CN111171082B - Nickel complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof - Google Patents
Nickel complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof Download PDFInfo
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- CN111171082B CN111171082B CN201811364814.8A CN201811364814A CN111171082B CN 111171082 B CN111171082 B CN 111171082B CN 201811364814 A CN201811364814 A CN 201811364814A CN 111171082 B CN111171082 B CN 111171082B
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- imidazolyl
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052759 nickel Inorganic materials 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
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 claims abstract description 13
- 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 abstract description 12
- -1 nickel metal complex Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- WHGYCGOFTBFDLW-UHFFFAOYSA-L nickel(2+);diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O WHGYCGOFTBFDLW-UHFFFAOYSA-L 0.000 claims description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 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
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000013110 organic ligand Substances 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000003446 ligand Substances 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 26
- 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 15
- 229940012189 methyl orange Drugs 0.000 description 15
- 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 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001308 synthesis method Methods 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
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000000987 azo dye Substances 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
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development 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
- 150000002815 nickel Chemical group 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- TYIWSFQPQRDHTJ-UHFFFAOYSA-N OCl(=O)(=O)=O.OCl(=O)(=O)=O.O Chemical group OCl(=O)(=O)=O.OCl(=O)(=O)=O.O TYIWSFQPQRDHTJ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 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
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 210000004916 vomit Anatomy 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention provides a nickel metal complex, a preparation method and application thereof in catalyzing photodegradation and adsorbing dye. The chemical formula of the complex is [ Ni (BMIOPE) 2·2ClO4]n; wherein BMIOPE = 4,4' -bis (2-methyl-1-imidazolyl) biphenyl ether. The nickel metal complex is a two-dimensional reticular structure formed by self-assembly of nickel ions through BMIOPE ligands. The experimental results show that: the nickel 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, provides a new means for treating harmful substances in the environment, and also provides a new thought 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 preparation of a nickel complex taking 4,4' -bis (2-methyl-1-imidazolyl) biphenyl ether as a ligand and application of the nickel complex in catalytic photodegradation and adsorption removal of organic dye in water.
Background
The rapid development of industry brings about serious ecological environment problems, and the living environment of human beings is continuously destroyed, so that the water pollution problem is serious. At present, the main source of water pollution in China is industrial wastewater, wherein the printing and dyeing wastewater accounts for more than 35% of the specific gravity of the industrial wastewater. The printing and dyeing wastewater has the characteristics of large wastewater quantity, high chromaticity, high toxicity, complex water quality and the like, and belongs to high-concentration organic wastewater difficult to degrade. Azo dyes such as Methylene Blue (MB) and Methyl Orange (MO) are extremely harmful in water, not only seriously endanger ecological balance of rivers and oceans, but also can be absorbed into human bodies through skin, so that headache, vomit and even irreversible injury or even cancer of various organs are caused. Therefore, the efficient treatment of azo-type dye contaminants in water is an important issue.
The traditional water treatment process is continuously innovated because of a series of defects of easy secondary pollution, high energy consumption, low efficiency and the like, and is gradually changed into new material development of water treatment from the innovation of the pure traditional treatment process. The method for catalyzing photodegradation of dye wastewater by using the environmental purification material can degrade a plurality of complex macromolecules which are difficult to biodegrade, and is attracting attention in the field of dye wastewater treatment. In addition, the separation and recycling of organic dyes from mixed dye wastewater is also a problem to be solved urgently, and the search for environmental purification materials with higher adsorption capacity is also a hot spot of current research. Therefore, it is an important challenge to design an environmental purification material with adsorption and photocatalytic properties that is environmentally friendly to synthesize, simple to synthesize.
A great deal of reports about the application of the complex in the field of photodegradable dyes show that the complex with different molecular structures has better application in the field of photodegradable 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 photodegradation dye; (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.
The advantage of the complex for dye adsorption over conventional inorganic adsorbents is: (1) The composition, structure and pore canal size can be regulated and controlled, so that the complex is suitable for dye adsorption with various sizes; (2) The electrical property and the electric quantity of the material are adjustable, various organic dyes can be adsorbed, the binding force is strong, and the material is not easy to fall off; (3) The adsorption quantity is large, the method is quick and efficient, and the interference from external conditions is small; and (4) the dye can be regenerated after being adsorbed, and the method is economically feasible. Therefore, the complex has high adsorption capacity, good selective adsorption capacity and simple synthesis method, and is an ideal adsorbent. 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 ether is a bridging ligand with strong coordination ability. This ligand has two distinct features: firstly, the ligand is V-shaped imidazole ligand with semi-flexibility, and two 2-methylimidazole groups are arranged at two ends of the ligand, so that the synthesis of a complex is facilitated; secondly, the C-C bond between the rigid benzene ring and the 2-methylimidazole can rotate to a certain extent to adapt to various coordination environments, so that metal complexes with different dimensions are easy to synthesize, 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 two-dimensional nickel complex, in particular to synthesis of a nickel complex with 4,4' -bis (2-methyl-1-imidazolyl) diphenyl ether as a ligand and application of the nickel complex in the aspects of catalyzing photodegradation and dye adsorption. The property of the complex for catalyzing photodegradation and removing organic dye in water by adsorption is explored by taking divalent nickel ions as a main body and 4,4' -di (2-methyl-1-imidazolyl) biphenyl ether as a ligand.
The nickel complex has stable and efficient property of catalyzing photodegradation dye at normal temperature, particularly for methylene blue dye, the methylene blue is basically degraded completely within 100 minutes under the condition of visible light, and the nickel complex is easy to separate and recycle for multiple times, and the catalytic efficiency is basically unchanged. The nickel complex has good adsorption performance on methyl orange in aqueous solution, and the removal rate of the aqueous solution of the methyl orange with the concentration of 15 mg/L, 17 mg/L and 20mg/L in 180 minutes is as high as 96.2%,98.7% and 99.4%. In addition, the nickel 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 nickel 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 ether ligand and nickel perchlorate to construct a complex with a two-dimensional structure. The compound has high catalytic activity, can efficiently degrade methylene blue in water under the condition of visible light, 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 which reaches more than 67 percent (based on metal Ni), 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 nickel complex with the properties of catalyzing photodegradation and adsorbing dye is as follows: [ Ni (BMIOPE) 2·2ClO4]n, wherein BMIOPE =4, 4' -bis (2-methyl-1-imidazolyl) biphenyl ether. BMIOPE has the structural formula:
The two-dimensional nickel 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 nickel complex of the invention belongs to tetragonal system, the space group is I-42d, and the unit cell parameter is Α=β=γ=90°; each nickel atom of the complex species coordinates with a nitrogen atom from four ligands 4,4' -bis (2-methyl-1-imidazolyl) biphenyl ether, two perchlorate oxygen atoms, forming an infinite two-dimensional network structure, as shown in fig. 1 (b).
The preparation method of the nickel complex comprises the following steps:
(1) The preparation method comprises the following steps: 4,4' -bis (2-methyl-1-imidazolyl) biphenyl ether: nickel perchlorate hexahydrate=1:1, methanol (5 mL) and water (5 mL) were added, and stirred to obtain a mixed solution;
(2) Standing and volatilizing the mixed solution for 3 days at normal temperature to obtain light green blocky crystals;
(3) The yield calculated on metallic Ni was 67%.
Furthermore, the invention provides application of the nickel complex in the aspects of removing methylene blue in water by catalytic photodegradation and removing methyl orange in water by adsorption, and the nickel complex 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 rapidly and effectively degrade methylene blue in the water body under visible light, the catalytic efficiency of repeated recycling is basically kept unchanged, methyl orange in the water body can be effectively adsorbed under dark conditions, and the method has the advantages of high efficiency, simplicity and convenience in operation, good removal effect and the like.
Brief description of the drawings
FIG. 1 (a) is a crystal structure diagram of a nickel complex of the present invention; FIG. 1 (b) is a two-dimensional network structure of the nickel complex of the present invention.
FIG. 2 is a graph showing the change in absorbance of 10mg/L methylene blue for photocatalytic degradation of a nickel complex according to the present invention.
FIG. 3 (a) is a graph showing the absorbance change of 10mg/L methyl orange adsorbed by the nickel complex of the present invention; FIG. 3 (b) is a graph showing the absorbance change of 15mg/L methyl orange adsorbed by the nickel complex of the present invention; FIG. 3 (c) is a graph showing the absorbance change of methyl orange adsorbed at 20mg/L by the nickel complex of the present invention.
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 ether (BMIOPE):
Preparing 4,4 '-bis (2-methyl-1-imidazolyl) biphenyl ether (BMIOPE) by adopting a one-pot method under a polar solvent and heating 4,4' -dibromodiphenyl ether, 2-methylimidazole, potassium carbonate and cuprous oxide;
Wherein the molar ratio of the 4,4' -dibromodiphenyl ether to the 2-methylimidazole to the potassium carbonate to the cuprous oxide is 2:8:8:1; the reaction temperature is 180 ℃ and the reaction time is 3 days.
Example 2 synthesis of complex:
18.29mg of nickel perchlorate hexahydrate (Ni (ClO 4)2·6H2 O), 16.51mg of 4,4' -bis (2-methyl-1-imidazolyl) biphenyl ether (BMIOPE) were dissolved in 5mL of methanol and 5mL of an aqueous solution, and left to stand at room temperature for 3 days by a solvent evaporation method, pale green bulk crystals were obtained in a yield of 67% based on metallic Ni.
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 and stacking scheme are shown in FIGS. 1 (a) and 1 (b). 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
R1=∑||Fo|-|Fc||/∑|Fo|.ωR2=∑[w(Fo 2-Fc 2)2]/∑[w(Fo 2)2]1/2
Example 4: visible light degradation methylene blue of complex
30Mg of the nickel complex synthesized according to the present invention was weighed into 50mL of an aqueous solution of methylene blue (10 mg/L), then 5uL of H 2O2 was added, stirring was performed in the dark for 30 minutes to allow the surface of the complex to reach adsorption-desorption equilibrium, then the complex was irradiated with a visible lamp while stirring, 1mL of an aqueous solution of methylene blue was taken every 5 minutes, and the change in absorbance was immediately measured (see FIG. 3). The photodegradation results show that the degradation rate of the complex to methylene blue in 100min is up to 94.3%, and the complex can be recycled for multiple times.
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 nickel 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 the activated nickel complex sample synthesized according to the present invention to 15mg/L, 17mg/L, and 20mg/L of methyl orange aqueous solution. The results show that the nickel complex synthesized by the invention has high removal rate of 96.2%,98.7% and 99.4% for methyl orange aqueous solution with concentration of 15, 17 and 20mg/L in 180min (as shown in figure 3).
Claims (2)
1. A nickel complex for catalytic photodegradation and adsorption removal of organic dye in water, characterized by the chemical formula [ Ni (BMIOPE) 2·2ClO4]n, wherein BMIOPE = 4,4' -bis (2-methyl-1-imidazolyl) biphenyl ether; the crystal of the nickel complex belongs to tetragonal system, the space group is I-42d, and the unit cell parameters are as follows: α=β=γ=90°; the central ion nickel is in a hexacoordinated octahedral configuration, and coordinates with the nitrogen atoms of four 4,4' -bis (2-methyl-1-imidazolyl) diphenyl ether and the oxygen atoms of two perchlorate radicals to form an infinite two-dimensional network structure.
2. The method for producing a nickel complex according to claim 1, characterized by comprising the steps of: the organic ligand 4,4' -bis (2-methyl-1-imidazolyl) biphenyl ether and nickel perchlorate hexahydrate are in a mixed solution of water and methanol, and a nickel complex is obtained through solvent volatilization, wherein: the molar ratio of the 4,4' -bis (2-methyl-1-imidazolyl) diphenyl ether to the nickel perchlorate hexahydrate is 1:1, each 0.05mmol of the nickel perchlorate hexahydrate corresponds to 5mL of a mixed solution of deionized water and 5mL of methanol, the mixed solution is volatilized at normal temperature, and the reaction time is three days.
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