG C with 5 ~ 10 DEG C per hour of heating rate 3 ~ 4 days；
（2）By reaction product natural cooling crystallization, crystal is rinsed with absolute ethyl alcohol, is filtered under diminished pressure to obtain white crystalline powder, put
Constant temperature obtains sodium after 3 hours in 60 DEG C of baking oven（I）Coordination polymer 3.
Comparative example 1
（1）By 0.1mmol potassium hydroxide, 0.1 mmol3,5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles, 13 mmolDMF
With 56 mmolH2In the enclosed reaction kettle of O mixing, 120 DEG C are heated to 10 DEG C per hour of rate, constant temperature 3 days；
（2）With 10 DEG C per hour of the near room temperature of rate, you can colourless powder microcrystal is obtained, crystal is rinsed with absolute ethyl alcohol,
It is filtered under diminished pressure to obtain white crystalline powder, being placed in 3 hours of constant temperature in 60 DEG C of baking oven obtains product 4, and yield is about 58%.
Effect example 1
Sodium is made in Example 3（I）Coordination polymer 3 further characterizes, and process is as follows：
（1）The crystal structure determination of coordination polymer
Suitable dimension is chosen under the microscope carry out X at room temperature for the monocrystalline of the mm of the mm of 0.21 mm × 0.15 × 0.14 penetrate
Line diffraction experiment.Diffraction data is collected in Bruker-Apex П X-rays single crystal diffractometer, with graphite monochromator monochromatizationMo-KαRay（λ = 0.71073 Å）, withω-2θScan mode collects point diffraction.Total data is through the factor and empirical absorption
Correction, crystal structure are solved using a program by direct method, and hydrogen atom is synthesized and is fixed on by difference Fourier and calculated most
Best placement determines.With mono- programs of SHELX-97, whole non-hydrogen atoms and its anisotropy thermal parameter have been carried out based on it is complete
Matrix least square method amendment.Detailed axonometry data are shown in Table 1, and important bond distance and bond angle data are shown in 2, and crystal structure is shown in
Fig. 1, Fig. 2 and Fig. 3.
1 sodium of table（I）The predominant crystal data of coordination polymer 3
| Molecular formula | C41H45Na4N9O12 |
| Molecular weight | 878.29 |
| Temperature | 293（2） K |
| Wavelength | 0.71073 Å |
| Monochromator | Graphite |
| Crystallographic system | Rectangle |
| Space group | Pbcn |
| Cell parameter | a=33.2423（15） Å |
| b=11.7066（6） Å | |
| c=14.1136（15） Å | |
| α= 90.00゜ | |
| β= 90.00゜ | |
| γ= 90.00゜ | |
| Volume | 5492.4（7） |
| Z | 4 |
| Density | 1.247 g·cm–3 |
| Absorption coefficient | 0.106 mm–1 |
| F（000） | 2144 |
| Crystal size | 0.21 × 0.15 × 0.14 mm3 |
| θ | 3.335 to 28.622° |
| Restriction factor | - 39≤h≤42, -15≤k≤7, -18≤l≤12 |
| Reflections collected | 14044 / 1628 |
| Data / restraints / parameters | 6255 / 375 / 3078 |
| GOOF values | 1.161 |
| Final R indices [I>2σ（I）] | R 1=0.1181,wR 2 = 0.3283 |
| RThe factor（All data） | R 1=0.1903,wR 2 =0.4011 |
| Maximum diffraction peak and the most weak value of electron density | 0.954 and -0.786 e Å-3 |
In table 1,R 1 =∑（||F o|-|F c||）/∑|F o|,wR 2 =[∑w（F o 2-| F c 2）2/∑w（F o）2]1/2。
2 sodium of table（I）The important bond distance of coordination polymer 3（Å）And bond angle（°）
| Na（1）-O（4） | 2.291（3） | O（4）-Na（1）-O（1） | 82.9（7） |
| Na（1）-O（5） | 2.264（6） | O（4）-Na（1）-O（5） | 133.8（3） |
| Na（1）-O（1） | 2.396（4） | O（4）-Na（1）-O（5W） | 119.3（2） |
| Na（1）-O（5W） | 2.404（5） | O（1）-Na（1）-O（5W） | 127.0（6） |
（2）The phase purity characterization of coordination polymer
The powder X-ray RD characterizations of coordination polymer show that it, with reliable phase purity, guarantor is provided for it as catalyst application
Card, is shown in Fig. 4（Instrument model：Bruker/D8Advance）.
（3）The thermal stability characterization of coordination polymer
Under the conditions of nitrogen atmosphere, from room temperature to 1000 DEG C of scope research coordination polymer thermal stabilities, room temperature to 100（C loses
8.41% is weighed, corresponding is to lose a DMF molecule for having neither part nor lot in coordination（Calculated value, 8.31%）.Afterwards, coordination polymer is extremely
380 DEG C of holding good stabilities, for it, as application material, further exploitation provides thermal stability guarantee, sees Fig. 5（Instrument type
Number：SDT Q600）.
Effect example 2
Using the coordination polymer 3 of gained in 10 mg embodiments 3 as catalyst, pulverize last 100 mL of volume, dense of being packed into
It spends for 20 mg/L rhodamine B aqueous solutions, is stirred under visible ray, normal temperature and pressure conditions, catalytic degradation rhodamine B, timing sampling
Supernatant is centrifuged to obtain, and with ultraviolet-uisible spectrophotometer in rhodamine B maximum absorption wave strong point（552 nm）Measurement is inhaled
Luminosity（As shown in Figure 6）, the concentration of rhodamine B aqueous solution is converted by absorbance-concentration working curve, is surveyed at interval of 10 min
Absorbance of the solution at 552 nm, be computed coordination polymer is as shown in Figure 7 to above-mentioned rhodamine B solution degradation rate.
It was found from Fig. 7 data, compared with no catalyst rhodamine B solution, catalyst of the invention can be effective under visible light conditions
Rhodamine B degradation dyestuff（Instrument model：UV-8000）.
100 mL, concentration are dissolved for 20 mg/L rhodamine Bs using the product 4 obtained in comparative example 1 as catalyst
It degrades, it is 46% to the degradation rate of rhodamine B solution under the same terms to measure it, and sodium is made in far smaller than embodiment 3（I）
Coordination polymer 3 is as catalyst to the degradation rate of rhodamine B solution.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of sodium（I）Coordination polymer, which is characterized in that the chemical expression of the coordination polymer is：{[Na4（µ2-H2O）
（DMF）2（BCT）2]·DMF}n；Wherein, n is the natural number not including 0；H2BCT is 3,5- bis-（4 '-carboxyl-phenyl）-
1,2,4- triazole；
The coordination polymer is with sodium（I）Centered on ion one one-dimensional sodium is constituted by hydrone and DMF molecule bridgings
Ion chain, by BCT2-Ligand constitutes the skeleton structure in a three-dimensional porous road.
2. sodium described in claim 1（I）The preparation method of coordination polymer, which is characterized in that this method comprises the following steps：
（1）By sodium hydroxide, 3,5- bis-（4 '-carboxyl-phenyl）- 1,2,4- triazoles, N, N '-dimethyl formamide and water mix
It closes, mixture carries out solvent thermal reaction 3 ~ 5 days at 120 ~ 160 DEG C；Wherein, it is described by sodium hydroxide, 3,5- bis-（4 '-carboxyl-
Phenyl）The molar ratio of -1,2,4- triazoles, N, N '-dimethyl formamide and water is（0.2~1）：（0.1~0.5）：（13~52）：
（0~220）；
（2）By reaction product natural cooling crystallization, sodium is obtained after the washed drying of crystal（I）Coordination polymer.
3. sodium as claimed in claim 2（I）The preparation method of coordination polymer, which is characterized in that in step（1）In, it is described
Mixture is placed in be sealed in autoclave is warming up to 120 ~ 160 DEG C with 5 ~ 10 DEG C per hour of heating rate.
4. sodium as claimed in claim 3（I）The preparation method of coordination polymer, which is characterized in that in step（1）In, it is described
The solvent thermal reaction time is 3 ~ 4 days.
5. sodium described in claim 1（I）Application of the coordination polymer in terms of photocatalysis degradation organic contaminant.
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| CN110064436A (en) * | 2019-05-29 | 2019-07-30 | 湘潭大学 | A kind of catalyst and preparation method and purposes based on pyridyl group tetrazine ring Base Metal coordination polymer |
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| CN104628751A (en) * | 2015-02-05 | 2015-05-20 | 云南师范大学 | Luminous porous coordination polymer as well as preparation method and application thereof |
| CN107474060A (en) * | 2017-08-11 | 2017-12-15 | 南开大学 | It is a kind of have be selectively adsorbing and separating metal-organic framework material of anionic dye performance and its preparation method and application |
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| CN104628751A (en) * | 2015-02-05 | 2015-05-20 | 云南师范大学 | Luminous porous coordination polymer as well as preparation method and application thereof |
| CN107474060A (en) * | 2017-08-11 | 2017-12-15 | 南开大学 | It is a kind of have be selectively adsorbing and separating metal-organic framework material of anionic dye performance and its preparation method and application |
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| CN110064436A (en) * | 2019-05-29 | 2019-07-30 | 湘潭大学 | A kind of catalyst and preparation method and purposes based on pyridyl group tetrazine ring Base Metal coordination polymer |
| CN110064436B (en) * | 2019-05-29 | 2021-12-07 | 湘潭大学 | Catalyst based on pyridyl tetrazine ring based metal coordination polymer and preparation method and application thereof |
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