CN109438718A - The preparation and its application of the two-dimensional channel zinc compound in active site - Google Patents
The preparation and its application of the two-dimensional channel zinc compound in active site Download PDFInfo
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- CN109438718A CN109438718A CN201811108465.3A CN201811108465A CN109438718A CN 109438718 A CN109438718 A CN 109438718A CN 201811108465 A CN201811108465 A CN 201811108465A CN 109438718 A CN109438718 A CN 109438718A
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Abstract
The present invention relates to a kind of two-dimensional channel zinc compound in active site, the chemical formula of the zinc compound is Zn (CH3COOH)2·2H2O, anorthic system, space group P-1, cell parameter are α=γ=100 °, β=96 °,Z=2.The two-dimensional channel of compound matches with arsenic ion in the present invention, and the active site in duct can interact with arsenic ion, therefore the compound has specificity to the probe of some substances, it is not influenced by other ions when detecting target metal ions, it is selectively good to target analytes.
Description
Technical field
The present invention relates to every compound technical more particularly to a kind of two-dimensional channel zinc compound in active site
Preparation and its application.
Background technique
Arsenic (III) ion is the heavy metal ion with significant and bio-toxicity, As3+Ion is not easy after entering environment
It is degraded by microorganisms, and various forms can only occur and mutually convert, disperse and enrichment process (migrate). As3+Ion will not
In the environment by fast decoupled as organic pollutant, but human body is entered by big gas and water, food etc., it is certain in human body
Accumulation, causes slow poisoning, is detrimental to health in organ, unfortunately, in the industrial production, often arsenic in industrial wastewater
Content is much exceeded.Poisonous effect will be generated since arsenic (III) ion concentration is excessively high, this people made is badly in need of developing a kind of high
Sensitivity, highly selective method detect As in environment3+The content of ion.In order to make As3+The detection of ion is limited in ppb water
Flat, various effective methods are developed by people.However, the equipment of current most of method or needs valuableness, multiple
Miscellaneous technology or relate to multisample operation and the consumption of time.
The method of electrochemistry is because simple, safety, fast, the advantage of inexpensive and low detection limit, it has also become a detection huge sum of money
Belong to one of technology most popular in ion.Electrochemical Detection As3+Ion is a selectable path, some chemical modifying electricity
Pole is used to detection As3+Ion.Up to the present, people always try to reduce As with chemically modified electrode3+The detection of ion
The limit.However, the searching of modified electrode material will be the largest challenge.
Therefore, it carries out in a deep going way by electrochemical sensing technology in conjunction with the organic duct polymer phase of metal-, to development high selection
Property, high sensitivity, micromation and practical new chemical/nanosensor analytical technology there is important theory and practical meaning
Justice.Meanwhile there is highly important application prospect in terms of measuring detection of heavy metal ion, monitoring and improvement.
Summary of the invention
Technical problems based on background technology propose a kind of for detecting the two dimension in the active site of arsenic ion
Duct zinc compound.
A kind of two-dimensional channel zinc compound in active site, the coordination mode of the zinc compound is as shown in Fig. 1.
Preferably, the chemical formula of the zinc compound is Zn (CH3COOH)2·2H2O, anorthic system, space group P-1,
Cell parameter isα=γ=100 °, β=96 °,Z=
2。
Preferably, the zinc compound has two-dimensional cellular structure, and structure is as shown in Figure 2.
Preferably, a kind of preparation method of the two-dimensional channel zinc compound in active site, method and step are as follows:
S1: by the bpyp ligand of 0.10mmol and the H of 0.10mmol2After the mixing of sba ligand obtained mixture with
Zn (the CH of 0.20mmol3COOH)2·2H2O is put into togerther in the reaction kettle of 10mL, and 1.5mLN, N'- dimethyl acetamide is added
(DMA) 3 drop HNO are added dropwise in solvent and 1mL acetonitrile solution3With 0.5mL deionized water, measuring its pH is 4.5-5.5, at this time solution
For transparency liquid；
S2: vial is heated to seal to 100-110 DEG C, continuous heating 5-10 days, is then dropped with the rate of 5 DEG C/h
To room temperature, there are colourless bulk crystals to be precipitated to get.
Preferably, the HNO3Mass concentration be 50-62%.
A kind of two-dimensional channel zinc compound in active site proposed by the present invention is in As3+Answering in the detection of ion
With.
Compared with prior art, the device have the advantages that being:
A kind of two-dimensional channel zinc compound in active site proposed by the present invention has high thermal stability, duct
Frame can be stabilized to 300 DEG C, can be stabilized in the water that pH is 3.5-11.5.Metal-organic nano duct polymer has
The advantages that stability height, large specific surface area, so that heavy metal ion is easy to be enriched in high-density on its duct, in addition nanometer
Duct material can reduce the overpotential of substrate, increase response current, increase the absorption of measured object and product in electrode surface, institute
To target analytes high sensitivity, fast response time.
The two-dimensional channel of compound matches with arsenic ion in the present invention, and the active site in duct can be with arsenic ion
Interact, therefore the compound has specificity to the probes of some substances, when detecting target metal ions not by
The influence of other ions is selectively good to target analytes.
Metal-organic nano duct polymer material is directly overlayed into interior reference surface of metal electrode, due to eliminating
Electrode internal-filling liquid effectively reduces to eliminate diffusion of the metal ion from internal-filling liquid through electrode film to sample solution
Influence of the metal ion flux to electrode detection limit, improves the sensitivity of detection.
In addition, the organic duct polymer of metal-is combined with electrochemical sensor, so that be easy to manipulate in use process,
Recycling also becomes convenient, not will cause secondary environmental pollution.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the coordination mode of zinc atom in embodiment 1；
Fig. 2 is the two-dimensional cellular structure of 1 zinc compound of embodiment；
Fig. 3 is the thermogravimetric curve of 1 zinc compound frame of embodiment；
Fig. 4 is the conductibility of each electrode of cyclic voltammetry (CVS) probe；
Fig. 5 be modified electrode AuNPs/MOF-1/GCE to the concentration of arsenic ion 5 × 10-13mol/L- 9×10-8mol/L
Detection curve；
Fig. 6 be modified electrode AuNPs/MOF-1/GCE to the concentration of arsenic ion 5 × 10-13mol/L- 9×10-8mol/L
Concentration range in show good linear relationship；
Fig. 7 is；Selectivity of the modified electrode AuNPs/1/GCE to different metal ions.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment 1
A kind of preparation method of the two-dimensional channel zinc compound in active site:
S1: by the bpyp ligand of 0.10mmol and the H of 0.10mmol2After the mixing of sba ligand obtained mixture with
Zn (the CH of 0.20mmol3COOH)2·2H2O is put into togerther in the reaction kettle of 10ml, and 1.5 mLN, N'- dimethyl acetamide is added
(DMA) 3 drop HNO are added dropwise in solvent and 1mL acetonitrile solution3(mass concentration 62%) and 0.5mL deionized water, measuring its pH is
5.0, solution is transparency liquid at this time；
S2: being heated to seal to 105 DEG C for vial, continuous heating 6 days, then drop to room temperature with the rate of 5 DEG C/h, this
When vial in there are colourless bulk crystals to be precipitated, yield 65%.
Complex [Zn2(bpyp)(sba)2]n·H2The structure determination of O:
After crystal DMF wash clean, selects quality and the suitable crystal of size is placed in Bruker-AXS SMART CCD
On X- monocrystalline instrument, two crystal datas are scanned (graphite monochromator) with the Mo-K alpha ray of monochrome purifying, and wherein λ isω is 0.3 °, collects the diffraction data of two crystal, and SAINT software carries out the reduction of diffraction data, is used
SADABS route carries out absorption correction.Crystal structure is parsed using direct method by SHELXTL software, with (F2) minimum two
Multiplication is to the non-hydrogen atom and hydrogen atom coordinates of zinc compound, and isotropic temperature factor and anisotropic temperature factor refine are extremely
Convergence.The parsing and refine of zinc compound are completed with SHELXL-97 program bag.The related crystalline data of zinc compound are listed in table
In 1.
The crystal data of 1 zinc compound of table
aR1=Σ | | Fo|–|Fc|)/Σ|Fo|；wR2=[Σ w (Fo 2–Fc 2)2/Σw(Fo 2)2]1/2
Complex [Zn2(bpyp)(sba)2]n·H2The structure of O describes
Two dimension (2D) duct zinc compound [Zn in the active site of an example has been obtained under hydrothermal synthesizing condition2
(bpyp)(sba)2]n·H2O(1).Single crystal diffraction is analysis shows zinc compound has P-1 anorthic system.As shown in fig. 1, zinc
Zn1 atom is the mode of pentacoordinate in compound, and space geometry is configured as the trigonal biyramid of distortion, wherein participating in four of coordination
The sba ligand that oxygen atom is protonated from four, a nitrogen-atoms come from bpyp ligand.In zinc compound, protonate completely
The mode and zinc atom that carboxyl on sba ligand takes bidentate list to be coordinated are coordinated, and the one-dimensional cyclic structure of shape, these are one-dimensional
Cyclic structure connects to form two-dimensional cellular structure by bpyp ligand, as shown in Figure 2.Through careful it has been observed that zinc impregnation is closed
There are two kinds of active group pyridyl groups and sulfonyls in object.
Complex [Zn2(bpyp)(sba)2]n·H2The stability of O
The crystal of synthesis is cleaned multiple times with DMF, until crystal is pure, is then dried at room temperature with spare.In order to grind
Study carefully compound [Zn2(bpyp)(sba)2]n·H2The stability of O (1) frame, has carried out thermogravimetric analysis, such as Fig. 3 to zinc compound.
Thermogravimetric curve analysis finds that the frame of zinc compound can be stabilized to 300 DEG C.In addition, being investigated zinc compound difference pH in water
Stability under value, research find that two-dimensional channel zinc compound can be stabilized in the water that pH is 3.5-11.5.
Complex [Zn2(bpyp)(sba)2]n·H2O is to As3+Ion electrochemical detection
Two-dimensional channel zinc compound due to more active sites, high thermal stability and can pH be 3.5-11.5
Water in be stabilized.Therefore, two-dimensional channel zinc compound synergic nano gold is covered on the surface glass-carbon electrode (GCE), developed
Model electrochemical modified electrode AuNPs/1/GCE.Glass-carbon electrode after modification is to As3+The detected representation of ion goes out selection well
Property, high stability and sensitivity and wide detection range.
The conductibility of each electrode of probe is gone with cyclic voltammetry (CVS).Fig. 4 is the CVs curve obtained under Different electrodes
(scanning speed 100mVs-1).Curve a is naked GCE.The current peak Ip of AuNPs/1/GCE electrode is increased, Voltage Peak spacing
Ep reduces relative to electrode GCE and 1/GCE.
In order to preferably be detected, it is investigated the optimum condition of experiment, research finds optimum optimizing condition are as follows: deposition
Golden number of segment is 6 sections, and electrolyte is Klorvess Liquid；Electrolyte concentration is the potassium chloride of 0.05M, and optimal quiescent time is 90
Second.
For SWASV under conditions of optimum optimization, modified electrode AuNPs/1/GCE is to As3+The concentration of ion is 5 × 10- 13mol/l to 9×10-8Good linear relationship is shown in the concentration range of mol/l, as shown in Fig. 5, Fig. 6.To As3+From
The minimum detection limit of son is 1 × 10-13mol/l(R2=0.993), this is far below U.S. environment administration (EPA) and the World Health Organization
(WHO) the limit concentration formulated.Especially modified electrode AuNPs/ 1/GCE is to As3+The wide range of linearity that ion is shown and
Low detection limit, this has greater advantage compared with mercury electrode and its detection method.To As3+The hypersensitivity of ion and low detection limit
Zinc compound should be attributed to and nanogold increases and exists in electrode surface specific surface area and two-dimensional channel zinc compound structure
Multiple active sites.
Modified electrode AuNPs/1/GCE is to As3+The concentration of ion is 5 × 10-13mol/l to 9×10-8Mol/l:
Good linear relationship and low detection limit (SWASV parameter: frequency 40Hz, 20 mV of amplitude, voltage increment are shown in range
4mV)。
Modified electrode AuNPs/1/GCE is to As3+Ion has good selectivity, and modified electrode is to other metal ions (As3 +,Zn2+,Cd2+,Hg2+,Ag+,Pb2+,Co2+, and Fe3+) detection electrochemical signals intensity it is very weak.The result shows modifications
Electrode A uNPs/1/GCE is to As3+Ion has selectivity well, sees Fig. 7.
Embodiment 2
A kind of preparation method of the two-dimensional channel zinc compound in active site:
S1: by the bpyp ligand of 0.10mmol and the H of 0.10mmol2After the mixing of sba ligand obtained mixture with
Zn (the CH of 0.20mmol3COOH)2·2H2O is put into togerther in the reaction kettle of 10ml, and 1.5 mLN, N'- dimethyl acetamide is added
(DMA) 3 drop HNO are added dropwise in solvent and 1mL acetonitrile solution3(mass concentration 55%) and 0.5mL deionized water, measuring its pH is
4.5, solution is transparency liquid at this time；
S2: being heated to seal to 100 DEG C for vial, continuous heating 5 days, then drop to room temperature with the rate of 5 DEG C/h, this
When vial in there are colourless bulk crystals to be precipitated, yield 64%.
Embodiment 3
A kind of preparation method of the two-dimensional channel zinc compound in active site:
S1: by the bpyp ligand of 0.10mmol and the H of 0.10mmol2After the mixing of sba ligand obtained mixture with
Zn (the CH of 0.20mmol3COOH)2·2H2O is put into togerther in the reaction kettle of 10ml, and 1.5 mLN, N'- dimethyl acetamide is added
(DMA) 3 drop HNO are added dropwise in solvent and 1mL acetonitrile solution3(mass concentration 65%) and 0.5mL deionized water, measuring its pH is
5.5, solution is transparency liquid at this time；
S2: being heated to seal to 110 DEG C for vial, continuous heating 10 days, then drop to room temperature with the rate of 5 DEG C/h,
There are colourless bulk crystals to be precipitated in vial at this time, yield 50%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of two-dimensional channel zinc compound in active site, which is characterized in that the coordination mode of the zinc compound is such as
Shown in Fig. 1.
2. a kind of two-dimentional zinc compound in active site according to claim 1, which is characterized in that the zinc impregnation is closed
The chemical formula of object is Zn (CH3COOH)2·2H2O, anorthic system, space group P-1, cell parameter areα=γ=100 °, β=96 °,Z=2.
3. a kind of two-dimensional channel zinc compound in active site according to claim 1, which is characterized in that the zinc
Compound has two-dimensional cellular structure, and structure is as shown in Figure 2.
4. a kind of preparation method of the two-dimensional channel zinc compound in active site according to claim 1, feature
It is, method and step is as follows:
S1: by the bpyp ligand of 0.10mmol and the H of 0.10mmol2Obtained mixture and 0.20mmol after the mixing of sba ligand
Zn(CH3COOH)2·2H2O is put into togerther in the reaction kettle of 10mL, be added 1.5mLN, N'- dimethyl acetamide (DMA) solvent and
3 drop HNO are added dropwise in 1mL acetonitrile solution3With 0.5mL deionized water, measuring its pH is 4.5-5.5, and solution is transparency liquid at this time；
S2: vial is heated to seal to 100-110 DEG C, continuous heating 5-10 days, room is then dropped to the rate of 5 DEG C/h
Temperature, there are colourless bulk crystals to be precipitated to get.
5. a kind of preparation method of the two-dimensional channel zinc compound in active site according to claim 4, feature
It is, the HNO3Mass concentration be 50-62%.
6. a kind of two-dimensional channel zinc compound in active site according to claim 1, which is characterized in that the zinc
Application of the compound in arsenic ion detection.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009030894A1 (en) * | 2007-09-04 | 2009-03-12 | Halliburton Energy Services, Inc. | Composition and method for removing metal contaminants |
| CN106243139A (en) * | 2016-08-01 | 2016-12-21 | 皖西学院 | The micropore cadmium compound in active site and preparation method thereof |
-
2018
- 2018-09-21 CN CN201811108465.3A patent/CN109438718B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009030894A1 (en) * | 2007-09-04 | 2009-03-12 | Halliburton Energy Services, Inc. | Composition and method for removing metal contaminants |
| CN106243139A (en) * | 2016-08-01 | 2016-12-21 | 皖西学院 | The micropore cadmium compound in active site and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BISWAJIT DEY: "Aluminescent-water soluble inorganic co-crystal for a selective pico-molar range arsenic(III) sensor in water medium", 《CHEMCOMM》 * |
| COSKUNER ORKID: "Dynamic and Structural Properties of Aqueous Arsenic Solutions", 《CHEMPHYSCHEM》 * |
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