CN109400893B - The preparation and its application of the two-dimentional micropore cadmium compound in active site - Google Patents
The preparation and its application of the two-dimentional micropore cadmium compound in active site Download PDFInfo
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- CN109400893B CN109400893B CN201811108463.4A CN201811108463A CN109400893B CN 109400893 B CN109400893 B CN 109400893B CN 201811108463 A CN201811108463 A CN 201811108463A CN 109400893 B CN109400893 B CN 109400893B
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Abstract
The present invention relates to a kind of two-dimentional micropore cadmium compound in active site, the chemical formula of the cadmium compound is C61H39Cd2N11O12, monoclinic system, space group P21/m, cell parameter is α=γ=90 °, β=104.75 °,Z=2.The two-dimensional channel and Fe of compound in the present invention3+Ion matches, and the active site in duct can be with Fe3+Ion interacts, therefore the compound has specificity to the probe of some substances, is not influenced by other ions when detecting target metal ions, selectively good to target analytes.
Description
Technical field
The present invention relates to the two-dimentional micropore cadmium compounds every compound technical more particularly to a kind of active site
Preparation and its application.
Background technique
Iron (III) ion is one of physiology course indispensable element, however the iron ion of high concentration can displace living body
Interior metal ion, the dynamic equilibrium by destroying substance in cell lead to disease or death.
In industrial production, all too busy to get away ferro element of the progress of many chemical reactions, and often iron in the industrial wastewater being discharged
Content it is much exceeded.Poisonous effect will be generated since iron (III) ion concentration is excessively high, this people made is badly in need of developing one kind
Highly sensitive, highly selective method detects the content of iron in environment (III) ion.In order to limit the detection of iron (III) ion
In ppb level, various effective methods are developed by people；But most of method or need expensive set at present
It is standby, complicated technology or relate to multisample operation and the consumption of time.
The method of electrochemistry because it is simple, safely, quickly, the advantage of low cost 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 iron (III) ion is a selectable path, and some chemistry change
Good electrode is used to detection iron (III) ion.Up to the present, people always try to reduce iron (III) with chemically modified electrode
The detectable limit of ion.However, the searching of modified electrode material will be the largest challenge.
It carries out in a deep going way by electrochemical sensing technology in conjunction with the organic duct polymer phase of metal-, it is highly selective, high to developing
Sensitivity, micromation and practical new chemical/nanosensor analytical technology have important theoretical and practical significance.Together
When, 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 iron ion
Micropore cadmium compound.
A kind of two-dimentional micropore cadmium compound in active site, the coordination mode of the cadmium compound are as follows:
Preferably, the chemical formula of the cadmium compound is C61H39Cd2N11O12, monoclinic system, space group P21/m, structure cell
Parameter isα=γ=90 °, β=104.75 °,
Z=2.
Preferably, the cadmium compound has two-dimensional cellular structure, under structure:
Preferably, a kind of preparation method of the two-dimentional micropore cadmium compound in active site, method and step are as follows:
S1: by (4- pyridyl group) pyrimidine (bpyp) ligand of 2,5- bis- of 0.10mmol and the 5- nitro isophthalic two of 0.10mmol
Formic acid (H2L-NO2) Cd (CH of mixture and 0.10mmol that obtains after ligand mixing3COOH)2·2H2O is put into togerther 10mL's
In reaction kettle, 2mLDMF solvent and 1mL acetonitrile solution is added, 2 drop HNO are added dropwise3With 0.2mL deionized water, measuring its pH is
5.5-6.5 solution is transparency liquid at this time；
S2: vial is heated to seal to 100-120 DEG C, continuous heating 5-10 days, is then dropped to the rate of 5 DEG C/h
Room temperature, there are colourless bulk crystals to be precipitated to get.
Preferably, the HNO3Mass concentration be 50-62%.
A kind of two-dimentional micropore cadmium compound in active site proposed by the present invention answering in ferric ion detection
With.
Compared with prior art, the device have the advantages that being:
A kind of two-dimentional micropore cadmium compound in active site proposed by the present invention, it is proposed by the present invention a kind of with work
Property site two-dimensional channel cadmium compound, there is high thermal stability, duct frame can be stabilized to 320 DEG C, can be 3.0- in pH
It is stabilized in 11.0 water.Metal-organic nano duct polymer has many advantages, such as stability height, large specific surface area, so that
Heavy metal ion is easy to be enriched in high-density on its duct, in addition nano pore material can reduce the overpotential of substrate,
Increase response current, increase measured object and product in the absorption of electrode surface, so to target analytes high sensitivity, response speed
Degree is fast.
The two-dimensional channel and Fe of compound in the present invention3+Ion matches, and the active site in duct can be with Fe3+
Ion interacts, therefore the compound has specificity to the probe of some substances, when detecting target metal ions
It is not influenced by other ions, it 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 cadmium atom in embodiment 1；
Fig. 2 is the two-dimensional cellular structure of 1 cadmium compound of embodiment；
Fig. 3 is the thermogravimetric curve of 1 cadmium compound frame of embodiment；
Fig. 4 is the conductibility of each electrode of cyclic voltammetry (CVS) probe；
Fig. 5 is modified electrode AuNPs/MOF-1/GCE to Fe3+The concentration of ion is 5 × 10-13mol/L-9×10-8mol/
The detection curve of L；
Fig. 6 is modified electrode AuNPs/MOF-1/GCE to Fe3+The concentration of ion is 5 × 10-13mol/L-9×10-8mol/
Good linear relationship is shown in the concentration range of L；
Fig. 7 is selectivity of the modified electrode AuNPs/MOF-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-dimentional micropore cadmium compound in active site:
S1: the 5- nitroisophthalic acid of (4- pyridyl group) pyrimidin ligand of 2,5- bis- of 0.10mmol and 0.10mmol is matched
Cd (the CH of the mixture and 0.10mmol that are obtained after body mixing3COOH)2·2H2O is put into togerther in the reaction kettle of 10ml, is added
2 drop HNO are added dropwise in 2mLDMF solvent and 1mL acetonitrile solution3(mass concentration 62%) and 0.2mL deionized water, measuring its pH is
6.0, 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 75%.
Compound (C61H39Cd2N11O12) elemental analysis (%): calculated value: C, 54.56；H,2.93；N, 11.43. experiment
Value: C, 54.23；H,2.77；N, 11.38. infrared analysis (KBr, cm–1): 3444 (m), 3312 (s), 2982 (m), 2764 (m),
2317(w),1886(m),1773(m),1621(m),1448(m),1253(s),1115(m),1007(w),952(m),873
(s),833(m),759(w),668(w),631(w),558(w),452(w)。
Complex [Cd2(bpyp)3(L-NO2)2]nStructure determination:
After crystal DMF wash clean, selects quality and the suitable crystal of size is placed in Bruker-AXSSMARTCCDX-
On 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 to the non-hydrogen atom and hydrogen atom coordinates of compound, extremely receive by isotropic temperature factor and anisotropic temperature factor refine
It holds back.The parsing and refine of compound are completed with SHELXL-97 program bag.The related crystalline number of compound made from embodiment 1
According to being listed in Table 1 below.
The crystal data of 1 cadmium compound of table
aR1=Σ | | Fo|–|Fc|)/Σ|Fo|；wR2=[Σ w (Fo 2–Fc 2)2/Σw(Fo 2)2]1/2
Complex [Cd2(bpyp)3(L-NO2)2]nStructure description
The two-dimentional micropore cadmium compound [Cd in the active site of an example has been obtained under hydrothermal synthesizing condition2(bpyp)3(L-
NO2)2]n(1).Single crystal diffraction is analysis shows cadmium compound has P21/m space group, and there are two participate in coordination in cadmium compound
Cadmium atom, as shown in fig. 1.Cd1 atom is the mode of seven coordinations, and space geometry is configured as the pentagonal bipyramid of distortion, wherein joining
From four oxygen atoms of coordination from two different L-NO2Ligand, three nitrogen-atoms come from three 2,5- bis- (4- pyridyl group)
The average bond length of pyrimidin ligand, Cd1-O and Cd1-N isWithCd2 atom is also the pentagonal bipyramid of distortion
The average bond length of structure, Cd2-O and Cd2-N isWithIn cadmium compound, the L-NO that protonates completely2Match
The mode and cadmium Atomic coordinate that carboxyl on body takes bidentate to chelate, and 2,5- bis- (4- pyridyl group) pyrimidin ligands are connected to two
Cadmium atom forms the cellular structure of 2D, as shown in Figure 2.It has been observed that there are active group-NO in cadmium compound2, and do not match
- the NO of position2Between there are hydrogen bond actions, compound can be constructed as the pore structure of higher dimension.
Complex [Cd2(bpyp)3(L-NO2)2] n stability
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 duct compound [Cd2(bpyp)3(L-NO2)2]n(1) stability of frame has carried out thermogravimetric analysis to cadmium compound, such as schemes
3.Thermogravimetric curve analysis finds that the frame of cadmium compound can be stabilized to 320 DEG C.In addition, we also studied cadmium compound in water
Stability under different pH value, research find that cadmium compound can be stabilized in the water that pH is 3.0-11.0.
Complex [Cd2(bpyp)3(L-NO2)2]nTo Fe3+Ion electrochemical detection
Two-dimentional micropore cadmium compound with more active sites is due to high thermal stability, big hole area and can be
It is stabilized in the water that pH is 3.0-11.0.Therefore, micropore cadmium compound synergic nano gold is covered on glass-carbon electrode by us
(GCE) surface, Development of Novel Electrochemical Modification electrode A uNPs/MOF-1/GCE.Glass-carbon electrode after modification is to Fe3+The inspection of ion
Survey shows good selectivity, high stability and sensitivity and wide detection range.
The conductibility of each electrode of probe is gone using cyclic voltammetry (CVS).Fig. 4 is the CVs song obtained under Different electrodes
Line (scanning speed 100mVs-1).Curve a is naked GCE.The current peak Ip of AuNPs/MOF-1/GCE electrode is increased, voltage
It is peak-to-peak to reduce away from Ep relative to electrode GCE and MOF-1/GCE.The possible reason is the structure of AuNPs/MOF-1/GCE can
Increase effective surface area.It is formed by nanogold to be evenly distributed in the gap of microporosity, the electricity with microcellular structure
Pole surface can cause the diffusion region of overlapping, thus smoothly be diffused into the multi-cellular structure of cadmium compound, and in AuNPs/
The surface MOF-1/GCE forms electrostatic induction.
In order to preferably be detected, the optimum condition of experiment is had studied, research finds optimum optimizing condition are as follows: deposition gold
Number of segment is 8 sections, and electrolyte is Klorvess Liquid；Electrolyte concentration is the potassium chloride of 0.05M, and optimal quiescent time is 80 seconds.
For SWASV under conditions of optimum optimization, modified electrode AuNPs/MOF-1/GCE is to Fe3+The concentration of ion 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 Fe3+
The minimum detection limit of ion is 1 × 10-13mol/l(R2=0.99912), this is far below U.S. environment administration (EPA) and world health
The limit concentration for organizing (WHO) to formulate.Especially modified electrode AuNPs/MOF-1/GCE is to Fe3+The wide line that ion is shown
Property range and low detection limit, this has greater advantage compared with mercury electrode and its detection method.To Fe3+The hypersensitivity of ion and
Low detection limit should be attributed to cadmium compound and nanogold increases and exists in electrode surface specific surface area and cadmium compound structure
Multiple active sites.
Modified electrode AuNPs/MOF-1/GCE is to Fe3+The concentration of ion is 5 × 10-13mol/l to 9×10-8mol/l:
In the range of show good linear relationship and low detection limit (SWASV parameter: frequency 40Hz, amplitude 20mV, voltage increment
4mV)
Modified electrode AuNPs/MOF-1/GCE is to Fe3+Ion has good selectivity, and modified electrode is to other metal ions
(Cu2+,Pb2+,Cd2+,Zn2+,Hg2+,As3+, and Co2+) detection electrochemical signals intensity it is very weak.The result shows modifications
Electrode A uNPs/MOF-1/GCE is to Fe3+Ion has selectivity well, sees Fig. 7.
We, which combine the two-dimentional micropore cadmium compound in active site with nanogold, carrys out modified glassy carbon electrode, modification
Glass-carbon electrode afterwards is to Fe3+The detected representation of ion goes out selectivity, high stability and sensitivity and wide detection well
Range.
Embodiment 2
A kind of preparation method of the two-dimentional micropore cadmium compound in active site:
S1: the 5- nitroisophthalic acid of (4- pyridyl group) pyrimidin ligand of 2,5- bis- of 0.10mmol and 0.10mmol is matched
Cd (the CH of the mixture and 0.10mmol that are obtained after body mixing3COOH)2·2H2O is put into togerther in the reaction kettle of 10ml, is added
2 drop HNO are added dropwise in 2mLDMF solvent and 1mL acetonitrile solution3(mass concentration 50%) and 0.2mL 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 7 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 73%.
Embodiment 3
A kind of preparation method of the two-dimentional micropore cadmium compound in active site:
S1: the 5- nitroisophthalic acid of (4- pyridyl group) pyrimidin ligand of 2,5- bis- of 0.10mmol and 0.10mmol is matched
Cd (the CH of the mixture and 0.10mmol that are obtained after body mixing3COOH)2·2H2O is put into togerther in the reaction kettle of 10ml, is added
2 drop HNO are added dropwise in 2mL DMF solvent and 1mL acetonitrile solution3(mass concentration 55%) and 0.2mL deionized water, measures its pH
It is 6.5, solution is transparency liquid at this time；
S2: being heated to seal to 120 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 72%.
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 (5)
1. a kind of two-dimentional micropore cadmium compound in active site, which is characterized in that the coordination mode of the cadmium compound is such as
Under:
The chemical formula of the cadmium compound is C61H39Cd2N11O12, monoclinic system, space group P21/m, cell parameter isα=γ=90 °, β=104.75 °,Z=2.
2. a kind of two-dimentional micropore cadmium compound in active site according to claim 1, which is characterized in that the cadmium
Compound has two-dimensional cellular structure.
3. a kind of preparation method of the two-dimentional micropore cadmium compound in active site according to claim 1, feature
It is, method and step is as follows:
S1: the 5- nitroisophthalic acid ligand of (4- pyridyl group) pyrimidin ligand of 2,5- bis- of 0.10mmol and 0.10mmol is mixed
Cd (the CH of the mixture and 0.10mmol that are obtained after conjunction3COOH)2·2H2O is put into togerther in the reaction kettle of 10mL, and 2mL is added
2 drop HNO are added dropwise in DMF solvent and 1mL acetonitrile solution3With 0.2mL deionized water, measuring its pH is 5.5-6.5, and solution is at this time
Transparency liquid；
S2: vial is heated to seal to 100-120 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.
4. a kind of preparation method of the two-dimentional micropore cadmium compound in active site according to claim 3, feature
It is, the HNO3Mass concentration be 50-62%.
5. a kind of two-dimentional micropore cadmium compound in active site according to claim 1, which is characterized in that the cadmium
Application of the compound in iron ion detection.
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