CN111171054B - Copper complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof - Google Patents
Copper complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof Download PDFInfo
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 36
- 238000001782 photodegradation Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- BJLUCDZIWWSFIB-UHFFFAOYSA-N 5-tert-butylbenzene-1,3-dicarboxylic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(O)=O)=C1 BJLUCDZIWWSFIB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 copper metal complex Chemical class 0.000 claims abstract description 7
- 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 claims description 13
- 239000013078 crystal Substances 0.000 claims description 10
- 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
- 239000011259 mixed solution Substances 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- RAYLUPYCGGKXQO-UHFFFAOYSA-N n,n-dimethylacetamide;hydrate Chemical compound O.CN(C)C(C)=O RAYLUPYCGGKXQO-UHFFFAOYSA-N 0.000 claims 1
- 239000013110 organic ligand Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 23
- 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 description 21
- 229940012189 methyl orange Drugs 0.000 description 21
- 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 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000000987 azo dye Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 238000002447 crystallographic data Methods 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 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
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010005003 Bladder cancer Diseases 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- 102100022365 NAD(P)H dehydrogenase [quinone] 1 Human genes 0.000 description 1
- 208000007097 Urinary Bladder Neoplasms Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 108010066657 azoreductase Proteins 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 210000000349 chromosome Anatomy 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 208000021550 spleen neoplasm Diseases 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 201000005112 urinary bladder cancer Diseases 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- 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
-
- 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
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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
- 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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- 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
- B01J2531/16—Copper
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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
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention provides a copper metal complex, a preparation method and application thereof in catalyzing photodegradation and adsorbing dye. The chemical formula of the complex is [ Cu ] 2 (4,4′‑BMIBP)(TBIP) 2 (H 2 O) 2 ·2DMA] n Wherein 4,4 '-bmibp=4, 4' -bis (2-methyl-1-imidazolyl) biphenyl, H 2 Tbip=5-t-butylisophthalic acid, dma=n, N-dimethylacetamide. The copper metal complex is copper ion passing 4,4' -BMIBP and H 2 The TBIP ligand self-assembles into a one-dimensional chain structure. The experimental results show that: the copper complex has good properties of catalyzing photodegradation and removing organic dye in water by adsorption, and has potential application value in the field of environmental pollution treatment. The complex has the advantages of simple synthesis process, mild reaction conditions and convenient use, and provides a new means for treating harmful substances in the environment.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and metal organic chemistry, and particularly relates to preparation of a copper complex taking 4,4' -bis (2-methyl-1-imidazolyl) biphenyl and 5-tertiary butyl isophthalic acid as ligands and application of the copper complex in catalyzing photodegradation and adsorbing to remove organic dye in water.
Background
Dye wastewater has high Chemical Oxygen Demand (COD), high organic matter content and poor biodegradability; the chromaticity is high; the components are complex, and the water quality such as pH value and the like has large fluctuation; the toxicity is high, the environmental pollution is serious, and the like, and the influence on the ecological environment and human health is very large.
The production and use amount of azo dyes are the largest of all dyes, and certain azo dyes have been proved to be capable of causing nucleic acid abnormality of human bladder cancer, spleen tumor, liver cancer and test animals and chromosome variation of mammals, and the degradation process of azo dyes is likely to be that azo groups are firstly broken by azo reductase to generate aniline substances, and biological carcinogenic, teratogenic and mutagenic effects of the substances are more serious.
Many reports on the use of zeolite, activated carbon and other materials as adsorbents are made, and little research on the use of complexes as adsorbents for treating dye wastewater is made. Aiming at the current research situation and the deficiency of the related field, the invention discloses a method for treating dye wastewater by using a copper complex, and the dye can be recycled. The complex is used as a novel adsorption material, not only has adsorption property, but also can selectively adsorb dye molecules. In addition, the complex adsorbed organic dye has the advantages of strong binding force, difficult falling, large adsorption capacity, rapidness, high efficiency, less interference by external conditions and the like. Therefore, the complex has potential application value as an adsorbent for treating dye wastewater.
Meanwhile, the complex has better application in the field of photodegradation dyes. The complex has many advantages in photodegradation of dyes compared to semiconductor materials conventionally used for photodegradation: (1) The precision of the crystal structure is beneficial to researching the relationship between the structure and the property of the complex photodegradation dye; (2) The active site capable of coordination promotes the efficient utilization of solar energy by the complex; (3) The porosity and larger specific surface area of the complex can allow dye molecules to pass through the channel rapidly, which is very effective for improving the efficiency of photocatalytic degradation; (4) The interaction of the metal ion of the complex and the ligand can effectively separate the photoelectric electron and the vacancy, thereby improving the photocatalytic activity. Therefore, the complex has high photocatalytic activity and chemical stability, and the synthesis method is simple, so that the complex is an ideal photoreaction catalyst. A series of complexes having photodegradation or dye adsorption properties have been reported, but few complexes having both photocatalytic photodegradation and dye adsorption properties have been reported.
4,4' -bis (2-methyl-1-imidazolyl) biphenyl is a bridging ligand with strong coordination ability: two methylimidazole are arranged at two ends of the ligand, which is beneficial to the synthesis of the complex; the 5-tertiary butyl isophthalic acid can be partially or completely deprotonated, allows different coordination models with metal ions, and is easy to synthesize metal complexes with different dimensions, and the synthesis of structures with different dimensions is a crucial step for completing the device.
The invention belongs to the technical field of organic synthesis and metal organic chemistry, and relates to synthesis of a one-dimensional copper complex, in particular to synthesis of a copper complex with 4,4' -bis (2-methyl-1-imidazolyl) biphenyl and 5-tertiary butyl isophthalic acid as ligands and application of the copper complex in the aspects of catalyzing photodegradation and dye adsorption.
The property of the complex to catalyze photodegradation and adsorb to remove organic dye in water is explored here with cupric ions as the main body and 4,4' -bis (2-methyl-1-imidazolyl) biphenyl and 5-tert-butyl isophthalic acid as ligands.
The copper complex has stable and efficient property of catalyzing photodegradation dye at normal temperature, particularly, the copper complex is used for photocatalysis aiming at methyl orange and methylene blue dye, the methyl orange is basically degraded completely within 70 minutes, the methylene blue is basically degraded completely within 105 minutes, the copper complex is easy to separate and recycle for multiple times, and the catalytic efficiency is basically kept unchanged. The copper complex has good adsorption performance on methyl orange in aqueous solution, and the removal rate of the copper complex for the aqueous solution of methyl orange with the concentration of 10, 15 and 20mg/L in 300 minutes is as high as 94.1%,95.8% and 96.3%. In addition, the copper complex has the advantages of simple preparation method, low cost, high efficiency, good reproducibility, high yield and the like.
Disclosure of Invention
The invention provides a copper complex with the properties of catalyzing photodegradation and adsorbing dye and a preparation method thereof. The invention adopts 4,4' -di (2-methyl-1-imidazolyl) biphenyl, 5-tertiary butyl isophthalic acid ligand and copper nitrate to construct a complex with one-dimensional structure. The compound has high catalytic activity, can efficiently degrade methyl orange and methylene blue in water, and is particularly important that the catalyst is insoluble in water and can be separated and recycled for multiple times. On the other hand, the compound has excellent adsorption performance, and can adsorb and remove methyl orange in water. Finally, the compound has the advantages of simple synthesis method, low cost, good reproducibility and high yield of more than 71 percent (based on metal Cu), can be applied to industrial production, and has potential application prospect in the aspect of removing organic dye in water.
The chemical formula of the copper complex with the properties of catalyzing photodegradation and adsorbing dye is as follows: [ Cu ] 2 (4,4′-BMIBP)(TBIP) 2 (H 2 O) 2 ·2DMA] n Wherein 4,4 '-bmibp=4, 4' -bis (2-methyl-1-imidazolyl) biphenyl, H 2 TBIP = 5-t-butylisophthalic acid. 4,4' -BMIBP, H 2 The structural formula of TBIP is as follows:
the one-dimensional copper complex with the properties of catalyzing photodegradation and adsorbing dye has the structure shown in the figure 1 (a), and the basic structural parameters are as follows:
the crystal of the copper complex of the invention belongs to monoclinic system, and the space group is P2 1 And/c, the unit cell parameters are α=γ=90°, β= 104.96 (2) °; each copper atom in the complex is coordinated with oxygen atoms from two 5-tertiary butyl isophthalic acid, a nitrogen atom of 4,4' -di (2-methyl-1-imidazolyl) biphenyl and an oxygen atom of one water molecule to form an infinite one-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) biphenyl:5-tertiary butyl isophthalic acid and copper nitrate trihydrate=1:1:1, N-dimethylacetamide (1.5 mL) and deionized water (1.5 mL) are added, ultrasonic oscillation is carried out for 5 minutes, the mixture is uniformly mixed, and the mixture is put into a polytetrafluoroethylene liner of a hydrothermal reaction kettle to obtain a mixed solution;
(2) Baking the mixed solution at 100 ℃ for 72 hours, taking out the product and separating the solid;
(3) By H 2 O the solid was washed three times to give blue transparent bulk crystals with yields as high as 71% based on Cu.
Furthermore, the invention provides application of the copper complex in the aspects of catalyzing photodegradation and absorbing and removing methylene blue and methyl orange in water, which is used for treating azo dye wastewater such as methylene blue, methyl orange and the like in natural water.
The invention has the advantages that: the preparation method has simple process, high yield and good reproducibility, can obtain the single-crystal-form and high-purity crystal material, and is easy for industrial production; the product can quickly and effectively degrade methyl orange and methylene blue in water body, the catalytic efficiency of repeated recycling is basically kept unchanged, and the product can effectively adsorb the methyl orange in the water body under dark conditions.
Brief description of the drawings
FIG. 1 (a) is a crystal structure diagram of the copper complex of the present invention; FIG. 1 (b) is a one-dimensional chain structure of the copper complex of the present invention.
FIG. 2 (a) is a graph showing the change in absorbance of 10mg/L methylene blue by photocatalysis of the copper complex of the invention; FIG. 2 (b) is a graph showing the change in absorbance of 10mg/L methyl orange by photocatalysis of the copper complex of the present invention.
FIG. 3 (a) is a graph showing the absorbance change when the copper complex of the present invention adsorbs 10mg/L methyl orange; FIG. 3 (b) is a graph showing the absorbance change when the copper complex of the present invention adsorbs 15mg/L methyl orange; FIG. 3 (c) is a graph showing the absorbance change when the copper complex of the present invention adsorbs 20mg/L methyl orange.
Detailed Description
For a better understanding of the present invention, the following description will further illustrate the present invention with reference to examples, but the present invention is not limited to the following examples.
Example 1 synthesis of ligand 4,4' -bis (2-methyl-1-imidazolyl) biphenyl:
preparing 4,4' -bis (2-methyl-1-imidazolyl) biphenyl (4, 4' -BMIBP) by adopting a one-pot method under a polar solvent and heating 4,4' -dibromobiphenyl, 2-methylimidazole, potassium carbonate and cuprous oxide;
wherein the molar ratio of 4,4' -dibromobiphenyl to 2-methylimidazole to potassium carbonate to cuprous oxide is 2:6:8:1; the reaction temperature is 150 ℃ and the reaction time is 3 days.
Example 2 synthesis of complex:
12.08mg of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.7mg of 4,4 '-bis (2-methyl-1-imidazolyl) biphenyl (4, 4' -BMIBP), 11.1mg of 5-tert-butylisophthalic acid (H) 2 TBIP) is dissolved in 1.5mL of N, N-dimethylacetamide and 1.5mL of aqueous solution, the mixture is stirred for 5 minutes by ultrasonic oscillation and is mixed uniformly, the mixture is put into a polytetrafluoroethylene liner of a hydrothermal reaction kettle to obtain a mixed solution, the mixed solution is baked for 72 hours at 100 ℃, the product is taken out, and the solid is separated, so that a blue blocky crystal can be obtained, and the yield calculated based on metal Cu is 71%.
Structural characterization of the complexes of example 3:
a single crystal of a suitable size was selected with a microscope, and a Siemens (Bruker) SMART CCD diffractometer (graphite monochromator, mo-Ka,) Diffraction data is collected. The diffraction data were corrected for absorbance using the sadbs procedure. Data reduction and structural parsing was done using SAINT and SHELXTL programs, respectively. And determining all non-hydrogen atom coordinates by a least square method, and obtaining the hydrogen atom positions by a theoretical hydrogenation method. And adopting a least square method to refine the crystal structure. The basic coordination is shown in FIG. 1 (a) and FIG. 1 (b)Conditions and stacking patterns. The parameters of the crystallographic diffraction point data collection and structure refinement are shown in the following table.
Table 1 Crystal data of the complexes
R 1 =∑||F o |-|F c ||/∑|F o |.ωR 2 =∑[w(F o 2 -F c 2 ) 2 ]/∑[w(F o 2 ) 2 ] 1/2
Example 4: photocatalytic degradation of complexes of 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 (10 mg/L), and then 5uL of H was added 2 O 2 Stirring in the dark for 30min to make the surface of the complex reach adsorption-desorption equilibrium, then stirring and photodegradation, taking 1mL of methylene blue water solution every 5min, and immediately testing the change of absorbance (figure 2 (a)). The photodegradation results show that the degradation rate of the complex to methylene blue in 105min is up to 98.3%, and the complex can be recycled for multiple times. The same procedure degraded methyl orange, and the degradation rate of the complex for methyl orange in 70min was as high as 97.1% (FIG. 2 (b)).
Example 5: adsorption of methyl orange by complex in darkness:
the specific experimental procedure for adsorption is as follows:
(1) Sample pretreatment: a sample of the copper complex synthesized according to the present invention was immersed in a dichloromethane solvent for 3 days and then dried in vacuo at 100 ℃ for 10 hours to drive off guest molecules in the pores of the sample.
(2) Accurately weighing a certain mass of adsorbent sample, placing the adsorbent sample in a conical flask, adding a certain mass concentration of methyl orange aqueous solution, and carrying out adsorption experiments.
(3) Separating the absorbed experimental sample turbid liquid by using a centrifugal machine, taking supernatant, and measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer.
An adsorption experiment was performed by adding 10mg of activated copper complex sample synthesized according to the present invention to 10mg/L, 15mg/L, and 20mg/L of methyl orange aqueous solution. The results show that the copper complex synthesized by the invention has high removal rate of 94.1%,95.8% and 96.3% for methyl orange aqueous solutions with the concentration of 10, 15 and 20mg/L in 300min (as shown in figure 3).
Claims (2)
1. A copper complex for catalyzing photodegradation and removing organic dye in water by adsorption is characterized in that the chemical formula is [ Cu ] 2 (4,4′-BMIBP)(TBIP) 2 (H 2 O) 2 ·2DMA] n Wherein 4,4 '-bmibp=4, 4' -bis (2-methyl-1-imidazolyl) biphenyl, H 2 TBIP = 5-t-butylisophthalic acid, DMA = N, N-dimethylacetamide; the crystal of the copper complex belongs to monoclinic system, and the space group is P2 1 And/c, the unit cell parameters are α=γ=90°, β= 104.96 (2) °; each copper atom in the complex is coordinated with an oxygen atom from two ligands of 5-tertiary butyl isophthalic acid, a nitrogen atom of 4,4' -di (2-methyl-1-imidazolyl) biphenyl and an oxygen atom of a water molecule to form an infinite one-dimensional network structure.
2. The method for producing a copper complex according to claim 1, characterized by comprising the steps of: the organic ligand 4,4' -di (2-methyl-1-imidazolyl) biphenyl and 5-tertiary butyl isophthalic acid are mixed with copper nitrate trihydrate in water and N, N-dimethylacetamide, and the copper complex is obtained by a solvent method, wherein: the molar ratio of 4,4' -bis (2-methyl-1-imidazolyl) biphenyl, 5-tert-butyl isophthalic acid and copper nitrate trihydrate is 1:1:1, each 0.05mmol of copper nitrate trihydrate corresponds to a mixed solution of 1.5mL of deionized water and 1.5mL of N, N-dimethylacetamide, the temperature is 100 ℃, and the reaction time is three days.
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