CN104098614B - Zinc coordination polymer as well as preparation method and application thereof - Google Patents
Zinc coordination polymer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a zinc coordination polymer as well as a preparation method and application thereof. According to the method, under a solvothermal condition, a zinc complex is prepared firstly, and then is doped with a small amount of cobalt ions, so that a doped complex is obtained. Compared with conventional method, the method disclosed by the invention has the advantages that a zinc complex catalyst doped with the small amount of cobalt ions is better in the reaction effect of catalyzing and light-degrading Rhodamine B, can realize recycling, and keep relatively high catalytic efficiency.
Description
Technical field
The present invention relates to the preparation method of coordination polymer and its application in catalysis light degradation are and in particular to a kind of zinc
Coordination polymer, its preparation method and its application in catalysis light degradation rhodamine b.
Background technology
Recently as the reinforcement of people's environmental protection consciousness, it is catalyzed light degradation pollutant and has become as photochemistry field very
An active research direction.Wherein organic dye molecule, such as rhodamine b (rhodamine b), also known as rose-red b, or alkali
Property rhodamine toner, is commonly called as that pollen is red, is a kind of dyestuff with fresh pinkish synthetic.Test through mouse and find, rhodamine b
Subcutaneous tissue raw meat tumor can be led to, under a cloud is carcinogen.Rhodamine b has strong fluorescence in the solution, as laboratory
The industries such as middle cell fluorescence stain, coloured glass, characteristic fireworks and firecrackers.Once it was used as food additive, but experiment card later
Bright rhodamine b can be carcinogenic, has not allowed now to dye as food.Therefore the organic dye pollutant in degraded water body is one
Important problem.
At present, the main method of degraded water pollutant has physisorphtion, biological degradation method, oxidation-reduction method, catalysis
Light degradation method etc..Catalysis light degradation method has that process capacity is big, strong to the toleration of environment, does not need to introduce other oxidations also
The advantages of active compound agent.
Design synthetic environment close friend's, synthetic method simple photoreaction catalyst is the crucial skill of catalysis light degradation method
Art.It is the effective ways of light degradation pollutant by the use of metal nano material as catalyst；However, nanoparticle is as photoreaction
Catalyst generally synthesis is complex, and the nanoparticle being synthesized may have sizes simultaneously, and metallic nanoparticle
Recycling of son has difficulties, so that this method is restricted in the application.It is steady that metal complex has higher light
Qualitative and chemical stability, nontoxic, synthetic method is generally straightforward, so metal complex is that a kind of preferable light is anti-
Answer catalyst.
Strong open report two kinds of two-dimentional cupprous coordination polymers, they are isomerss and to methyl
Indigo plant, rhodamine b and methyl orange all have preferable catalysis light degradation reactivity worth, and two kinds of coordination polymers all may be used to three kinds of dyestuffs
Recycling (referring to: tian wen, de xiang zhang, jian zhang, inorg. chem. 2013,52,
12 14)；But its cyclic utilization rate in the reaction of photocatalytic degradation rhodamine b is low.
Content of the invention
The purpose of the present invention is to disclose a kind of preparation method of the zinc coordination polymer of ZnO thin film.
To achieve the above object of the invention, the technical solution used in the present invention is:
A kind of preparation method of the zinc coordination polymer of ZnO thin film, comprises the following steps:
(1) by the mixing of zinc nitrate hexahydrate, M-phthalic acid, four [4- (1- imidazole radicals) phenyl] methane and acetonitrile/water
Solvent is put in reactor, after closing, reacts 2 days in 150 DEG C；Reaction is cooled to room temperature after terminating, and obtains product 1；
In molar ratio, zinc nitrate hexahydrate: M-phthalic acid: four [4- (1- imidazole radicals) phenyl] methane=(2～2.5): 1:
2；
(2) above-mentioned product 1 is placed in the acetonitrile/water mixed solution of cobalt nitrate, after closing, reacts 24 hours in 80 DEG C,
Obtain the zinc coordination polymer of ZnO thin film, its molecular formula is c53h36n8o8zn1.952co0.048.
In technique scheme, the molecular formula of product 1 is c53h36n8o8zn2.
In technique scheme, in the mixed solvent of acetonitrile/water, acetonitrile and the volume ratio of water are 1: 1.
In technique scheme, in step (1), rate of temperature fall is 5 DEG C/h.
Preferably technical scheme, in step (1), according to mol ratio, zinc nitrate hexahydrate: M-phthalic acid: four [4- (1-
Imidazole radicals) phenyl] methane=2: 1: 2.
In technique scheme, in step (2), according to mol ratio, product 1: cobalt nitrate=1: 5.
The present invention is also claimed a kind of preparation method of zinc coordination polymer, comprises the following steps, by six nitric hydrates
Zinc, the mixed solvent of M-phthalic acid, four [4- (1- imidazole radicals) phenyl] methane and acetonitrile/water are put in reactor, after closing,
React 2 days in 150 DEG C；Reaction is cooled to room temperature after terminating, and obtains zinc coordination polymer, and molecular formula is c53h36n8o8zn2；Massage
You compare, zinc nitrate hexahydrate: M-phthalic acid: four [4- (1- imidazole radicals) phenyl] methane=(2～2.5): 1: 2.
In technique scheme, in the mixed solvent of acetonitrile/water, acetonitrile and the volume ratio of water are 1: 1.
In technique scheme, rate of temperature fall is 5 DEG C/h.
Preferably technical scheme, according to mol ratio, zinc nitrate hexahydrate: M-phthalic acid: four [4- (1- imidazole radicals) benzene
Base] methane=2: 1: 2.
The present invention is also claimed the zinc coordination polymer that above-mentioned preparation method prepares.Described zinc coordination polymer is
c53h36n8o8zn1.952co0.048Or c53h36n8o8zn2.
By above-mentioned zinc coordination polymer c53h36n8o8zn2Or the zinc coordination polymer of ZnO thin film
c53h36n8o8zn1.952co0.048Add in rhodamine b aqueous solution, can carry out being catalyzed light degradation rhodamine b under uviol lamp；So
The present invention is also claimed application in catalysis light degradation rhodamine b for the above-mentioned zinc coordination polymer.
In technique scheme, catalysis light degradation rhodamine b is carried out under 400w ultraviolet.
In the present invention, the structural formula of four [4- (1- imidazole radicals) phenyl] methane is:
The structural formula of rhodamine b is:
Because technique scheme is used, the present invention compared with prior art has the advantage that
1. the present invention, first under the conditions of solvent thermal, prepares zinc coordination polymer, then passes through a small amount of cobalt ion that adulterates, obtains
To a kind of zinc coordination polymer of ZnO thin film；Products therefrom Stability Analysis of Structures, superior performance, it is possible to recycling, is followed for 5 times
After ring uses, catalytic efficiency and structure all do not change；
2. the zinc coordination polymer that the inventive method prepares has a performance of excellent catalysis light degradation rhodamine b, and 2
Hour reaches 70% to the degradation rate of rhodamine b；And its catalytic performance is improve by a small amount of cobalt ion that adulterates, degradation time reduces
Half, the degradation rate to rhodamine b is up to 96% within 2 hours；
3. preparation method disclosed by the invention is simple, is conducive to purification, product yield high, easily the recovery profit again of product
With suitable industrial operation.
Brief description
Fig. 1 is c in embodiment one53h36n8o8zn2Solid UV Diffuse Reflectance Spectroscopy figure；
Fig. 2 is c in embodiment two53h36n8o8zn1.952co0.048Solid UV Diffuse Reflectance Spectroscopy figure；
Fig. 3 is c in embodiment three53h36n8o8zn2Catalysis light degradation rhb uv absorption spectra；
Fig. 4 is c in embodiment three53h36n8o8zn2Catalysis light degradation rhb five times circulation concentration change figure；
Fig. 5 is c in embodiment three53h36n8o8zn2Powder x-ray diffraction (pxrd) figure；
Fig. 6 is c in example IV53h36n8o8zn1.952co0.048Catalysis light degradation rhb uv absorption spectra；
Fig. 7 is c in example IV53h36n8o8zn1.952co0.048Catalysis light degradation rhb five times circulation concentration change
Figure；
Fig. 8 is c in example IV53h36n8o8zn1.952co0.048Pxrd figure；
Fig. 9 is c in embodiment three and four53h36n8o8zn2And c53h36n8o8zn1.952co0.048Catalytic degradation rhb concentration
Rate of change figure.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described:
Embodiment one: the synthesis of zinc coordination polymer
Take zinc nitrate hexahydrate zn (no3)2· 6h2O(0.030g, 0.1mmol), M-phthalic acid 1,3-h2bdc
(0.016g, 0.1mmol) and four [4- (1- imidazole radicals) phenyl] methane (0.029g, 0.05mmol) puts into the heat resistant glass of 8ml
Guan Zhong, adds the mixed solvent acetonitrile/water rear enclosed of 3ml volume ratio 1: 1.150 DEG C of isothermal reactions 2 days in baking oven, with 5 DEG C/
Hour speed is slowly dropped to room temperature, obtains yellow crystals for product 1 through filtration, distilled water wash, drying, i.e. zinc coordination polymerization
Thing, molecular formula is c53h36n8o8zn2.
Infrared analysiss are carried out 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.
Make use of x- ray single crystal diffraction that product 1 structure is analyzed, the results are shown in Table 1, confirmed the list of product by table 1
Crystal structure.
Accompanying drawing 1 is zinc coordination polymer c53h36n8o8zn2Solid UV Diffuse Reflectance Spectroscopy k-m equation, can from accompanying drawing 1
Know, the band gap value of zinc coordination polymer is 2.27ev, illustrate that it excites required energy size, general edge energy eg is less than
3.40ev is it is possible to carry out light-catalyzed reaction using the ultraviolet light of 365nm.
The crystallographic parameter of table 1 zinc coordination polymer
The synthesis of the zinc coordination polymer of embodiment two: co ion doping
Take zinc coordination polymer c53h36n8o8zn2It is placed in cobalt nitrate co (no3)2·6h2In the acetonitrile/water mixed solution of o,
And be sealed in heat-resistant glass tube, in baking oven, 80 DEG C of constant temperature 24 hours, through filtration, distilled water wash, drying, obtains orange
Compound, is the zinc coordination polymer of ZnO thin film, and molecular formula is c53h36n8o8zn1.952co0.048.Icp analysis finds, cobalt
In the zinc coordination polymer of ion doping containing 97.60% zn2+With 2.40% co2+.Zinc coordination polymerization to ZnO thin film
Thing c53h36n8o8zn1.952co0.048Carry out infrared analysiss, result is as follows:
ir: v(kbr)/cm-13445m, 3133w, 1615s, 1562w, 1523s, 1373s, 1314w,
1270w, 1126w, 1068m, 966m, 826m, 762s, 656m, 561m.
Make use of the zinc coordination polymer c to ZnO thin film for the x- ray single crystal diffraction53h36n8o8zn1.952co0.048Structure
It is analyzed, the results are shown in Table 2, as shown in Table 2 the crystal structure of the zinc coordination polymer of ZnO thin film and zinc coordination polymer
Identical.
Accompanying drawing 2 is the zinc coordination polymer c of ZnO thin film53h36n8o8zn1.952co0.048Solid ultraviolet diffuse
Spectrum k-m equation, understands, c from accompanying drawing 253h36n8o8zn1.952co0.048Band gap value be 2.13ev.
The crystallographic parameter of the zinc coordination polymer of table 2 ZnO thin film
Embodiment three: zinc coordination polymer catalysis light degradation rhodamine b
Take the zinc coordination polymer c of 10mg53h36n8o8zn2It is 3 × 10 in 50ml concentration-4mol·l-1Rhodamine b water-soluble
In liquid, carry out being catalyzed light degradation reaction under 400w uviol lamp, sample 1ml every 30min, surveyed with distilled water diluting to 10ml purple
Outer absorption.Accompanying drawing 3 is the uv absorption spectra of rhodamine b aqueous solution it can be seen that zinc coordination polymer is catalyzed light degradation sieve
Red bright b needs 240min.
By zinc coordination polymer through filtration, washing, dried recovered after the completion of degraded, carry out again being catalyzed light degradation Luo Dan
Bright b experiment.Accompanying drawing 4 is the concentration change figure of cycle-index and rhodamine b, and in figure vertical coordinate refers to the change of the concentration of rhodamine b
Change value；Time is longer, and the variable quantity of the concentration of rhodamine b solution is bigger, and rhodamine b degradation amount is higher, the concentration of its aqueous solution
Lower；It can be seen that after circulating 5 times, catalytic efficiency is basically unchanged.After 5 times recycle, zinc coordination polymer is through powder
X-ray diffraction confirms, structure does not change, and sees accompanying drawing 5, and one simulation curve in figure bottom refers to according to crystal list
The theoretical diagram that brilliant data matching obtains, a middle actual measurement refers to zinc coordination polymer c53h36n8o8zn2Survey before doing Catalysis experiments
, topmost refer to zinc coordination polymer c after a catalysis53h36n8o8zn2Record after 5 circulation catalysis；Article three, curve
Basically identical show that crystal structure after catalysis is not destroyed.
Example IV: the zinc coordination polymer catalysis light degradation rhodamine b of ZnO thin film
Take the zinc coordination polymer c of the ZnO thin film of 10mg53h36n8o8zn1.952co0.048It is 3 × 10 in 50ml concentration- 4mol·l-1Rhodamine b aqueous solution in, carry out under 400w uviol lamp be catalyzed light degradation reaction, every 30min sample 1ml,
Survey uv absorption with distilled water diluting to 10ml.Accompanying drawing 6 is the uv absorption spectra of rhodamine b aqueous solution it can be seen that cobalt
The zinc coordination polymer catalysis light degradation rhodamine b of ion doping only needs 120min.After the completion of degraded, catalyst cobalt ion is mixed
Miscellaneous zinc coordination polymer is through filtering, washing, dried recovered, carries out again being catalyzed light degradation rhodamine b experiment.Accompanying drawing 7 is
The concentration change figure of cycle-index and rhodamine b is it can be seen that catalytic efficiency is basically unchanged.Through 5 times recycle after, cobalt from
The zinc coordination polymer of son doping confirms, structure does not change, and sees accompanying drawing 8 through Powder x-ray diffraction.
Accompanying drawing 9 is c in embodiment three and four53h36n8o8zn2And c53h36n8o8zn1.952co0.048Catalytic degradation rhb dense
Degree rate of change figure, as can be seen from Fig., c53h36n8o8zn2With 4 hours, rhodamine b is degraded to 4%, and
c53h36n8o8zn1.952co0.048Only just rhodamine b was degraded to 4% with 2 hours.
Result shows, zinc coordination polymer can be catalyzed light degradation rhodamine b effectively, and through too small amount of co2+Mix
Miscellaneous, the catalytic effect of the coordination polymer of zn is significantly improved.
Claims (7)
1. a kind of preparation method of the zinc coordination polymer of ZnO thin film is it is characterised in that comprise the following steps:
(1) by the mixed solvent of zinc nitrate hexahydrate, M-phthalic acid, four [4- (1- imidazole radicals) phenyl] methane and acetonitrile/water
Put in reactor, after closing, react 2 days in 150 DEG C；Reaction is cooled to room temperature after terminating, and obtains product 1；
In molar ratio, zinc nitrate hexahydrate: M-phthalic acid: four [4- (1- imidazole radicals) phenyl] methane=(2～2.5): 1: 2；
(2) above-mentioned product 1 is placed in the acetonitrile/water mixed solution of cobalt nitrate, after closing, reacts 24 hours in 80 DEG C, obtain
The zinc coordination polymer of ZnO thin film, its molecular formula is c53h36n8o8zn1.952co0.048.
2. according to claim 1 the zinc coordination polymer of ZnO thin film preparation method it is characterised in that: step (1)
In, in molar ratio, zinc nitrate hexahydrate: M-phthalic acid: four [4- (1- imidazole radicals) phenyl] methane=2: 1: 2.
3. according to claim 1 the zinc coordination polymer of ZnO thin film preparation method it is characterised in that: acetonitrile/water
Mixed solvent in the volume ratio of acetonitrile and water be 1: 1.
4. according to claim 1 the zinc coordination polymer of ZnO thin film preparation method it is characterised in that: step (1)
In, rate of temperature fall is 5 DEG C/h.
5. according to claim 1 the zinc coordination polymer of ZnO thin film preparation method it is characterised in that: step (2)
In, in molar ratio, the ratio 1: 5 of product 1 and cobalt nitrate.
6. the zinc coordination polymer that any one preparation method according to claims 1 to 5 prepares；Described zinc polycomplexation
The molecular formula of compound is c53h36n8o8zn1.952co0.048；Crystallographic parameter is: monoclinic system, and space group isc2/c, cell parameter
Fora=4. 0999(8)nm、b=1. 4353(3)nm、c=2. 0257(4)nm、β= 108.8(3)˚.
7. application in catalysis light degradation rhodamine b for the zinc coordination polymer described in claim 6.
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| CN104693224B (en) * | 2014-10-31 | 2016-07-20 | 安阳师范学院 | There is cadmium metal complex of catalysis light degradation dye property and preparation method thereof |
| CN104558059A (en) * | 2014-12-15 | 2015-04-29 | 常熟市新腾化工有限公司 | Copper-zinc double coordination polymer |
| CN104528873A (en) * | 2014-12-15 | 2015-04-22 | 常熟市新腾化工有限公司 | Application of copper and zinc bi-coordination polymer |
| CN104530140A (en) * | 2014-12-15 | 2015-04-22 | 常熟市新腾化工有限公司 | Preparation method of copper and zinc bi-coordination polymer |
| CN105669773B (en) * | 2015-12-31 | 2018-01-26 | 郑州大学 | A kind of Co MOF materials and preparation method thereof, purposes |
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| CN107501535B (en) * | 2017-08-14 | 2019-11-12 | 常州大学 | Zn complex catalyst and preparation method thereof for ring-opening polymerisation preparation polylactic acid |
| CN109762178A (en) * | 2019-02-11 | 2019-05-17 | 洛阳师范学院 | A kind of metal-organic framework materials, metal-organic framework materials of rhodamine B-sensitized and its preparation method and application |
| CN110330515B (en) * | 2019-07-31 | 2021-06-25 | 商丘师范学院 | Nitrogen-oxygen mixed ligand zinc complex and preparation method thereof |
| CN111393663B (en) * | 2020-04-07 | 2021-10-08 | 曲靖师范学院 | Perylene bisimide base coordination polymer, preparation method and application thereof |
| CN113336956B (en) * | 2021-04-12 | 2022-05-31 | 皖西学院 | Metal-organic pore cobalt compound, preparation method and application thereof |
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