CN104693224A - Cadmium metal complex with dye catalytic light degradation property and preparation method of cadmium metal complex - Google Patents
Cadmium metal complex with dye catalytic light degradation property and preparation method of cadmium metal complex Download PDFInfo
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- CN104693224A CN104693224A CN201410597646.2A CN201410597646A CN104693224A CN 104693224 A CN104693224 A CN 104693224A CN 201410597646 A CN201410597646 A CN 201410597646A CN 104693224 A CN104693224 A CN 104693224A
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- metal complex
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Abstract
The invention discloses a cadmium coordination polymer adopting 1,3-bi(pyridine-3-methoxyl) benzene and 5-methyl isophthalic acid as ligands, and belongs to the chemical field. The chemical formula of the compound is as follows: [Cd2(5-Me-1,3-BDC)2(bpmb)2]n, wherein 5-Me-1,3-H2BDC is 5-methyl isophthalic acid; bpmb is 1, 3-bi(pyridine-3-methoxyl) benzene. The cadmium metal complex is prepared by adopting cadmium acetate dehydrate, 5-methyl isophthalic acid and 1,3-bi(pyridine-3-methoxyl) benzene. The preparation method of the complex is simple in process and relatively high in yield. The cadmium metal complex is stable in light catalytic degradation dye performance at a normal temperature and can be used for further developing a novel dye degradation material, so that novel vitality can be brought to the field of the material science.
Description
Technical field
The present invention relates to a kind of cadmium coordination polymer, being specifically related to a kind of is the cadmium coordination polymer of part with 1,3-bis-(pyridine-3-methoxyl group) benzene and oreinol dioctyl phthalate, belongs to chemical field.
Background technology
In recent years, due to industrialized fast development, many have more highly toxic various dyestuff and enter water body environment, and therefore research and development have the great interest that functional materials that photocatalytic degradation pollutes causes numerous chemists.But current most of photocatalyst Problems existing have: (l) energy gap is too wide, can only respond the ultraviolet region of not enough solar radiation 5%, and in relative sun power, the visible ray utilization ratio of 47% is very low; (2) current potential of valence band and conduction band is difficult to the current potential simultaneously meeting complete decomposing pollutant, needs Na
2s, Na
2sO
3, the sacrifice agent such as KI and Organic Alcohol could realize H
2or O
2generation; (3) the easy compound of photo-generate electron-hole, quantum yield very low (M. R. Hoffmann, S. T. Martin, W.Choi, D. W. Bahnemann,
chem. Rev., 1995,
95, 69 – 96.).The technical problem of above-mentioned various key is the major cause of restriction photocatalyst.Research finds that most semi-conductor is owing to being subject to the speed of optical excitation generation light induced electron and hole very fast, and the valence band of the electronics be excited from conduction band transitions to semi-conductor has very strong reducing power, can decomposing organic matter (H. Wang, S. Li effectively, L. Zhang, Z. Chen, J. Hu, R. Zou, K. Xu, G. Song, H. Zhao and J. Yang
crystEngComm, 2013,
15, 9011 – 9019.).Due to the light induced electron of the semi-conductor of lattice perfection and hole-recombination rate high, thus photocatalytic water catalytic activity is strong, needs surface deposition promotor.The compound in light induced electron and hole suppresses the principal element of photocatalytic activity.Modification is carried out as carried noble metal, oxide compound to catalyzer, doping or with other semiconductors coupling, and the compound in light induced electron and hole effectively can be suppressed to reaction system interpolation sacrifice agent etc., improve photocatalysis efficiency (Q. Li, B. Guo, J. Yu, J. Ran, B. Zhang, H. Yan and J. R. Gong
j. Am. Chem. Soc.,2011,
133, 10878 – 10884.).Research in recent years shows, functional complexes can not only be with broadband adjustable, not only can strengthen the photo absorption performance of half functional complexes, and effectively can be separated light induced electron and vacancy (G. M. Michael, T. Takashi, K. Tim, M. Alexandra, L. Wang and T. V. Voorhis
inorg. Chem., 2014,
53, 6386 – 6397.).The low dimensional structures of functional complexes not only can increase the specific surface area of material, can improve the transfer rate of material simultaneously; Metal ion and the part of functional complexes directly interact and can be separated light induced electron-vacancy with effectively improving, and then improve light-catalyzed reaction activity (D. K. Dogutan, R. M. Jr and D. G. Nocera
j. Am.Chem. Soc.,2011,
133, 9178 – 9180.).Therefore, prepare the cadmium metal complex with catalysis photodegradation pollutent energy and become raising photodegradation pollutent effective ways (D. L. Reger, A. E. Pascui, P. J. Pellechia, M. D. Smith, J. Jezierska and A. Ozarowski
inorg. Chem., 2014,
53, 4325 – 4339.).
Summary of the invention
For overcoming defect of the prior art, the invention provides and a kind of there is cadmium metal complex of catalysis photodegradation dye property and preparation method thereof.
For realizing object of the present invention, the technical solution adopted in the present invention is: the cadmium metal complex with catalysis photodegradation dye property, and the chemical formula of described title complex is: [Cd
2(5-Me-1,3-BDC)
2(bpmb)
2]
n , wherein: 5-Me-1,3-H
2bDC=5-methylresorcinol dioctyl phthalate; Bpmb=1,3-bis-(pyridine-3-methoxyl group) benzene; The infrared absorption peak that described title complex has comprises: 3450cm
-1, 3122 cm
-1, 1606cm
-1, 1570 cm
-1, 1543cm
-1, 1466cm
-1, 1398cm
-1, 1295cm
-1, 1114cm
-1, 1019cm
-1, 992cm
-1, 770cm
-1, 687cm
-1, 665cm
-1, 609cm
-1the crystal of described title complex belongs to triclinic(crystalline)system, spacer is P-1, unit cell parameters is: a=10.293 (2), b=13.662 (3), c=16.976 (3), α=84.12 (3) °, β=78.31 (3) °, γ=84.81 (3) °; The each cadmium atom of described cooperation species and two come from ligand 1, the nitrogen-atoms of 3-bis-(pyridine-3-methoxyl group) benzene, four come from ligand 1, the oxygen atom ligand of 4-phthalic acid, form unlimited two-dirnentional structure.
There is the preparation method of the cadmium metal complex of catalysis photodegradation dye property, comprise the steps: two acetate hydrate cadmiums, oreinol dioctyl phthalate, 1, 3-bis-(pyridine-3-methoxyl group) benzene and distilled water put into horminess glass tube and tube sealing, subsequently Glass tubing is put into baking oven 170 DEG C of reactions four days, Glass tubing slow cooling is made with the speed of 5 DEG C/h after having reacted, after temperature is down to room temperature, obtain cadmium coordination polymer, collect colourless bulk crystals, naturally dry in atmosphere, further, the mol ratio that described raw material adopts is: two acetate hydrate cadmiums: oreinol dioctyl phthalate: 1, 3-bis-(pyridine-3-methoxyl group) benzene=2: 1: 1, further, described distilled water consumption rise 100 times that number is the mole number of two acetate hydrate cadmiums.
Complex preparation method technique of the present invention is simple, and yield is higher.The cadmium metal complex with catalysis photodegradation dye property provided by the invention, there is under normal temperature stable photocatalytic degradation of dye performance, further can develop as novel dye degrades material, thus inject new vitality for material science.
Accompanying drawing explanation
Fig. 1 is title complex Cd (II) coordination environment figure of the present invention.
Fig. 2 is complex crystal structure iron of the present invention.
Fig. 3 is the absorbancy variation diagram of complex-catalyzed photodegradation methylene blue of the present invention.
Embodiment
In order to explain enforcement of the present invention more fully, provide embodiment of the present invention, these embodiments are only to elaboration of the present invention, do not limit the scope of the invention.
Have the cadmium metal complex of catalysis photodegradation dye property, the chemical formula of described title complex is: [Cd
2(5-Me-1,3-BDC)
2(bpmb)
2]
n , wherein: 5-Me-1,3-H
2bDC=5-methylresorcinol dioctyl phthalate; Bpmb=1,3-bis-(pyridine-3-methoxyl group) benzene; The infrared absorption peak that described title complex has comprises: 3450cm
-1, 3122 cm
-1, 1606cm
-1, 1570 cm
-1, 1543cm
-1, 1466cm
-1, 1398cm
-1, 1295cm
-1, 1114cm
-1, 1019cm
-1, 992cm
-1, 770cm
-1, 687cm
-1, 665cm
-1, 609cm
-1the crystal of described title complex belongs to triclinic(crystalline)system, spacer is P-1, unit cell parameters is: a=10.293 (2), b=13.662 (3), c=16.976 (3), α=84.12 (3) °, β=78.31 (3) °, γ=84.81 (3) °; The each cadmium atom of described cooperation species and two come from ligand 1, the nitrogen-atoms of 3-bis-(pyridine-3-methoxyl group) benzene, four come from ligand 1, the oxygen atom ligand of 4-phthalic acid, form unlimited two-dirnentional structure, the coordination environment of Cd (II) is the octahedral coordination environment of distortion, as shown in Figure 1.
There is the preparation method of the cadmium metal complex of catalysis photodegradation dye property, comprise the steps: two acetate hydrate cadmiums, oreinol dioctyl phthalate, 1, 3-bis-(pyridine-3-methoxyl group) benzene and distilled water put into horminess glass tube and tube sealing, subsequently Glass tubing is put into baking oven 170 DEG C of reactions four days, Glass tubing slow cooling is made with the speed of 5 DEG C/h after having reacted, after temperature is down to room temperature, obtain cadmium coordination polymer, collect colourless bulk crystals, naturally dry in atmosphere, further, the mol ratio that described raw material adopts is: two acetate hydrate cadmiums: oreinol dioctyl phthalate: 1, 3-bis-(pyridine-3-methoxyl group) benzene=2: 1: 1, further, described distilled water consumption rise 100 times that number is the mole number of two acetate hydrate cadmiums.
Have the cadmium metal complex of catalysis photodegradation dye property, described title complex is used for the photodegradation of dyestuff.
Embodiment 1: the synthesis of title complex:
By two acetate hydrate cadmium (11 mg, 0.04 mmol), oreinol dioctyl phthalate (4 mg, 0.02 mmol), 1,3-bis-(pyridine-3-methoxyl group) benzene (6 mg, 0.02 mmol) and 4mL distilled water put into horminess glass tube tube sealing, subsequently Glass tubing is put into baking oven 170 DEG C of reactions four days, Glass tubing slow cooling is made with the speed of 5 DEG C/h after having reacted, after temperature is down to room temperature, collect colourless bulk crystals, naturally dry in atmosphere, obtain cadmium coordination polymer.Productive rate about 43%.Circulation ratio through test of many times present method is better.
Embodiment 2: the sign of title complex:
The structure determination of title complex: the monocrystalline choosing suitable size under the microscope at room temperature carries out X – ray diffraction experiments.On Bruker Smart Apex-II CCD diffractometer, with the Mo – K through graphite monochromator monochromatization
αray (wavelength=0.71073), Yi φ – ω mode collects diffraction data.Reduction of data is carried out by Bruker SAINT program.The diffraction data SADABS program of part-structure carries out absorption correction.Crystalline structure is solved in conjunction with difference Fourier synthesis by direct method.Whole non-hydrogen atom coordinate and anisotropic parameters carry out complete matrix least-squares refinement, and C – H atom position is determined by theoretical mode computation, and detailed axonometry data are in table 1.The crystalline structure of title complex is shown in Fig. 2.Mo – K
αin K under be designated as α, the element of portion has been shown in Fig. 2.
Embodiment 3: catalyzed degradation character
Adopt the xenon lamp of 350W as ultraviolet source, the outside of xenon lamp is lowered the temperature by circulating condensing water.Get 50mL concentration and be about 4 × 10
-5the aqueous solution of methylene blue of mol/L is placed in quartz test tube, adds and the photoresponse catalyzer of 20 mg (i.e. cadmium coordination polymer of the present invention), stirs 30 minutes under dark surrounds.After reaching absorption-desorption balance, be placed in photoreactor and react, every 30min carries out absorbancy test.This title complex makes the methylene blue time completely of substantially degrading be 120 minutes, as shown in Figure 3.
The crystallographic data of table 1 title complex
After detailed description embodiments of the present invention, the personage being familiar with this technology can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention, and the present invention is not also limited to the embodiment of example in specification sheets.
Claims (4)
1. there is the cadmium metal complex of catalysis photodegradation dye property, it is characterized in that: the chemical formula of described title complex is: [Cd
2(5-Me-1,3-BDC)
2(bpmb)
2]
n , wherein: 5-Me-1,3-H
2bDC=5-methylresorcinol dioctyl phthalate; Bpmb=1,3-bis-(pyridine-3-methoxyl group) benzene; The infrared absorption peak that described title complex has comprises: 3450cm
-1, 3122 cm
-1, 1606cm
-1, 1570 cm
-1, 1543cm
-1, 1466cm
-1, 1398cm
-1, 1295cm
-1, 1114cm
-1, 1019cm
-1, 992cm
-1, 770cm
-1, 687cm
-1, 665cm
-1, 609cm
-1the crystal of described title complex belongs to triclinic(crystalline)system, spacer is P-1, unit cell parameters is: a=10.293 (2), b=13.662 (3), c=16.976 (3), α=84.12 (3) °, β=78.31 (3) °, γ=84.81 (3) °; The each cadmium atom of described cooperation species and two come from ligand 1, the nitrogen-atoms of 3-bis-(pyridine-3-methoxyl group) benzene, four come from ligand 1, the oxygen atom ligand of 4-phthalic acid, form unlimited two-dirnentional structure.
2. there is the preparation method of the cadmium metal complex of catalysis photodegradation dye property as claimed in claim 1, it is characterized in that: comprise the steps: two acetate hydrate cadmiums, oreinol dioctyl phthalate, 1,3-bis-(pyridine-3-methoxyl group) benzene and distilled water put into horminess glass tube and tube sealing, subsequently Glass tubing is put into baking oven 170 DEG C of reactions four days, Glass tubing slow cooling is made with the speed of 5 DEG C/h after having reacted, after temperature is down to room temperature, obtain cadmium coordination polymer, collect colourless bulk crystals, naturally dry in atmosphere.
3. there is the preparation method of the cadmium metal complex of catalysis photodegradation dye property as claimed in claim 3, it is characterized in that: the mol ratio that described raw material adopts is: two acetate hydrate cadmiums: oreinol dioctyl phthalate: 1,3-bis-(pyridine-3-methoxyl group) benzene=2: 1: 1.
4. there is the preparation method of the cadmium metal complex of catalysis photodegradation dye property as claimed in claim 2, it is characterized in that: described distilled water consumption rise 100 times that number is the mole number of two acetate hydrate cadmiums.
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Cited By (9)
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|---|---|---|---|---|
| CN105367591A (en) * | 2015-12-08 | 2016-03-02 | 安阳师范学院 | Cadimium complex monocrystal capable of catalyzing photodegradation of methylene blue, and preparation method thereof |
| CN105713019A (en) * | 2016-02-13 | 2016-06-29 | 陈锦 | LED yellow light fluorescent powder, preparation method and application to white light LED |
| CN107619417A (en) * | 2017-08-29 | 2018-01-23 | 中国科学院福建物质结构研究所 | A kind of cadmium organic coordination compound with photocatalytic activity and preparation method and application |
| CN107617420A (en) * | 2016-07-16 | 2018-01-23 | 天津师范大学 | Application of thiocyanate radical Cd (II) complexs based on 4 (oxadiazole of 5 methyl 1,3,4) pyridines in dyestuff is adsorbed |
| CN108654584A (en) * | 2018-06-04 | 2018-10-16 | 江苏新瀚新材料股份有限公司 | A kind of regeneration method of hydroxy-ketone active carbon for decolorization |
| CN111171054A (en) * | 2018-11-09 | 2020-05-19 | 盐城师范学院 | Copper complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof |
| CN111454283A (en) * | 2019-01-22 | 2020-07-28 | 盐城师范学院 | Copper complex synthesis and application of copper complex as photodegradation catalyst |
| CN111825850A (en) * | 2020-06-15 | 2020-10-27 | 上海大学 | Preparation method of three-dimensional manganese coordination polymer |
| CN111925532A (en) * | 2020-08-21 | 2020-11-13 | 河南理工大学 | Adjustable dual-mode composite fluorescent material and preparation method and anti-counterfeiting application thereof |
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| CN105367591A (en) * | 2015-12-08 | 2016-03-02 | 安阳师范学院 | Cadimium complex monocrystal capable of catalyzing photodegradation of methylene blue, and preparation method thereof |
| CN105713019A (en) * | 2016-02-13 | 2016-06-29 | 陈锦 | LED yellow light fluorescent powder, preparation method and application to white light LED |
| CN107617420A (en) * | 2016-07-16 | 2018-01-23 | 天津师范大学 | Application of thiocyanate radical Cd (II) complexs based on 4 (oxadiazole of 5 methyl 1,3,4) pyridines in dyestuff is adsorbed |
| CN107619417A (en) * | 2017-08-29 | 2018-01-23 | 中国科学院福建物质结构研究所 | A kind of cadmium organic coordination compound with photocatalytic activity and preparation method and application |
| CN108654584B (en) * | 2018-06-04 | 2020-12-08 | 江苏新瀚新材料股份有限公司 | Regeneration method of activated carbon for decolorizing hydroxyketone |
| CN108654584A (en) * | 2018-06-04 | 2018-10-16 | 江苏新瀚新材料股份有限公司 | A kind of regeneration method of hydroxy-ketone active carbon for decolorization |
| CN111171054A (en) * | 2018-11-09 | 2020-05-19 | 盐城师范学院 | Copper complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof |
| CN111171054B (en) * | 2018-11-09 | 2024-04-09 | 盐城师范学院 | Copper complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof |
| CN111454283A (en) * | 2019-01-22 | 2020-07-28 | 盐城师范学院 | Copper complex synthesis and application of copper complex as photodegradation catalyst |
| CN111825850A (en) * | 2020-06-15 | 2020-10-27 | 上海大学 | Preparation method of three-dimensional manganese coordination polymer |
| CN111925532A (en) * | 2020-08-21 | 2020-11-13 | 河南理工大学 | Adjustable dual-mode composite fluorescent material and preparation method and anti-counterfeiting application thereof |
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