CN112415066A - Cobalt-based complex for detecting heavy metal ions and application of cobalt-based complex in electroanalytical chemical sensor - Google Patents
Cobalt-based complex for detecting heavy metal ions and application of cobalt-based complex in electroanalytical chemical sensor Download PDFInfo
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Abstract
A cobalt-based complex for detecting heavy metal ions and its use in an electroanalytical chemical sensor, the cobalt-based complex having the formula: [ Co ] A2(4‑dptb)2(1,3‑BDC)2]·2H2O, wherein 4-dppb is N, N' -bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid; 1,3-BDC is isophthalic acid; the cobalt-based complex can be used for rapidly and sensitively detecting heavy metal ions Fe in room temperature environment3+And Cr2O7 2‑And has extremely low detection limit, and can be applied to an electroanalytical chemical sensor. The synthesized complex has low solubility in water and can be recycled. The complex can be used as an electrochemical sensing material and can be applied to detecting Fe in an aqueous solution3+/Cr2O7 2‑Ions. Short response time and low detection limit, and can be applied to practiceAnd (4) detecting heavy metal ions in the inter-life.
Description
Technical Field
The invention belongs to the field of electrochemical analysis materials, relates to a cobalt complex for detecting heavy metal ions and application thereof in an electroanalytical chemical sensor, and particularly relates to synthesis of a multifunctional cobalt complex constructed based on a nitrogen-containing ligand and a carboxylic acid ligand for detecting heavy metal ions and application thereof in the electroanalytical chemical sensor.
Background
The rapid development of the industry has led to an increase in the content of heavy metal ions, such as Fe, in water3+，Cr2O7 2-And the like. Fe3+、Cr6+Heavy metal ions have high toxicity, biodegradability and in vivo accumulation. Once entering the human body, the health of the human body is endangered. To avoid the harm of heavy metal ions to the environment and human beings, Fe was developed3+、Cr6+The heavy metal detection technology is very significant. Therefore, how to selectively, rapidly and sensitively detect these contaminants can be a critical issue.
At present, the detection of trace heavy metal ions comprises an inductive ion coupling plasma mass spectrometry method, an inductive coupling plasma optical emission spectrum, an atomic absorption/emission spectrum, an X-ray fluorescence spectrometry method and an electrochemical method. The electrochemical method has the characteristics of portable instrument, simplicity in operation, high response speed and high sensitivity, has great potential in real-time and on-site detection, and draws wide attention of researchers.
Complexes (CPs) are a novel material with a periodic network structure and are composed of metal nodes (metal ions or clusters) and organic ligands. The microporous structure is rich and adjustable, so that the microporous structure has large specific surface area and open metal active sites. The complex attracts a great deal of attention and becomes a hot spot of material research in the 21 st century. Meanwhile, the complex material has wide application prospects in various applications, such as gas storage and separation, energy storage, chemical sensing, drug delivery, catalysis and the like. The synthesis of a complex which is selective, rapid and sensitive and can detect heavy metal ions is of great significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cobalt-based complex for detecting heavy metal ions and application thereof in an electroanalytical chemical sensor, wherein the complex can be used for quickly and sensitively detecting the heavy metal ions Fe in a room temperature environment3 +，Cr2O7 2-And has an extremely low detection limit.
The technical solution of the invention is as follows:
a cobalt-based complex constructed by a nitrogen-containing ligand and a carboxylic acid ligand for detecting heavy metal ions has the following molecular formula:
[Co2(4-dptb)2(1,3-BDC)2]·2H2O
wherein 4-dptb is N, N' -bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid; 1,3-BDC is isophthalic acid; the cobalt-based complex can be used for rapidly and sensitively detecting heavy metal ions Fe in room temperature environment3+And Cr2O7 2-And has an extremely low detection limit.
Further, the complex measurement finds that the complex is Fe3+Detection limit is 5.84 μ M for Cr2O7 2-The ion detection limit was 1.84. mu.M.
Further, the specific synthetic steps of the cobalt-based complex are as follows:
mixing Co (NO)3)2·6H2Placing O, N, N' -bis (4-pyridine carboxamide) -3, 4-thiophene dicarboxylic acid and isophthalic acid into an autoclave with a polytetrafluoroethylene lining according to a molar ratio of 0.1649:0.048:0.1986, adding deionized water and 0.1mol/L NaOH solution according to a volume ratio of 3:2, heating to 120 ℃, keeping the temperature for 4 days, cooling to room temperature to obtain pink blocky crystals, washing and drying to obtain the cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand.
Further, the temperature rise rate was 10 ℃/h.
An application of a cobalt complex constructed by a nitrogen-containing ligand and a carboxylic acid ligand for detecting heavy metal ions in an electroanalytical chemical sensor.
The application of a cobalt complex constructed by a nitrogen-containing ligand and a carboxylic acid ligand for detecting heavy metal ions in an electroanalytical chemical sensor is characterized in that Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a carbon paste electrode is used as a working electrode as a three-electrode of the sensor, and the cobalt complex is characterized in that: the preparation steps of the carbon paste electrode are as follows:
0.01g of a nitrogen-containing ligand, a cobalt-based complex constituted by a carboxylic acid ligand and 0.10g of graphite powder were mixed, ground in a mortar for 40 minutes to form a uniform mixture, 5. mu.L of paraffin oil was added, and stirred with a copper rod to form a paste. And putting the paste into a glass tube with the diameter of 3mm, compacting by using a copper rod, and fixing the copper rod in a quartz tube to obtain the cobalt-based complex carbon paste electrode.
The application of cobalt complex based on nitrogen-containing ligand and carboxylic acid ligand in electric analysis chemical sensor for detecting heavy metal ion adopts three-electrode method, and its voltage is 700 mV-100 mV, and 0.5M Na2SO4And 0.1M H2SO4In a buffer solution, cyclic voltammetry is carried out on a solution to be detected at different sweep rates of 60mV/s, and the volume ratio of the buffer solution to the solution to be detected is 1: 1. Average peak potential E based on cobalt complex constructed by nitrogen-containing ligand and carboxylic acid ligand1/2At a rate of 300mV (sweep rate of 60mV/s) for (Epa + Epc)/2. The peak potential is gradually changed along with the increase of the sweeping speed; the cathodic peak shifts to the negative electrode and the corresponding anodic peak shifts to the positive electrode.
Further, the optimum voltage was determined to be 250 mV.
For Fe3+，Cr2O7 2-Redox assay of (2): at 0.5M Na2SO4+0.1M H2SO4To the buffer solution, 0mM, 2mM, 4mM, 6mM, and 8mM Fe were added3+/Cr2O7 2-Ionic solution, said buffer solution and Fe3+/Cr2O7 2-The volume ratio of the ionic solution was 1: 1. With the addition of the ions,the reduction peak current value of the cobalt-based complex carbon paste electrode is increased, and the corresponding oxidation peak current is reduced. Illustrating the cobalt-based complex pair Fe3+And Cr2O7 2-Has good electrocatalytic activity.
Blank experiment determination: 0.10g of graphite powder was ground in a mortar for 40 minutes, 5. mu.L of paraffin oil was added, and stirred with a copper rod to form a paste. Placing the paste into a glass tube with a diameter of 3mm, compacting with a copper rod, fixing the copper rod in a quartz tube to obtain a graphite electrode, using the graphite electrode as a blank electrode, adding different amounts of metal ions, and finding Fe3+，Cr2O7 2-The redox effect of (a) is not significant, indicating that the cobalt-based complex which is mainly constructed by the nitrogen-containing ligand and the carboxylic acid ligand plays a role.
Determination of optimum voltage: with Fe3+For example, the optimum voltage is determined by the time-current curve (I-t). To the solution was added 0.1M 100. mu.L Fe every minute3+. The current response was found to vary maximally at 0.25V, indicating that 0.25V is the optimum voltage for the i-t measurement.
Time-current curves (i-t) and selectivity measurements: at 0.5M Na2SO4+0.1M H2SO4To the solution, Fe was added every minute3+/Cr2O7 2-The ions are found to continuously increase along with the continuous increase of the ion concentration, and the complex proves to be Fe3 +/Cr2O7 2-Has good current response effect. At the same time, the same concentration of Na is added+、Al3+、Cd2+、Co2+、Bi3+And Zn2+The cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand does not have any current response basically when finding the interfering ions, which indicates that the cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand can still selectively detect Fe in the presence of the interfering ions3+/Cr2O7 2-Ions.
Detection limit determination: at 0.5M Na2SO4+0.1M H2SO4Every other in the solutionMinute, adding Fe3+/Cr2O7 2-Ion, current constantly changes. It was subjected to a calibration curve showing Fe between 10. mu.M and 100. mu.M3+/Cr2O7 2-The linear response relation and the correlation coefficient are all above 0.99. Meanwhile, the complex measurement finds that the Fe is para3+Detection limit is 5.84 μ M for Cr2O7 2-The ion detection limit was 1.84. mu.M. Meanwhile, the compound has response time lower than 5s, can quickly respond and is beneficial to practical application.
The invention has the beneficial effects that:
(1) the metal cobalt complex has a one-dimensional chain structure, has rich and adjustable pore structures to promote the diffusion of heavy metal ions in the Complex (CPs), increases the contact area and the mutual exchange of a host structure and an object molecule, and is beneficial to the pre-enrichment of the heavy metal ions; and the organic ligand of the metal center can be used for the specific recognition of heavy metal ions. The synthesis method is simple and the test conditions are convenient.
(2) The synthesized complex has low solubility in water and can be recycled. Meanwhile, the complex can be used as an electrochemical sensing material for Fe3+/Cr2O7 2-The current intensity has an exponential relation with the solution concentration, and can be applied to the detection of Fe in the aqueous solution3 +/Cr2O7 2-Ions. Short response time, low detection limit, and detection of complex to find Fe3+Detection limit is 5.84 μ M for Cr2O7 2-The ion detection limit is 1.84 mu M, and the method can be applied to detection of heavy metal ions in actual life.
Drawings
FIG. 1 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2A powder X-ray diffraction pattern of O;
FIG. 2 is [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2An infrared spectrum of O;
FIG. 3 is [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2A thermogram of O;
FIG. 4 is [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2A coordination environment diagram of O;
FIG. 5 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2A one-dimensional chain structure diagram of O;
FIG. 6 is a cyclic voltammogram of a [ Co2(4-dptb)2(1,3-BDC)2 ]. 2H2O modified electrode of the invention in a 0.5M Na2SO4+0.1M H2SO4 solution at different sweep rates (from inside to outside: 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450, 500 mV/s);
FIG. 7 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2An optimal voltage profile of O;
FIG. 8 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Modified electrode of O with Cr2O7 2-The concentration of (A) is increased to 0.5M Na2SO4+0.1M H2SO4Cyclic voltammogram in solution (sweep rate: 60 mV/s);
FIG. 9 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Modified electrode of O with Fe3+The concentration of (A) is increased to 0.5M Na2SO4+0.1M H2SO4Cyclic voltammogram in solution (sweep rate: 60 mV/s);
FIG. 10 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Fe of O3+Time-current response graph of;
FIG. 11 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Cr of O2O7 2-Time-current response graph of;
FIG. 12 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2P of O to Fe3+Selective detection of map (2);
FIG. 13 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2p-Cr of O2O7 2-Selective detection of map (2);
FIG. 14 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Fe of O3+A detection limit measurement map of (1);
FIG. 15 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Fe of O3+Time-current linear graph of (a);
FIG. 16 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Cr of O2O7 2-A detection limit measurement map of (1);
FIG. 17 shows [ Co ] of the present invention2(4-dptb)2(1,3-BDC)2]·2H2Cr of O2O7 2-Time-current linear graph of (a);
FIG. 18 shows the present invention without [ Co ]2(4-dptb)2(1,3-BDC)2]·2H2Blank electrode of O with Fe3+The concentration of (A) is increased to 0.5M Na2SO4+0.1M H2SO4Cyclic voltammogram in solution (sweep rate: 60 mV/s);
FIG. 19 shows the present invention without [ Co ]2(4-dptb)2(1,3-BDC)2]·2H2Blank electrode of O with Cr2O7 2-The concentration of (A) is increased to 0.5M Na2SO4+0.1M H2SO4Cyclic voltammogram in solution (sweep rate: 60 mV/s).
Detailed Description
EXAMPLE 1 Synthesis of [ Co2(4-dptb)2(1,3-BDC)2]·2H2O
Mixing Co (NO)3)2·6H20.048g of O, 0.017g of N, N' -bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid and 0.033g of isophthalic acid are placed in a 23mL autoclave lined with polytetrafluoroethylene, 6mL of deionized water and 4mL of 0.1mol/L NaOH solution are added, then the temperature is raised to 120 ℃ at the heating rate of 10 ℃/h, and the temperature is maintained for 4 daysThen slowly cooling to room temperature to obtain pink blocky crystals, washing and airing to obtain a cobalt-based complex (CP1) constructed by the nitrogen-containing ligand and the carboxylic acid ligand, wherein the molecular formula is as follows: [ Co ] A2(4-dptb)2(1,3-BDC)2]·2H2O; wherein 4-dptb is N, N' -bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid; 1,3-BDC is isophthalic acid. A PXRD diffraction pattern of the cobalt-based complex (CP1) is shown in figure 1, and a coordination environment diagram and a one-dimensional chain structure of the cobalt-based complex are shown in figures 4 and 5.
Characterization of cobalt-based Complex (CP1) based on example 1 of the invention
(1) Powder diffraction characterization phase purity
The complete powder diffraction data were collected on a RigakuUltima IV powder X-ray diffractometer operating at 40mA and 40 kV. Copper target X-rays were used. Scanning was fixed and the receiving slit was 0.1mm wide. The density data collection scan ranges from 5 ° to 50 °. Data were fitted using the Cerius2 program and single crystal structure powder diffraction spectrum simulated transformation using Mercury 1.4.1.
As shown in FIG. 1, the experimental value of the powder X-ray diffraction spectrum of the complex is consistent with the fitted PXRD spectrum, which shows that the phase purity of the complex is good.
(2) Characterization of phase Components by Infrared Spectroscopy
Testing the infrared spectrum of the complex material by using an FT-IR spectrometer, wherein the scanning range is 400-4000 cm-1. The carboxyl absorption peak in the 1,3-BDC ligand as shown in FIG. 2 appears at 1598cm-1～1426cm-1The v (C-N) bond stretching movement characteristic peak in the 4-dptb ligand is 1410cm-1～1080cm-1The complex is shown to be synthesized from the corresponding raw materials.
(3) Thermogravimetric characterization of material stability
The thermal stability is completed by using a PE-Pyris Diamond S-II thermal analyzer, the heating rate is 10 ℃/min, and the temperature range is 30-800 ℃. FIG. 3 shows that the complex synthesized by the invention keeps stable structure at 330 ℃ and the decomposition temperature ranges from 330 ℃ to 450 ℃.
Secondly, determination of crystal structure
Selecting single crystal with proper size by microscope, chamberDiffraction data were collected at room temperature using a Bruker SMART APEX II diffractometer (graphite monochromator, Mo-Ka). Scanning mode
The diffraction data were corrected for absorption using the SADABS program. Data reduction and structure resolution were done using SAINT and Olex-2 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. Some parameters of the collection of crystallographic diffraction point data and the structure refinement are shown in table 1:
TABLE 1
Electrochemical sensing test based on cobalt complex and constructed by nitrogen-containing ligand and carboxylic acid ligand
For synthetic [ Co2(4-dptb)2(1,3-BDC)2]·2H2Cyclic voltammetry and redox measurement of O (cobalt-based complex CP1) show that cobalt-based complex (CP1) is relative to Fe3+/Cr2O7 2-The ions have sensing function and can be applied to electrochemical sensing materials.
(1) The cyclic voltammetry experiment of the cobalt-based complex (CP1) comprises the following specific steps:
the modified carbon paste electrode (1-CPE) was prepared as follows: mixing 0.10g of graphite powder and 10mg of complex, and grinding in an agate mortar for 40min to obtain a uniform mixture; to the mixture was added 5. mu.L of paraffin oil, and the mixture was stirred with a copper rod to be uniform, and then the carbon paste was packed in a glass tube having an inner diameter of 3mm and a packing length of 2 cm. Lightly compacted from the back with a copper rod and the surface wiped flat with a weighing paper.
(2) Blank experimental group: 0.10g of graphite powder was ground in a mortar for 40 minutes, 5. mu.L of paraffin oil was added, and stirred with a copper rod to form a paste. The paste was placed in a glass tube of 3mm diameter, compacted with a copper rod, and the copper rod was fixed in a quartz tube to obtain a graphite electrode as a working electrode for the blank experimental group.
As shown in FIG. 6, the carbon paste electrode was modified at 0.5M Na2SO4+0.1M H2SO4In solution, measurements were made at different sweep rates: 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450, 500mV/s cyclic voltammogram. Determining the Fe of the complex pair at the concentration of 0-8 mM and under the condition of 60mV/s3+/Cr2O7 2-Cyclic voltammogram of ions (fig. 8, fig. 9). In FIGS. 16 and 17, under the same conditions, the graphite electrode was used as the working electrode of the blank experimental group for Fe3+/Cr2O7 2-When ions are subjected to cyclic voltammetry, the current response change is found to be small, and the cobalt-based complex (CP1) plays a main role in ion sensing.
(3) Cobalt-based complex (CP1) vs. Fe3+/Cr2O7 2-Time-current curve of ion
With Fe3+For example, the effect of different voltages on the time-current curve was determined. At 0.5M Na2SO4+0.1M H2SO4To the solution, Fe was added every minute3+/Cr2O7 2-Ions. As shown in fig. 7, at 0.25V, the current response is graded with increasing concentration and the degree of change is greatest with increasing time. Therefore, under the optimum voltage condition, for Fe3+/Cr2O7 2-The ions were subjected to time-current curve measurements. FIG. 10 continuous addition of Fe3+FIG. 11 continuous addition of Cr2O7 2-Time-current profile of; as shown in FIGS. 10 and 11, the complex pair Fe3+/Cr2O7 2-The continuous addition of ions shows a linear relationship.
(4) Anti-interference capability of cobalt-based complex (CP1)
Into solutionFirst, 0.1M 100. mu.L of Fe was added3+/Cr2O7 2-Ions are added, then Fe with the same concentration is added2+、Na+、Al3+、Cd2+、Co2+、Bi3+、Zn2+Interfering ions, FIG. 12 is the compound pair Fe with continuous addition of other interfering ions3+FIG. 13 is a time-current graph of compound pairs Cr with continuous addition of other anti-interference ions2O7 2-The time-current curve of (2) shows that the complex has no current response to it, which indicates that the complex can still selectively detect Fe in the presence of interfering ions3+/Cr2O7 2-Ions.
(6) Determination of detection Limit of cobalt-based Complex (CP1)
Adding metal ions with different concentrations, measuring the response degree of the current to the concentration change, and calculating the detection limit. As shown in FIGS. 14, 15, 16 and 17, in FIG. 14, Fe was continuously added at different concentrations3+Time-current diagram of time, FIG. 15 continuous addition of different concentrations of Fe3+Time-current-time linear graph, FIG. 16 continuous addition of Cr at different concentrations2O7 2-Time-current diagram of time, FIG. 17 continuous addition of Cr of different concentrations2O7 2-A current-time linear graph of time; complex pair Fe3+Detection limit is 5.84 μ M for Cr2O7 2-The ion detection limit is 1.84 mu M, the response time is 1s and 5s respectively, and the response is rapid. At the same time, the current intensity of the cobalt-based complex (CP1) is equal to that of Fe3+Cr2O7 2-The ion content is linear. Thus Fe at different concentrations depending on the complex3+The current intensity in the/Cr 2O 72-solution can be used to estimate Fe in the water solution3+/Cr2O7 2-As Fe3+And Cr2O7 2-The detection material of (1).
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A cobalt-based complex constructed by a nitrogen-containing ligand and a carboxylic acid ligand for detecting heavy metal ions is characterized in that:
the cobalt-based complex has the following molecular formula:
[Co2(4-dptb)2(1,3-BDC)2]·2H2O；
wherein 4-dptb is N, N' -bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid; 1,3-BDC is isophthalic acid; the cobalt-based complex can be used for rapidly and sensitively detecting heavy metal ions Fe in room temperature environment3+And Cr2O7 2-And has an extremely low detection limit.
2. The cobalt-based complex structured by nitrogen-containing ligand and carboxylic acid ligand for detecting heavy metal ions according to claim 1, wherein: the complex measurement finds that the Fe is p-Fe3+Detection limit is 5.84 μ M for Cr2O7 2-The ion detection limit was 1.84. mu.M.
3. The cobalt-based complex structured by nitrogen-containing ligand and carboxylic acid ligand for detecting heavy metal ions according to claim 1, wherein:
the specific synthetic steps of the cobalt-based complex are as follows:
mixing Co (NO)3)2·6H2Placing O, N, N' -bis (4-pyridine carboxamide) -3, 4-thiophene dicarboxylic acid and isophthalic acid into an autoclave with a polytetrafluoroethylene lining according to a molar ratio of 0.1649:0.048:0.1986, adding deionized water and 0.1mol/L NaOH solution according to a volume ratio of 3:2, heating to 120 ℃, keeping the temperature for 4 days, cooling to room temperature to obtain pink blocky crystals, washing and drying to obtain the cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand.
4. The cobalt-based complex structured by nitrogen-containing ligand and carboxylic acid ligand for detecting heavy metal ions according to claim 3, wherein: the temperature rise rate was 10 ℃/h.
5. Use of the cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand for detecting heavy metal ions according to claim 1 in an electroanalytical chemical sensor.
6. The application of the cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand for detecting the heavy metal ions in the electroanalytical chemical sensor, which is disclosed by claim 5, is characterized in that Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a carbon paste electrode is used as a working electrode and is used as a three-electrode of the sensor, wherein the three-electrode is characterized in that:
the preparation steps of the carbon paste electrode are as follows:
mixing 0.01g of nitrogen-containing ligand, cobalt complex constructed by carboxylic acid ligand and 0.10g of graphite powder, grinding in a mortar for 40 minutes to form a uniform mixture, adding 5 mu L of paraffin oil, and stirring with a copper rod to form paste; and putting the paste into a glass tube with the diameter of 3mm, compacting by using a copper rod, and fixing the copper rod in a quartz tube to obtain the cobalt-based complex carbon paste electrode.
7. The use of the cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand for detecting heavy metal ions according to claim 5 in an electroanalytical chemical sensor, wherein:
by adopting a three-electrode method, the voltage is between 700mV and-100 mV and the voltage is 0.5M Na2SO4And 0.1M H2SO4In a buffer solution, cyclic voltammetry is carried out on a solution to be detected at different sweep rates of 60mV/s, and the volume ratio of the buffer solution to the solution to be detected is 1: 1.
8. The use of the cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand for detecting heavy metal ions according to claim 7 in an electroanalytical chemical sensor, wherein: the measurement voltage was 250 mV.
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