CN111171082A - 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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- CN111171082A CN111171082A CN201811364814.8A CN201811364814A CN111171082A CN 111171082 A CN111171082 A CN 111171082A CN 201811364814 A CN201811364814 A CN 201811364814A CN 111171082 A CN111171082 A CN 111171082A
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- nickel
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- nickel complex
- 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
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 nickel metal complex Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 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
- 239000011259 mixed solution Substances 0.000 claims description 4
- 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 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 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 2
- 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 description 2
- 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
- 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 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- 239000013110 organic ligand Substances 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 28
- 239000003446 ligand Substances 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 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
- 238000001179 sorption measurement Methods 0.000 description 18
- 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 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal 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
- 238000001308 synthesis method Methods 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000000746 purification 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
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 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
- 238000002474 experimental method 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
- 150000008614 2-methylimidazoles Chemical class 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 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
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect 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
- 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
- 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 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
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent 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
- 238000012360 testing method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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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- 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
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- 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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- 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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- 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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Abstract
Hair brushThe invention provides a nickel metal complex, a preparation method and an application thereof in catalyzing photodegradation and absorbing dye. The chemical formula of the complex is [ Ni (BMIOPE)2·2ClO4]n(ii) a Wherein BMIOPE ═ 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether. The nickel metal complex is a two-dimensional network structure formed by self-assembly of nickel ions through a BMIOPE ligand. The experimental results show that: the nickel complex has good properties of catalyzing photodegradation and adsorbing and removing organic dyes in water, 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 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 nickel complex with 4, 4' -di (2-methyl-1-imidazolyl) diphenyl ether as a ligand and application of the nickel complex in the aspects of catalytic photodegradation and adsorption removal of organic dyes in water.
Background
The rapid development of the industry brings about a growing problem of ecological environment, and the living environment of human beings is continuously damaged, so that the problem of water pollution is growing. 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 traditional water treatment process is continuously reformed due to a series of defects of easy generation of secondary pollution, high energy consumption, low efficiency and the like, and the reformation of the simple traditional treatment process is gradually changed into the research and development of new materials for water treatment. The method for degrading dye wastewater by using the environmental purification material to catalyze light can degrade a plurality of complex macromolecules which are difficult to be biodegraded, and attracts more and more 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, and the search for an environmental purification material with higher adsorption capacity is also a hot spot of current research. Therefore, it is an important challenge to design an environment purification material with adsorption and photocatalytic properties that is environment-friendly and simple in synthesis method.
A great number of reports about the application of the complex in the field of photodegradation dyes show that the complex with different molecular structures has better application in the field of photodegradation dyes. Compared with the traditional semiconductor materials for photodegradation, the complex has many advantages in the aspect of photodegradation of dyes: (1) the precision of the crystal structure is beneficial to researching the relationship between the structure and the property of the ligand photodegradation dye; (2) the coordinative active sites promote the efficient utilization of solar energy by the ligand photodegradation dye; (3) the porosity and the larger specific surface area of the complex can allow dye molecules to rapidly pass through a channel, which is very effective for improving the efficiency of photocatalytic degradation; (4) the interaction of the metal ions of the complex and the ligand can effectively separate photoelectrons and vacancies, 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 catalyst for photoreaction.
Compared with the traditional inorganic adsorbent, the complex has the advantages of dye adsorption: (1) the composition, the structure and the size of the pore channel can be regulated, so that the complex is suitable for dye adsorption of various sizes; (2) the material has adjustable electrical property and electric quantity, can adsorb various organic dyes, has strong binding force and is not easy to fall off; (3) the adsorption capacity is large, the method is rapid and efficient, and the interference of external conditions is small; (4) the dye can be regenerated after being adsorbed, and is economical and 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 with photodegradation or dye adsorption properties have been reported, but less complexes with catalytic photodegradation and dye adsorption properties have been reported.
4, 4' -di (2-methyl-1-imidazolyl) diphenyl ether is a bridging ligand with strong coordination capacity. This ligand has two distinct features: firstly, the ligand is a V-type imidazole ligand with semi-flexibility, and two 2-methylimidazoles 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 degree to adapt to various coordination environments, metal complexes with different dimensions are easy to synthesize, and the synthesis of structures with different dimensions is a crucial step for 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 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 catalytic photodegradation and dye adsorption. Divalent nickel ions are respectively used as a main body, 4' -di (2-methyl-1-imidazolyl) diphenyl ether is used as a ligand, and the properties of the complex for catalyzing photodegradation and adsorbing to remove organic dyes in water are researched.
The nickel complex has stable and efficient dye degradation catalysis property at normal temperature, particularly for methylene blue dye, under the condition of visible light, the methylene blue is basically and completely degraded within 100 minutes, the nickel complex is easy to separate and is recycled for multiple times, and the catalysis efficiency is basically kept unchanged. The nickel complex has good adsorption performance on methyl orange in an aqueous solution, and the removal rate of the methyl orange aqueous solution with the concentration of 15, 17 and 20mg/L in 180 minutes is up to 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 selects 4, 4' -di (2-methyl-1-imidazolyl) diphenyl 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 particularly, the catalyst is insoluble in water, 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 (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 dyes in water.
The chemical formula of the nickel complex with the properties of catalyzing photodegradation and adsorbing the dye is as follows: [ Ni (BMIOPE)2·2ClO4]nWherein BMIOPE ═ 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether. The structural formula of BMIOPE is as follows:
the structure of the two-dimensional nickel complex with the properties of catalyzing photodegradation and adsorbing the dye is shown in figure 1(a), and the basic structural parameters are as follows:
the crystal of the nickel complex belongs to a tetragonal system, the space group is I-42d, and the unit cell parameter is
and each nickel atom of the coordinating species is coordinated with a nitrogen atom from four ligands, namely 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether and an oxygen atom from two perchlorates to form 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) diphenyl ether and nickel perchlorate hexahydrate are added to the mixture of 1: 1, and methanol (5mL) and water (5mL) are added and stirred to obtain a mixed solution;
(2) standing the mixed solution at normal temperature for volatilizing for 3 days to obtain light green blocky crystals;
(3) the yield calculated on the basis of metallic Ni was 67%.
Furthermore, the invention provides application of the nickel complex in the aspects of removing methylene blue in water by catalytic photo-degradation and removing methyl orange in water by adsorption, and the nickel 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 the advantages of simple process, high yield and good reproducibility, can obtain a single crystal form and high-purity crystal material, and is easy for industrial production; the product can rapidly and effectively degrade methylene blue in a 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 a dark condition, and the method has the advantages of high efficiency, simplicity and convenience in operation, good removing 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 diagram of the nickel complex of the present invention.
FIG. 2 is a graph showing the change in absorbance of 10mg/L methylene blue by photocatalytic degradation of a nickel complex according to the present invention.
FIG. 3(a) is a graph showing the absorbance change of a nickel complex of the present invention adsorbing 10mg/L methyl orange; 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 change in absorbance of 20mg/L methyl orange adsorbed by the nickel 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 4, 4' -bis (2-methyl-1-imidazolyl) biphenyl ether (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 in a polar solvent under the heating condition;
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: 1; the reaction temperature is 180 ℃, and the reaction time is 3 days.
Example 2 synthesis of the complex:
18.29mg of Nickel perchlorate (Ni (ClO) hexahydrate4)2·6H2O), 16.51mg of 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether (BMIOPE) was dissolved in 5mL of methanol and 5mL of an aqueous solution by a solvent evaporation methodAfter 3 days at room temperature, a greenish block crystal was obtained with a yield of 67% calculated on the metallic Ni.
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: visible light degradation methylene blue of complex
30mg of the nickel complex synthesized according to the invention were weighed into 50mL of an aqueous solution of methylene blue (10mg/L), and 5uL of H was added2O2Stirring in the dark for 30min to make the surface of the complex reach adsorption-desorption equilibrium, then irradiating with a visible light while stirring, taking 1mL of methylene blue aqueous solution every 5min, and immediately testing the change of absorbance (as shown in FIG. 3). The result of photodegradation shows that the complex is 100mThe degradation rate of methylene blue in the in is as high as 94.3 percent, and the methylene blue can be recycled for many times.
Example 5: adsorption of the complex in the dark on methyl orange:
the adsorption was carried out as follows:
(1) sample pretreatment: samples of the synthesized nickel complexes of the present invention were soaked in dichloromethane solvent for 3 days and then vacuum dried at 100 ℃ for 10 hours to drive off the guest molecules in the pores of the samples.
(2) Accurately weighing a certain mass of adsorbent sample, placing the adsorbent sample in a conical flask, adding a methyl orange aqueous solution with a certain mass concentration, and carrying out an adsorption experiment.
(3) And separating the adsorbed turbid liquid of the experimental sample by using a centrifugal machine, taking the 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 sample of the synthesized nickel complex of the present invention to 15mg/L, 17mg/L, and 20mg/L methyl orange aqueous solutions. The results show that the removal rate of the synthesized nickel complex in 180min for methyl orange aqueous solution with the concentration of 15, 17 and 20mg/L is as high as 96.2%, 98.7% and 99.4% (as shown in figure 3).
Claims (3)
1. A nickel complex used for catalyzing photodegradation and adsorbing and removing organic dye in water is characterized in that the chemical formula is [ Ni (BMIOPE)2·2ClO4]nWherein BMIOPE ═ 4, 4' -bis (2-methyl-1-imidazolyl) biphenyl ether; the crystal of the nickel complex belongs to a tetragonal system, the space group is I-42d, and the unit cell parameters are as follows:
the central ion nickel is in a hexa-coordinated octahedral configuration and is coordinated with four nitrogen atoms of 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether and two oxygen atoms of perchlorate to form an infinite two-dimensional network structure.
2. The method for preparing a nickel complex according to claim 1, characterized by the steps of: the organic ligand 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether and nickel perchlorate hexahydrate are volatilized in a mixed solution of water and methanol to obtain a nickel complex.
3. The method of claim 2, wherein: the molar ratio of the 4, 4' -bis (2-methyl-1-imidazolyl) diphenyl ether to the nickel perchlorate is 1: 1, 5mL of deionized water and 5mL of methanol mixed solution correspond to each 0.05mmol of nickel perchlorate, and the mixture is volatilized at normal temperature and reacted for three days.
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