CN112415066B - 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 ] A 2 (4‑dptb) 2 (1,3‑BDC) 2 ]·2H 2 O, 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 environment 3+ And Cr 2 O 7 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 solution 3+ /Cr 2 O 7 2‑ Ions. The response time is short, the detection limit is low, and the method can be applied to detection of heavy metal ions in actual 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 heavy metal ions in waterIncrease in content, e.g. Fe 3+ ，Cr 2 O 7 2- And the like. Fe 3+ 、Cr 6+ 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 developed 3+ 、Cr 6+ 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.
The Complexes (CPs) are novel materials with periodic network structures, and consist 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 provide a cobalt-based complex for detecting heavy metal ions and application thereof in an electroanalytical chemical sensor, wherein the complex can be used for rapidly and sensitively detecting heavy metal ions Fe in a room-temperature environment 3 + ，Cr 2 O 7 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 a molecular formula as follows:
[Co 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 O
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 environment 3+ And Cr 2 O 7 2- And has an extremely low detection limit.
Further, the complex measurement finds that the complex is Fe 3+ Detection limit is 5.84 μ M for Cr 2 O 7 2- The ion detection limit was 1.84. Mu.M.
Further, the specific synthesis steps of the cobalt-based complex are as follows:
mixing Co (NO) 3 ) 2 ·6H 2 Placing O, N, N' -bis (4-pyridine carboxamide) -3, 4-thiophene dicarboxylic acid and isophthalic acid in an autoclave with a polytetrafluoroethylene lining according to a molar ratio of 0.1649 to 0.048.
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 homogeneous mixture, 5. Mu.L of paraffin oil were 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.
An application of cobalt complex based on nitrogen-containing ligand and carboxylic acid ligand in electrochemical sensor for detecting heavy metal ions is prepared through three-electrode method at 700-100 mV voltage and 0.5M Na 2 SO 4 And 0.1M H 2 SO 4 In a buffer solution, cyclic voltammetry is carried out on a solution to be tested at different sweep rates of 60mV/s, and the volume ratio of the buffer solution to the solution to be tested is 1. Average peak potential E based on cobalt complex constructed by nitrogen-containing ligand and carboxylic acid ligand 1/2 = 300mV (sweep rate of 60 mV/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 250mV.
For Fe 3+ ，Cr 2 O 7 2- Redox assay of (2): at 0.5M Na 2 SO 4 +0.1M H 2 SO 4 To the buffer solution were added 0mM, 2mM, 4mM, 6mM, and 8mM Fe, respectively 3+ /Cr 2 O 7 2- Ionic solution, said buffer solution and Fe 3+ /Cr 2 O 7 2- The volume ratio of the ionic solution is 1. With the addition of 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 Fe 3+ And Cr 2 O 7 2- Has good electrocatalytic activity.
Blank test 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. Putting 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 Fe 3+ ，Cr 2 O 7 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 Fe 3+ For example, the optimum voltage is determined by the time-current curve (I-t). To the solution was added 0.1M 100. Mu.L of Fe every minute 3+ . The largest change in current response was found 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 Na 2 SO 4 +0.1M H 2 SO 4 Adding Fe into the solution every other minute 3+ /Cr 2 O 7 2- The ions are found to continuously increase along with the continuous increase of the ion concentration, and the complex proves to be Fe 3 + /Cr 2 O 7 2- Has good current response effect. At the same time, the same concentration of Na is added + 、Al 3+ 、Cd 2+ 、Co 2+ 、Bi 3+ And Zn 2+ The cobalt-based complex constructed by the nitrogen-containing ligand and the carboxylic acid ligand basically has no current response to 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 ions 3+ /Cr 2 O 7 2- Ions.
Detection limit determination: at 0.5M Na 2 SO 4 +0.1M H 2 SO 4 To the solution, fe was added every minute 3+ /Cr 2 O 7 2- Ion, current constantly changes. It was subjected to a calibration curve showing Fe between 10. Mu.M and 100. Mu.M 3+ /Cr 2 O 7 2- The linear response relation, the correlation coefficient is above 0.99. Meanwhile, the complex measurement finds that the complex is Fe 3+ Detection limit is 5.84 μ M for Cr 2 O 7 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 abundant 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 favorable for the pre-enrichment of the heavy metal ions; and the organic ligand of the metal center can be used for 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 Fe 3+ /Cr 2 O 7 2- The current intensity has an exponential relation with the solution concentration, and can be applied to the detection of Fe in the aqueous solution 3 + /Cr 2 O 7 2- Ions. Short response time, low detection limit, and detection of complex to find Fe 3+ Detection limit is 5.84 μ M for Cr 2 O 7 2- The ion detection limit is 1.84 mu M, and the method can be applied to the detection of heavy metal ions in actual life.
Drawings
FIG. 1 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 A powder X-ray diffraction pattern of O;
FIG. 2 is [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 An infrared spectrum of O;
FIG. 3 is [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 A thermogram of O;
FIG. 4 is [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 A coordination environment diagram of O;
FIG. 5 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 A one-dimensional chain structure diagram of O;
FIG. 6 is a cyclic voltammogram of a modified electrode of [ Co2 (4-dptb) 2 (1, 3-BDC) 2 ]. 2H2O of the invention in a 0.5M solution of Na2SO4+0.1M solution of H2SO4 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 invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 O optimum voltage plot;
FIG. 8 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Modified electrode of O with Cr 2 O 7 2- The concentration of (A) is increased to 0.5M Na 2 SO 4 +0.1M H 2 SO 4 Cyclic voltammogram in solution (sweep rate: 60 mV/s);
FIG. 9 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Modified electrode of O with Fe 3+ The concentration of (A) is increased to 0.5M Na 2 SO 4 +0.1M H 2 SO 4 Cyclic voltammogram in solution (sweep rate: 60 mV/s);
FIG. 10 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Fe of O 3+ Time-current response graph of;
FIG. 11 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Cr of O 2 O 7 2- Time-current response graph of;
FIG. 12 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 P of O to Fe 3+ Selective detection maps of;
FIG. 13 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 p-Cr of O 2 O 7 2- Selective detection of map (2);
FIG. 14 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Fe of O 3+ A detection limit measurement map of (1);
FIG. 15 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Fe of O 3+ Time-current linear graph of (a);
FIG. 16 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Cr of O 2 O 7 2- A detection limit measurement map of (1);
FIG. 17 shows [ Co ] of the present invention 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Cr of O 2 O 7 2- Time-current linear graph of (a);
FIG. 18 shows the present invention without [ Co ] 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Blank electrode of O with Fe 3+ The concentration of (A) is increased to 0.5M Na 2 SO 4 +0.1M H 2 SO 4 Cyclic voltammogram in solution (sweep rate: 60 mV/s);
FIG. 19 shows the present invention without [ Co ] 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 Blank electrode of O with Cr 2 O 7 2- In the presence of 0.5M Na 2 SO 4 +0.1M H 2 SO 4 Cyclic voltammogram in solution (sweep rate: 60 mV/s).
Detailed Description
EXAMPLE 1 Synthesis of [ Co 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 O
Mixing Co (NO) 3 ) 2 ·6H 2 Placing 0.017g of O0.048g and 0.033g of N, N' -bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid and 0.033g of isophthalic acid in a 23mL autoclave lined with polytetrafluoroethylene, adding 6mL of deionized water and 4mL of 0.1mol/L NaOH solution, heating to 120 ℃ at the heating rate of 10 ℃/h, keeping the temperature for 4 days, then slowly cooling to room temperature to obtain pink blocky crystals, washing and airing to obtain a cobalt-based complex (CP 1) constructed by a nitrogen-containing ligand and a carboxylic acid ligand, wherein the molecular formula of the cobalt-based complex is as follows: [ Co ] A 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 O; wherein 4-dptb is N, N' -bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid; 1,3-BDC is isophthalic acid. The PXRD diffraction pattern of the cobalt-based complex (CP 1) is shown in figure 1, and the coordination environment pattern and the one-dimensional chain structure of the cobalt-based complex are shown in figures 4 and 5.
1. Characterization of cobalt-based Complex (CP 1) 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 40kV. 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 values of the powder X-ray diffraction spectrum of the complex are 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
The FT-IR spectrometer is used for testing the infrared spectrum of the complex material, and 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 -1 The v (C-N) bond stretching movement characteristic peak in the 4-dptb ligand is 1410cm -1 ～1080cm -1 It shows that the complex is 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 ℃.
2. Determination of Crystal Structure
A single crystal of an appropriate size was selected by a microscope, and diffraction data was collected at room temperature by 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 (3) 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
3. Cobalt complex-based electrochemical sensing test constructed by nitrogen-containing ligand and carboxylic acid ligand
For synthetic [ Co 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 The cyclic voltammetry and redox measurement of O (cobalt-based complex CP 1) shows that the cobalt-based complex CP1 is used for Fe 3+ /Cr 2 O 7 2- The ions have sensing function and can be applied to electrochemical sensing materials.
(1) The cyclic voltammetry experiment of the cobalt-based complex (CP 1) 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 stirred with a copper rod, and then the carbon paste was packed in a glass tube having an inner diameter of 3mm and a packing length of 2cm. 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. 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 a graphite electrode serving as a blank experiment group working electrode.
As shown in FIG. 6, the carbon paste electrode was modified at 0.5M Na 2 SO 4 +0.1M H 2 SO 4 In 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. Determination of complex-pair Fe at a concentration of 0-8 mM at 60mV/s 3+ /Cr 2 O 7 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 Fe 3+ /Cr 2 O 7 2- The cyclic voltammetry measurement of the ions shows that the current response change is small, which indicates that the cobalt-based complex (CP 1) plays a main role in ion sensing.
(3) Cobalt-based complex (CP 1) to Fe 3+ /Cr 2 O 7 2- Time-current curve of ion
With Fe 3+ For example, the effect of different voltages on the time-current curve was determined. At 0.5M Na 2 SO 4 +0.1M H 2 SO 4 Adding Fe into the solution every other minute 3+ /Cr 2 O 7 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 optimum voltage conditions, for Fe 3+ /Cr 2 O 7 2- The ions were subjected to time-current curve measurement. FIG. 10 continuous addition of Fe 3+ Time-current graph of (1), FIG. 11 continuous addition of Cr 2 O 7 2- Time-current profile of; as shown in FIGS. 10 and 11, the complex pair Fe 3+ /Cr 2 O 7 2- The continuous addition of ions shows a linear relationship.
(4) Anti-interference capability of cobalt-based complex (CP 1)
To the solution was added 0.1M 100. Mu.L of Fe 3+ /Cr 2 O 7 2- Ions, then adding Fe of the same concentration 2+ 、Na + 、Al 3+ 、Cd 2+ 、Co 2+ 、Bi 3+ 、Zn 2+ Interfering ions, FIG. 12 is the compound pair Fe with continuous addition of other interfering ions 3+ FIG. 13 is a time-current graph of compound pairs Cr with continuous addition of other anti-interference ions 2 O 7 2- The time-current curve of (A) is shown in FIGS. 12 and 13, and it can be seen that the complex has substantially no current response to it, indicating that the complex is in the presence of interfering ionsIn the presence of Fe, the selective detection of Fe is still possible 3+ /Cr 2 O 7 2- Ions.
(6) Determination of detection limit of cobalt-based complex (CP 1)
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, FIG. 14 continuously added Fe of different concentrations 3+ Time-current diagram of time, FIG. 15 continuous addition of different concentrations of Fe 3+ Time-current-time linear graph, FIG. 16 continuous addition of Cr at different concentrations 2 O 7 2- Time-current graph of time, FIG. 17 continuous addition of Cr of different concentrations 2 O 7 2- A time-current linear graph; complex pair Fe 3+ Detection limit is 5.84 μ M for Cr 2 O 7 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 (CP 1) is equal to that of Fe 3+ Cr 2 O 7 2- The ion content is linear. Thus Fe at different concentrations depending on the complex 3+ The current intensity in the/Cr 2O 72-solution can be used for estimating Fe in the water solution 3+ /Cr 2 O 7 2- As Fe 3+ And Cr 2 O 7 2- The detection material of (1).
The present invention is not limited to the above embodiments, but various modifications and changes can 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 formula:
[Co 2 (4-dptb) 2 (1,3-BDC) 2 ]·2H 2 O；
wherein 4-dpptb isN,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 environment 3+ And Cr 2 O 7 2- 。
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-Fe 3+ Detection limit of 5.84 mu M for Cr 2 O 7 2- The ion detection limit is 1.84 mu M.
3. The cobalt-based complex structured by nitrogen-containing ligand and carboxylic acid ligand for detecting heavy metal ion according to claim 1, wherein:
the specific synthetic steps of the cobalt-based complex are as follows:
mixing Co (NO) 3 ) 2 ·6H 2 O，N,N’Putting bis (4-pyridinecarboxamide) -3, 4-thiophenedicarboxylic acid and isophthalic acid into an autoclave with a polytetrafluoroethylene lining according to a molar ratio of 0.1649 to 0.048, adding deionized water and 0.1mol/L NaOH solution according to a volume ratio of 3.
4. The cobalt-based complex structured by nitrogen-containing ligand and carboxylic acid ligand for detecting heavy metal ion 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 to construct a three-electrode of the sensor, and 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 and 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 a three-electrode method, the voltage is between 700mV and-100 mV and the Na is 0.5M 2 SO 4 And 0.1M H 2 SO 4 In the buffer solution, cyclic voltammetry is carried out on a solution to be tested at different sweep rates of 60mV/s, and the volume ratio of the buffer solution to the solution to be tested is 1.
8. The use of cobalt-based complex constructed by nitrogen-containing ligand and carboxylic acid ligand for detecting heavy metal ions according to claim 7 in an electroanalytical chemical sensor, wherein: the measurement voltage was 250mV.
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