CN111171055A - Copper complex with dye catalytic photodegradation property and preparation method thereof - Google Patents
Copper complex with dye catalytic photodegradation property and preparation method thereof Download PDFInfo
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 30
- 238000001782 photodegradation Methods 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 25
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 copper metal complex Chemical class 0.000 claims abstract description 19
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 19
- 229940012189 methyl orange Drugs 0.000 claims abstract description 19
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 19
- 239000000975 dye Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- JATKASGNRMGFSW-UHFFFAOYSA-N 5-bromobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(Br)=CC(C(O)=O)=C1 JATKASGNRMGFSW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000001048 orange dye Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- RTWTZOFGFKORRR-UHFFFAOYSA-N 2-methyl-1-[4-[4-(2-methylimidazol-1-yl)phenyl]phenyl]imidazole Chemical group CC=1N(C=CN=1)C1=CC=C(C=C1)C1=CC=C(C=C1)N1C(=NC=C1)C RTWTZOFGFKORRR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000037384 skin absorption Effects 0.000 description 1
- 231100000274 skin absorption Toxicity 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- 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
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- 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
- B01J2531/16—Copper
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- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention provides a copper metal complex, a preparation method and application thereof in catalyzing light to degrade methylene blue and methyl orange organic dyes. The chemical formula of the complex is [ Cu (BMIOPE) (Br-BDC)]nWherein BMIOPE is 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether, Br-H2BDC ═ 5-bromoisophthalic acid. The copper metal complex is prepared by allowing copper ions to pass through BMIOPE and Br-H2BDC ligands are self-assembled into a two-dimensional network structure. The experimental results show that: the copper complex has good property of catalyzing photodegradation to remove organic dye in water, and has potential application value in the field of environmental pollution treatment. The complex has simple synthesis process and mild reaction condition,the method is convenient to use, provides a new means for treating harmful substances in the environment, and also provides a new idea for the application of the porous material in environmental engineering.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and metal organic chemistry, and particularly relates to a preparation method of a copper complex with 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether and 5-bromoisophthalic acid as ligands and application of the copper complex in removing methylene blue and methyl orange organic dyes in water through catalytic photodegradation.
Background
Energy shortage and environmental pollution are key problems faced by human beings entering the new century, and the development of new energy sources, such as wind energy, solar energy, nuclear energy and the like, is a main way for solving the problems. Photocatalysis is an important means for solving the current global energy shortage and environmental crisis by utilizing solar energy. In recent years, in order to further improve the photocatalytic activity, semiconductor-like photocatalysts with different structural types are developed, and particularly, porous materials show attractive prospects in the field of photocatalysis. The porous structure of the photocatalyst allows to expose as many reactive active sites as possible and facilitates the contact of the reaction substrate with the active sites by reducing the diffusion resistance; more importantly, the transmission distance of the photoproduction electrons and the holes is greatly shortened by the inner surface with rich porous structure, and bulk phase recombination in the photocatalysis process is avoided to a certain extent, so that the separation and utilization efficiency of the photoproduction electrons and the holes is improved, and the photocatalysis performance is greatly improved.
The rapid development of the industry brings about increasingly severe ecological environment problems, the living environment of human beings is continuously damaged, and the water pollution problem is increasingly serious. At present, the main source of water pollution in China is industrial wastewater, wherein the proportion of printing and dyeing wastewater in the industrial wastewater exceeds 35%. The printing and dyeing wastewater has the characteristics of large wastewater quantity, high chroma, high toxicity, complex water quality and the like, and belongs to high-concentration degradation-resistant organic wastewater. Azo dyes such as Methylene Blue (MB) and Methyl Orange (MO) are extremely harmful in water, seriously harm the ecological balance of rivers and oceans, and enter human bodies through skin absorption, so that headache, vomiting and even irreversible damage to various organs and even carcinogenesis are caused. Therefore, the efficient treatment of azo-type dye pollutants in water is an important issue.
The complex formed by self-assembly of metal ions or metal cluster compounds and organic ligands is a novel porous crystalline solid material, has the advantages of high porosity, high specific surface area, structure cuttability, easy functionalization, multiple active sites and the like, and shows an important application prospect in the field of catalytic photodegradation dyes. A series of complexes with photodegradable dye properties have been reported, but less complexes are reported which can simultaneously catalyze the photodegradation of multiple dyes.
4, 4' -bis (2-methyl-1-imidazolyl) biphenyl ether is a bridging ligand with strong coordination capacity: two methylimidazole groups are arranged at two ends of the ligand, so that the synthesis of the complex is facilitated; 5-bromoisophthalic acid can be partially or completely deprotonated, allows different coordination models with metal ions, and facilitates synthesis of metal complexes with different dimensions, which is a crucial step in completing device formation.
The invention belongs to the technical field of organic synthesis and metal organic chemistry, and relates to synthesis of a two-dimensional copper complex, in particular to synthesis of a copper complex taking 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether and 5-bromoisophthalic acid as ligands and application of the copper complex in catalyzing photo-degradation of methylene blue and methyl orange dyes. The property of the complex for removing methylene blue and methyl orange organic dyes in water by catalyzing photodegradation is explored by using bivalent copper ions as a main body and 4, 4' -di (2-methyl-1-imidazolyl) diphenyl ether and 5-bromoisophthalic acid as ligands.
The copper complex has stable and efficient catalytic photodegradation dye properties at normal temperature, particularly for methylene blue and methyl orange dyes, the methylene blue and the methyl orange are basically and completely degraded within 70 minutes, the degradation rates are 91.48% and 90.61% respectively, the copper complex is easy to separate and recycle for many times, and the catalytic efficiency is basically kept unchanged. In addition, the copper complex has the advantages of simple preparation method, low cost, good reproducibility and the like.
Disclosure of Invention
The invention provides a copper complex with the property of catalyzing photodegradation of dye and a preparation method thereof. The invention selects 4, 4' -di (2-methyl-1-imidazolyl) diphenyl ether, 5-bromoisophthalic acid ligand and copper nitrate trihydrate to construct a complex with a two-dimensional structure. The compound has high catalytic activity, can efficiently degrade methylene blue and methyl orange in water, and particularly, the catalyst is insoluble in water, can be separated and recycled for multiple times. The compound has the advantages of simple synthesis method, low cost and good reproducibility, can be applied to industrial production, and has potential application prospect in the aspect of removing organic dyes in water.
The chemical formula of the copper complex with the property of catalyzing the photodegradation of the dye is as follows: [ Cu (BMIOPE) (Br-BDC)]nWherein BMIOPE is 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether, Br-H2BDC ═ 5-bromoisophthalic acid. BMIOPE and Br-H2The structural formula of BDC is as follows:
the structure of the two-dimensional copper complex with the property of catalyzing the photodegradation of the dye is shown in figure 1(a), and the basic structural parameters are as follows:
the crystal of the copper complex belongs to a monoclinic system, the space group is C2/C, and the unit cell parameters are as follows:
α is 90 °, β is 102.19(3 °), γ is 90 °, and each copper atom in the complex is coordinated with a nitrogen atom derived from two 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ethers and an oxygen atom derived from two 5-bromoisophthalic acids to form an infinite two-dimensional network structure, as shown in fig. 1 (b).
The preparation method of the copper complex comprises the following steps:
(1) the preparation method comprises the following steps: 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether 5-bromoisophthalic acid copper nitrate trihydrate 1: 1, dimethylformamide (DMF, 0.5mL) and H were added2O (2.5mL), uniformly mixing by ultrasonic oscillation for 5 minutes, and putting the mixture into a polytetrafluoroethylene inner container of a hydrothermal reaction kettle to obtain a mixed solution;
(2) drying the mixed solution at 100 ℃ for 72 hours, taking out the product, and separating the solid;
(3) by H2O wash the solid three times to give a pale blue transparent bulk crystal.
Further, the invention provides an application of the copper complex in removing methylene blue and methyl orange in water by catalytic photodegradation, and the copper complex is used for treating azo dye wastewater of methylene blue, methyl orange and the like in natural water.
The invention has the advantages that: the preparation method has simple process and good reproducibility, can obtain a single crystal form and high-purity crystal material, and is easy for industrial production; the product can quickly and effectively degrade methylene blue and methyl orange in water, and the catalytic efficiency of repeated recycling is basically kept unchanged.
Brief description of the drawings
FIG. 1(a) is a crystal structure diagram of a copper complex of the present invention; FIG. 1(b) is a two-dimensional network structure diagram of the copper complex of the present invention.
FIG. 2(a) is a graph showing the change in absorbance of photocatalytic 10mg/L methylene blue of a copper complex according to the present invention; FIG. 1(b) is a graph showing the change in absorbance of a copper complex of the present invention at a photocatalytic level of 10mg/L methyl orange.
FIG. 3(a) is a graph showing the photocatalytic 10mg/L degradation rate of methylene blue by a copper complex according to the present invention; FIG. 3(b) is a graph showing the photocatalytic 10mg/L methyl orange degradation rate of the copper complex of the present invention.
Detailed Description
In order to better understand the invention, the following description is further provided in connection with the examples, but the invention is not limited to the following examples.
Example 1 synthesis of ligand BMIOPE:
preparing 4, 4 '-bis (2-methyl-1-imidazolyl) diphenyl ether (BMIOPE) from 4, 4' -dibromodiphenyl ether, 2-methylimidazole, potassium carbonate and cuprous oxide by a one-pot method under the condition of heating in a polar solvent;
wherein the mol ratio of the 4, 4' -dibromo diphenyl ether to the 2-methylimidazole to the potassium carbonate to the cuprous oxide is 2: 6: 8: 1; the reaction temperature was 150 ℃ and the reaction time was 3 days.
Example 2 synthesis of the complex:
12.08mg of copper nitrate trihydrate (Cu (NO)3)2·3H2O), 16.5mg of 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether (BMIOPE), 12.3mg of 5-bromoisophthalic acid (H)2TBIP) is dissolved in 0.5mL of Dimethylformamide (DMF) and 2.5mL of aqueous solution, the mixture is evenly mixed by ultrasonic oscillation for 5 minutes, the mixture is put into a polytetrafluoroethylene inner container of a hydrothermal reaction kettle to obtain a mixed solution, the mixed solution is dried for 72 hours at 100 ℃, a product is taken out, and the solid is separated to obtain a blue blocky crystal.
Example 3 structural characterization of the complex:
single crystals of appropriate size were selected with a microscope and analyzed at room temperature using a Siemens (Bruker) SMART CCD diffractometer (graphite monochromator, Mo-Ka,
) Diffraction data was collected. The diffraction data were corrected for absorption using the SADABS program. Data reduction and structure resolution were done using SAINT and SHELXTL programs, respectively. And determining all non-hydrogen atom coordinates by a least square method, and obtaining the hydrogen atom position by a theoretical hydrogenation method. And (5) refining the crystal structure by adopting a least square method. The basic coordination and stacking scheme are shown in FIG. 1(a) and FIG. 1 (b). Some of the parameters for crystallographic diffraction point data collection and structure refinement are shown in the table below.
TABLE 1 crystallographic data for the complexes
R1＝∑||Fo|-|Fc||/∑|Fo|.ωR2＝∑[w(Fo 2-Fc 2)2]/∑[w(Fo 2)2]1/2
Example 4: photodegradation of complexes with methylene blue and methyl orange
30mg of the copper complex synthesized according to the present invention was weighed into 50mL of an aqueous solution of methylene blue and methyl orange (10mg/L), and then 5uL of H was added2O2Stirring in the dark for 30min to make the surface of the complex reach adsorption-desorption equilibrium, then stirring while irradiating, taking 1mL of methylene blue and methyl orange aqueous solution every 10min, and immediately testing the change of absorbance. The results of the photodegradation showed that the methylene blue and methyl orange were substantially completely degraded within 70 minutes, with the degradation rates of 91.48% and 90.61%, respectively (see fig. 3).
Claims (3)
1. A copper complex used for removing methylene blue and methyl orange organic dyes in water by catalytic photodegradation is characterized in that the copper complex has a chemical formula of [ Cu (BMIOPE) (Br-BDC)]nWherein BMIOPE is 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether, Br-H2BDC ═ 5-bromoisophthalic acid; the crystal of the copper complex belongs to a monoclinic system, the space group is C2/C, and the unit cell parameters are as follows:
α is 90 °, β is 102.19(3 °), γ is 90 °, and the central ion copper has a four-coordinate tetrahedral configuration, and coordinates with two nitrogen atoms of 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether and two oxygen atoms of 5-bromoisophthalic acid to form an infinite two-dimensional network structure.
2. The method for producing a copper complex according to claim 1, characterized by comprising the steps of: the copper complex is obtained by a hydrothermal method by mixing organic ligand 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether and 5-bromoisophthalic acid with copper nitrate trihydrate in a mixed solution of water and Dimethylformamide (DMF).
3. The method of claim 2, wherein: the molar ratio of 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether, 5-bromoisophthalic acid and copper nitrate trihydrate was 1: 1, 2.5mL of a mixed solution of deionized water and 0.5mL of DMMF per 0.05mmol of copper nitrate trihydrate, the temperature was 100 ℃ and the reaction time was three days.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456398A (en) * | 2022-03-04 | 2022-05-10 | 四川轻化工大学 | Copper transition metal coordination polymer and preparation method and application thereof |
| CN114713288A (en) * | 2022-04-24 | 2022-07-08 | 南京工业大学 | Photoresponse metal organic polyhedral catalyst, preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456398A (en) * | 2022-03-04 | 2022-05-10 | 四川轻化工大学 | Copper transition metal coordination polymer and preparation method and application thereof |
| CN114456398B (en) * | 2022-03-04 | 2022-08-16 | 四川轻化工大学 | Copper transition metal coordination polymer and preparation method and application thereof |
| CN114713288A (en) * | 2022-04-24 | 2022-07-08 | 南京工业大学 | Photoresponse metal organic polyhedral catalyst, preparation method and application thereof |
| CN114713288B (en) * | 2022-04-24 | 2023-04-28 | 南京工业大学 | Photo-responsive metal-organic polyhedral catalyst, preparation method and application thereof |
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