CN113671005A - Copper ion selective electrode based on MOF, and preparation method and application thereof - Google Patents
Copper ion selective electrode based on MOF, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113671005A CN113671005A CN202110748139.4A CN202110748139A CN113671005A CN 113671005 A CN113671005 A CN 113671005A CN 202110748139 A CN202110748139 A CN 202110748139A CN 113671005 A CN113671005 A CN 113671005A
- Authority
- CN
- China
- Prior art keywords
- selective electrode
- ion selective
- hhtp
- copper
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
Abstract
The invention discloses a copper ion selective electrode based on MOF (metal-organic framework), a preparation method and application thereof3(HHTP)2. The ion selective electrode prepared by the invention has the rapid response capability; meanwhile, the product can still maintain good detection performance after being soaked in an organic solvent, and has the capability of storage and detection in a complex environment; and long-time ion balance process is not needed, and the method has the prospect of application and detection in the field of instant detection. Meanwhile, the preparation method is simple, the process flow is short, the production efficiency is effectively improved, and the industrial large-scale production is facilitated. The ion selective electrode has great potential and market prospect in the fields of environmental monitoring, instant detection and the like.
Description
Technical Field
The invention relates to the field of electrochemical analysis, in particular to a copper ion selective electrode based on MOF and a preparation method and application thereof.
Background
Nowadays, with the proposition of an environment-friendly society, the development mode of high economic effect and low pollution emission is emphasized. Therefore, there is an increasing demand for environmental monitoring and pollutant emission detection systems, so that researchers have attracted extensive attention to design and development of new sensor devices. As is well known, copper ion (Cu)2+) The biological toxicity is high, and the damage of the biological function can be caused even under low concentration. Cu2+Excessive accumulation in the human body may also cause various diseases such as Meniere's disease, Alzheimer's disease, hepatolenticular degeneration and the like. In the industrial field, the consumption of copper is ranked third after iron and aluminum. And the discharge of wastewater under the regulation, resulting in Cu2+The pollution to the living environment of people is also becoming serious. If the copper-containing wastewater is not treated properly, large-area environmental pollution is caused, and the normal production and life of people are seriously influenced. Not only in industrial terms, but also in many other aspects, leads to an excess of copper ions in the water: such as antifouling paints widely used for ships and underwater structures, which are used to prevent corrosion of the structures and ships, but the components thereof also cause diffusion of copper ions in water. Against this background, a set of tests was developed for Cu2+The rapid and accurate detection system is necessary, and can be used for detecting and controlling the pollution of copper ions in water and ensuring the human health and the environment not to be polluted.
In the related technology, the detection of copper ions selects all-solid-state ion selective electrodes (SC-ISEs), and the electrodes have the advantages of easiness in miniaturization, high portability, mass production and the like, and can promote the life of people to be faster and more convenient. A typical SC-ISE device comprises an Ion Selective Membrane (ISM) for specifically recognizing ions and establishing a stable membrane potential, and an all-solid-state switching layer material for stabilizing the SC-ISE potential. The earliest solid state switching layer materials were conductive polymers and their derivatives, which have large redox capacitance; in addition, carbon materials having high capacitance and strong hydrophobicity, such as carbon nanotubes, fullerenes and graphene and derivatives thereof; as well as gold nanoparticles and gold nanoclusters, and the like. Conventional solid-state ion-selective electrodes have various advantages, but one of the structural features of conventional conductive substrate-solid-state transduction layer-ion-selective membrane (ISM) causes a series of disadvantages: the ISM mechanical strength may be destroyed during long-term use; possibility of leakage of ISM components into the analytical solution; during application in the biomedical field, the material will directly contact the skin, which requires the ISM to be bio-friendly; a water layer and the like are easy to appear between the ISM and the solid switching layer, and the application prospect of the electrode in the field of on-site rapid detection is limited. Particularly, due to the existence of the polymer Ion Selective Membrane (ISM), SC-ISEs have a series of defects of complex preparation process, high component price, long detection response time, complicated pretreatment before storage and electrode detection and the like, and the defects become obstacles for constructing a new generation of all-solid-state ion selective electrode with stability and repeatability.
There is therefore a need to develop a MOF based copper ion selective electrode that is chemically stable.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a copper ion selective electrode based on MOF, and the ion selective electrode has good chemical stability.
The invention also provides a preparation method of the copper ion selective electrode based on the MOF.
The invention also provides application of the copper ion selective electrode based on the MOF.
The invention provides a copper ion selective electrode based on MOF (metal organic framework), which comprises a conductive substrate and a sensing layer covered on the surface of the conductive substrate, wherein the active ingredient of the sensing layer is Cu3(HHTP)2。
In the invention, MOF is a metal organic framework compound.
The novel membrane-free all-solid-state ion selective electrode (Cu-ISE) with the two-dimensional conductive metal organic framework (Cu-MOF) completely abandons ISM in the traditional ISE structure, and optimizes a classic membrane electrode system (conductive substrate-transfer layer-ISM) into a single-layer structure of conductive substrate-sensing layer, thereby constructing the all-solid-state membrane-free ion selective electrode.
The ion selective electrode of the present invention exhibits excellent detection performance, good Nernst response and superior long-term stability of potential. Most importantly, the film-free all-solid-state ion selective electrode based on the MOF does not need a pretreatment process required by a traditional electrode, does not need ion balance in a solution with a specific ion concentration, can also show Nernst response capability when being directly used for detection, and shows a faster potential response speed.
According to some embodiments of the invention, the MOF based copper ion-selective electrode further comprises a binder.
According to some embodiments of the invention, the binder comprises at least one of PVDF (polyvinylidene fluoride), PVC (polyvinyl chloride) and PTFE (polytetrafluoroethylene).
According to some embodiments of the invention, the mass ratio of the active ingredient to the binder is 7.5-8.5: 1.5-2.5.
According to some embodiments of the invention, the electrically conductive substrate comprises one of a glassy carbon material and a metallic material.
The glassy carbon material has the advantages of good electrical conductivity, high chemical stability, small thermal expansion coefficient, hard texture, wide potential application range and the like.
According to some embodiments of the invention, the metallic material comprises at least one of gold and silver.
The second aspect of the invention provides a preparation method of the copper ion selective electrode based on the MOF, which comprises the following steps:
dispersing the active ingredients and the adhesive into a solvent to obtain a dispersion liquid, coating the dispersion liquid on the surface of the conductive substrate, and drying.
According to some embodiments of the invention, the active ingredient, the method of preparation, comprises the steps of: reacting copper salt and organic ligand at 60-80 ℃, carrying out solid-liquid separation, and collecting a solid-phase product to obtain the active component;
wherein the organic ligand is 2,3,6,7,10, 11-hexahydroxy triphenyl.
According to some embodiments of the invention, the copper salt is a water soluble copper salt.
According to some embodiments of the invention, the water soluble copper salt is at least one of copper acetate, copper nitrate, copper chloride and copper sulfate.
According to some embodiments of the invention, the solvent is N-methylpyrrolidone (NMP).
NMP has the advantages of low toxicity, excellent dissolving capacity, good stability and the like.
According to some embodiments of the invention, the concentration of the active ingredient in the dispersion is between 5mg/mL and 15 mg/mL.
According to some embodiments of the invention, the temperature of the drying is 50 ℃ to 70 ℃; the drying time is 2-3 h.
In a third aspect, the invention provides the use of a MOF-based copper ion-selective electrode as described above in the manufacture of a copper ion detector.
The invention has at least the following beneficial effects:
the copper ion selective electrode prepared by the method has short response time and quick response capability; meanwhile, the product can still maintain good detection performance after being soaked in an organic solvent, and has the capability of storage and detection in a complex environment; and long-time ion balance process is not needed, and the method has the prospect of application and detection in the field of instant detection. Meanwhile, the preparation method is simple, the process flow is short, the production efficiency is effectively improved, and the industrial large-scale production is facilitated. The ion selective electrode has great potential and market prospect in the fields of environmental monitoring, instant detection and the like.
Drawings
FIG. 1 is Cu3(HHTP)2Characterizing the appearance of a scanning electron microscope;
FIG. 2 is Cu3(HHTP)2XRD test results;
FIG. 3 shows an ion selective electrode Cu3(HHTP)2For different Cu2+A potential response curve in a concentrated aqueous solution;
FIG. 4 shows an ion selective electrode Cu3(HHTP)2For different Cu2+Calibration curves in aqueous concentration solutions;
FIG. 5 shows an ion selective electrode Cu3(HHTP)2Potential response capability and response time diagram of/ISM;
FIG. 6 shows an ion selective electrode Cu3(HHTP)2ISM to different Cu2+A potential response curve in a concentrated aqueous solution;
FIG. 7 shows an ion selective electrode (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2Plot of selectivity coefficients for different ions,/ISM);
FIG. 8 shows an ion selective electrode (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) water layer test curve;
FIG. 9 shows an ion selective electrode (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) interference rejection performance of both to gas;
FIG. 10 shows an ion selective electrode (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) interference rejection performance for illumination;
FIG. 11 shows an ion selective electrode (Cu)3(HHTP)2ISM) potential response capability before and after soaking in organic solvent (ethanol) was tested;
FIG. 12 shows an ion selective electrode (Cu)3(HHTP)2) Testing the potential response capability before and after soaking in an organic solvent (ethanol);
FIG. 13 shows an ion selective electrode (Cu)3(HHTP)2) Potential response curves without ion-balancing treatment;
FIG. 14 shows an ion selective electrode (Cu)3(HHTP)2) Response time plot without ion equilibration treatment;
FIG. 15 shows an ion selective electrode Cu3(HHTP)2Potential response curves of the ISM without ion-balancing treatment;
FIG. 16 shows an ion selective electrode Cu3(HHTP)2And Cu3(HHTP)2ISM detection of Cu at different concentrations without ion balance2+The calibration curve of (1).
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the embodiment of the invention, the following reagents are selected:
copper acetate monohydrate (Cu (COOCH)3)2·H2O), diisooctyl sebacate (bis (2-ethylhexyl) rebaudinate, DOS), polyvinylidene fluoride resin (PVDF), sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (natfbb), Tetrahydrofuran (THF), copper chloride (CuCl)2·2H2O), copper ion (II) carrier I (O-XBDiBDTC), lithium chloride (LiCl), potassium chloride (KCl), sodium chloride (NaCl), zinc chloride (ZnCl)2) Magnesium chloride (MgCl)2) Nickel chloride (NiCl)2) Are all purchased from sigma-ori limited; 2,3,6,7,10, 11-hexahydroxytriphenyl (HHTP) purchased from Chishiai (Shanghai) chemical industry development Co., Ltd; n-methyl pyrrolidone (NMP) and other related solvents are available from the national pharmaceutical group, Inc., of China.
The polishing treatment method of the glassy carbon electrode in the embodiment of the invention comprises the following steps: applying 5mm glassy carbon electrode on nylon cloth with Al2O3Polishing with 0.3 μm polishing powder, cleaning, and adding Al2O3Polishing with 0.05 μm polishing powder, and washing with clear water and ethanol.
Example 1
The embodiment is a preparation method of an ion selective electrode, which comprises the following steps:
s1, mixing a metal center (copper acetate monohydrate) and an organic ligand (2,3,6,7,10, 11-hexahydroxy triphenyl) in an aqueous solution (the molar ratio of the two is about 1:1), reacting for 24 hours at 70 ℃ in an air environment to obtain a metal organic framework solid material, centrifugally filtering, washing with water, ethanol and acetone in sequence, and drying to obtain Cu3(HHTP)2。
S2, preparing a copper ion selective electrode: subjecting the two-dimensional conductive metal organic framework (Cu) prepared in step S13HHTP2) And PVDF (polyvinylidene fluoride) in a mass ratio of 8: 2 dispersing in NMP solution, ultrasonic dispersing for 2h to obtain dispersion, and controlling Cu in the dispersion3HHTP2The mass concentration of (3) is 10 mg/mL. Dropping 15 μ L of the dispersion liquid on the polished glassy carbon electrode, drying in a 60 deg.C oven for 2h, and storing in dark to obtain ion selective electrode Cu3(HHTP)2。
Example 2
The embodiment is a preparation method of an ion selective electrode, which comprises the following steps:
s1, preparation of an electronic transfer layer: mixing a metal center (copper acetate monohydrate) and an organic ligand (2,3,6,7,10, 11-hexahydroxy triphenyl) in an aqueous solution (the molar ratio of the two is about 1:1), reacting for 24 hours at 70 ℃ in an air environment to obtain a metal organic framework solid material, centrifugally filtering, washing with water, ethanol and acetone in sequence, and drying to obtain Cu3(HHTP)2。
S2、Cu2+Preparation of the selective membrane: 65.7 wt% DOS, 32.9 wt% PVC, 1.00 wt% copper ion (II) carrier I and 0.86 wt% NaTFPB, the total mass of the membrane components being 100mg, were dissolved in 1mL of tetrahydrofuran solution.
S3, preparation of a copper ion selective electrode: two-dimensional conductive metal organic framework Cu is dripped on the polished glassy carbon electrode3(HHTP)2As an electron transfer layer, 50. mu.L of Cu was transferred2+Dropping the selective membrane solution on the dried electrode, and drying at room temperature for 24h to obtain the ion selective electrode Cu3(HHTP)2/ISM。
Test example
The ion-selective electrode prepared in the embodiment 1-2 of the invention is used as a working electrode, and a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode; all electrochemical tests were performed using a Gamry electrochemical workstation with a three-electrode system.
The prepared Cu was characterized by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD), respectively3(HHTP)2The conductive metal organic frame material has the test results shown in the figures 1-2; wherein FIG. 1 shows SEM test results showing a self-assembled structure in a rod shape. FIG. 2 is a XRD test result showing that Cu is prepared3(HHTP)2Is a crystal structure, and has no other ligand and impurity residue.
Testing of ion-selective electrode Cu using electrochemical open circuit potential detection method using Gamry electrochemical workstation3(HHTP)2And ion selective electrode Cu3(HHTP)2Potential response capability and response time of the/ISM. The test results are shown in FIGS. 3-6; wherein, FIG. 3 shows an ion selective electrode Cu3(HHTP)2For different Cu2+A potential response curve in a concentrated aqueous solution; the inset in fig. 3 is the potential response time of its electrodes. FIG. 4 shows an ion selective electrode Cu3(HHTP)2For different Cu2+Calibration curves in aqueous concentration solutions. FIG. 5 shows an ion selective electrode Cu3(HHTP)2ISM to different Cu2+Potential response curves in aqueous concentration solutions. The inset in fig. 5 is the potential response time of its electrodes. FIG. 6 shows an ion selective electrode Cu3(HHTP)2ISM to different Cu2+Calibration curves in aqueous concentration solutions. From FIGS. 3 to 4, the ion selective electrode Cu is shown3(HHTP)2The response slope of (A) is 29.46. + -. 0.26mV/decade (R)20.9998), detection limit reaches 10-4.50And M. And the potential response time thereof is less than 10 s. From FIGS. 5 to 6, the ion selective electrode Cu is shown3(HHTP)2The response slope of/ISM is 30.56 + -0.36 mV/decade (R)20.9995) detection limit of 10-6.48And M. The potential response time is long, and the time for the potential signal to reach stability is more than 100 s. As can be seen from the results of the tests shown in FIGS. 3 to 6, the product obtained in example 1 was obtainedIon selective electrode pair Cu2+The response time is greatly reduced while the potentiometric Nernst response is kept, and the device has a quick response capability.
Ion selective electrode (Cu) using electrochemical open circuit potential detection3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) and the aqueous layer, and the interference rejection of the above ion-selective electrode against gas and light was examined.
The selectivity coefficient calculation method comprises the following steps: testing target electrodes for interfering ions (Li) at different concentrations+,Na+,K+,Co2+,Ni2 +,Zn2+,Mg2+) Observing whether the response exists or not, and then calculating the respective selectivity coefficients by the following formula:
in the formula, EjAnd Ei，ZjAnd Zi，ajAnd aiRespectively representing the potential, charge number and ion activity of the interfering ion and the target ion; f is the faraday constant, R is the ideal gas constant, and T is temperature).
FIG. 7 shows an ion selective electrode (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) selectivity coefficient for different ions. From the test results in FIG. 7, it can be seen that the ion selective electrode (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) compared with specific recognition performance, but still has better ion selectivity.
Water layer test curve: the test method is firstly to use 0.01M CuCl2The open circuit potential was measured in solution, after which the test solution was changed to 0.01M LiCl solution and finally 0.01M CuCl2And (4) testing in the solution.
FIG. 8 shows an ion selective electrode (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2/ISM) both water layer test curves; from the water layer test curve, Cu3(HHTP)2The electrode has no obvious water layer formation, which is benefited by two phase interface response, less than Cu3(HHTP)2Three phase interfaces of the/ISM electrode.
FIGS. 9 to 10 show ion selective electrodes (Cu)3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) has anti-interference performance to gas and light. From the results in fig. 9 to 10, it is found that both have good interference resistance to light and gas. Wherein the ion selective electrode Cu3(HHTP)2The anti-interference performance is more excellent.
Ion selective electrode (Cu) using electrochemical open circuit potential detection3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) potential response capability before and after soaking in organic solvent (ethanol). The test results are shown in FIGS. 9 to 10.
FIG. 11 shows an ion selective electrode Cu3(HHTP)2Cu leaching in ethanol solvent before and after 4 hours of ISM2+Potential response curve of (2). FIG. 12 shows an ion selective electrode Cu3(HHTP)2Soaking Cu in ethanol solvent for 4 hr2+Potential response curve of (2). In FIG. 11, the ion selective electrode Cu is shown3(HHTP)2After soaking in ethanol solvent for 4 hours, the/ISM (with membrane electrode) lost its Cu couple before soaking2+The detection capability of (1). The potential response slope before soaking is 31.66mV decade-1And soaking, ion selective electrode Cu3(HHTP)2ISM (with Membrane electrode) to Cu2+The concentration changes, there is no corresponding change in the potential signal. From the comparison of the results of FIGS. 11 and 12, it is understood that the ion selective electrode Cu3(HHTP)2(without membrane electrode) after 4 hours of ethanol solvent soaking, to Cu2+The concentration variation still shows good nernst potential response capability. The potential response slope before soaking is 32.76mV/decade, and the electrode after soaking is against Cu2+Still maintain a 30.94mV/decade responseThe slope. From the above results, it is clear that the ion selective electrode Cu3(HHTP)2The (membrane-free ion selective electrode) can still maintain good detection performance after being soaked in an organic solvent, and has the capability of storage and detection in a complex environment.
Ion selective electrode (Cu) using electrochemical open circuit potential detection3(HHTP)2) And ion selective electrode (Cu)3(HHTP)2ISM) after the ion-balancing process in the simplified pretreatment, the test results are shown in FIGS. 13-15.
Conventional membrane electrodes (ion selective electrodes (Cu)3(HHTP)2ISM)), often require a long soak in an aqueous solution of a specific concentration of ions before testing can be performed for ion equilibration purposes in the selective membrane. This balancing process is simplified and the response capabilities of the two electrodes are compared.
FIGS. 13 to 14 show ion selective electrodes (Cu)3(HHTP)2) Potential response curve and response time chart without ion balance treatment, wherein, FIG. 13 is ion selective electrode Cu3(HHTP)2Directly used for Cu without ion balance2+The measured potential response curve. FIG. 14 shows an ion selective electrode Cu3(HHTP)2And testing the result of the response time in the response process. FIG. 15 shows an ion selective electrode Cu3(HHTP)2the/ISM electrode is not ion-balanced and is used directly for Cu2+The measured potential response curve. FIG. 16 shows an ion selective electrode Cu3(HHTP)2And Cu3(HHTP)2Ion balance of/ISM electrode to detect Cu at different concentrations2+The calibration curve of (1). The results of the tests shown in FIGS. 13 to 16 show that the ion selective electrode Cu3(HHTP)2(membraneless electrode) without ion-balancing this pretreatment process, it can still be applied to Cu2+Good potential response capability is maintained, and the response curve conforms to the Nernst slope (28.77 +/-0.85 mV/decade). While maintaining good responsiveness, the response time is not affected (<10 s). In contrast, the ion selective electrode Cu3(HHTP)2(with membrane electrode) ofBy the pretreatment process of ion balance, Cu is lost2+Potential response capability of Cu could not be realized2+Detection of (3). This result indicates that the ion selective electrode Cu3(HHTP)2(Membrane-free electrode) ion-selective electrode Cu in comparison with3(HHTP)2The membrane electrode of the/ISM (with the membrane electrode) does not need a long-time ion balance process, and has a prospect of application and detection in the field of instant detection.
Ion selective electrode Cu3(HHTP)2The complex three-layer structure of the/ISM needs ion exchange and electron transduction to cause long response time of detection, the middle transduction layer causes water layer to influence the potential stability of the electrode, and the ion selective electrode Cu3(HHTP)2the/ISM requires a long time soaking in the target solution to reach the ion equilibrium in the membrane, and the pretreatment process before detection seriously affects the application of the electrode to the real-time detection.
The invention provides a novel membrane-free all-solid-state ion selective electrode (Cu-ISE) based on a two-dimensional conductive metal organic framework (Cu-MOF) for the first time, and discloses detection and analysis performances of the novel membrane-free all-solid-state ion selective electrode. The Cu-ISE completely abandons ISM in the traditional ISE structure, and optimizes a classical membrane electrode system (conductive substrate-transfer layer-ISM) into a single-layer structure of conductive substrate-sensing layer.
Meanwhile, the all-solid-state membrane-free ion selective electrode constructed by the invention shows excellent detection performance, good Nernst response and superior long-term potential stability. Most importantly, the film-free all-solid-state ion selective electrode based on the MOF does not need a pretreatment process required by a traditional electrode, does not need ion balance in a solution with a specific ion concentration, can also show Nernst response capability when being directly used for detection, and shows a faster potential response speed. The results show the application potential of the all-solid-state membrane-free ion selective electrode prepared by the invention in environmental detection.
Further, the application uses two-dimensional conductive Cu-MOF as an electrode modification material for Cu2+The membrane-free solid-state ion-selective potential sensor of (1). The Cu-MOF material is utilized, and a potential method is adopted to detect Cu2+In a manner ofThe two-dimensional conductive Cu-MOF is used as a transfer layer and a recognition layer for the first time, and a membrane-free solid ion selective electrode is prepared and used for ion potential detection.
In conclusion, the ion selective electrode prepared by the invention has the rapid response capability; meanwhile, the product can still maintain good detection performance after being soaked in an organic solvent, and has the capability of storage and detection in a complex environment; and long-time ion balance process is not needed, and the method has the prospect of application and detection in the field of instant detection. Meanwhile, the preparation method is simple, the process flow is short, the production efficiency is effectively improved, and the industrial large-scale production is facilitated. The ion selective electrode has great potential and market prospect in the fields of environmental monitoring, instant detection and the like.
While the embodiments of the present invention have been described in detail with reference to the description and the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A copper ion selective electrode based on MOF is characterized by comprising a conductive substrate and a sensing layer covering the surface of the conductive substrate; the active component of the sensing layer is Cu3(HHTP)2。
2. A MOF-based copper ion-selective electrode according to claim 1, wherein: the sensing layer further comprises an adhesive; preferably, the binder comprises at least one of PVDF, PVC and PTFE; the mass ratio of the active ingredients to the adhesive is 7.5-8.5: 1.5-2.5.
3. A MOF-based copper ion-selective electrode according to claim 2, wherein: the conductive substrate includes one of a glassy carbon material and a metal material.
4. A method of making a MOF based copper ion selective electrode of claim 2 or 3, comprising the steps of:
dispersing the active ingredients and the adhesive into a solvent to obtain a dispersion liquid, coating the dispersion liquid on the surface of the conductive substrate, and drying.
5. The method of claim 4, wherein: the preparation method of the active ingredient comprises the following steps: reacting copper salt and organic ligand at 60-80 ℃, carrying out solid-liquid separation, and collecting a solid-phase product to obtain the active component;
wherein the organic ligand is 2,3,6,7,10, 11-hexahydroxy triphenyl.
6. The method of claim 5, wherein: the copper salt is water-soluble copper salt; preferably, the water-soluble copper salt is at least one of copper acetate, copper nitrate, copper chloride and copper sulfate.
7. The method of claim 4, wherein: the solvent is N-methylpyrrolidone (NMP).
8. The method of claim 4, wherein: the concentration of the active ingredient in the dispersion liquid is 5 mg/mL-15 mg/mL.
9. The method of claim 4, wherein: the drying temperature is 50-70 ℃; the drying time is 2-3 h.
10. A copper ion detector, characterized by: comprising a MOF-based copper ion-selective electrode according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110748139.4A CN113671005A (en) | 2021-07-01 | 2021-07-01 | Copper ion selective electrode based on MOF, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110748139.4A CN113671005A (en) | 2021-07-01 | 2021-07-01 | Copper ion selective electrode based on MOF, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113671005A true CN113671005A (en) | 2021-11-19 |
Family
ID=78538438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110748139.4A Pending CN113671005A (en) | 2021-07-01 | 2021-07-01 | Copper ion selective electrode based on MOF, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113671005A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114632547A (en) * | 2022-02-25 | 2022-06-17 | 武汉工程大学 | Preparation method and application of two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material |
| CN114805912A (en) * | 2022-04-07 | 2022-07-29 | 福建师范大学 | For K + Preparation method of MOF composite porous sensitive membrane of electrochemical sensor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037283A (en) * | 2015-07-09 | 2015-11-11 | 山东师范大学 | Metal organic framework based on Cu(II) ion, synthetic method therefor and application thereof |
| CN111579617A (en) * | 2020-05-11 | 2020-08-25 | 中国科学院烟台海岸带研究所 | Preparation and application of solid contact type polymer film copper ion selective electrode |
| CN112285183A (en) * | 2020-10-10 | 2021-01-29 | 广州大学 | Membrane-free all-solid-state ion selective electrode and preparation method and application thereof |
| CN112326759A (en) * | 2020-10-30 | 2021-02-05 | 宁波大学 | Preparation method and application of cadmium ion selective electrode based on MOF material |
-
2021
- 2021-07-01 CN CN202110748139.4A patent/CN113671005A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037283A (en) * | 2015-07-09 | 2015-11-11 | 山东师范大学 | Metal organic framework based on Cu(II) ion, synthetic method therefor and application thereof |
| CN111579617A (en) * | 2020-05-11 | 2020-08-25 | 中国科学院烟台海岸带研究所 | Preparation and application of solid contact type polymer film copper ion selective electrode |
| CN112285183A (en) * | 2020-10-10 | 2021-01-29 | 广州大学 | Membrane-free all-solid-state ion selective electrode and preparation method and application thereof |
| CN112326759A (en) * | 2020-10-30 | 2021-02-05 | 宁波大学 | Preparation method and application of cadmium ion selective electrode based on MOF material |
Non-Patent Citations (3)
| Title |
|---|
| FEI WU 等: "Two-dimensional π-conjugated metal-organic framework with high electrical conductivity for electrochemical sensing", 《J CHIN CHEM SOC.》 * |
| MARIA DE LOURDES GONZALEZ-JUAREZ 等: "Electrochemical deposition and thermoelectric characterisation of a semiconducting 2-D metal–organic framework thin film", 《J. MATER. CHEM. A》 * |
| MING-SHUI YAO 等: "Layer-by-Layer Assembled Conductive Metal–Organic Framework Nanofilms for Room-Temperature Chemiresistive Sensing", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114632547A (en) * | 2022-02-25 | 2022-06-17 | 武汉工程大学 | Preparation method and application of two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material |
| CN114805912A (en) * | 2022-04-07 | 2022-07-29 | 福建师范大学 | For K + Preparation method of MOF composite porous sensitive membrane of electrochemical sensor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Alkaline intercalation of Ti3C2 MXene for simultaneous electrochemical detection of Cd (II), Pb (II), Cu (II) and Hg (II) | |
| CN113671005A (en) | Copper ion selective electrode based on MOF, and preparation method and application thereof | |
| CN110672684B (en) | Electrochemical sensor for detecting nitrite with high sensitivity and preparation method and application thereof | |
| Li et al. | An effective solid contact for an all-solid-state polymeric membrane Cd2+-selective electrode: Three-dimensional porous graphene-mesoporous platinum nanoparticle composite | |
| Naik et al. | Electrodeposition of ZnCo 2 O 4 nanoparticles for biosensing applications | |
| CN111239214B (en) | Three-electrode type Pb (II) and Cu (II) electrochemical sensor, preparation method and application thereof | |
| Legeai et al. | Economic bismuth-film microsensor for anodic stripping analysis of trace heavy metals using differential pulse voltammetry | |
| Zeng et al. | Stable Pb2+ ion-selective electrodes based on polyaniline-TiO2 solid contacts | |
| Xu et al. | Electrochemical preparation of a three dimensional PEDOT–Cu x O hybrid for enhanced oxidation and sensitive detection of hydrazine | |
| CN108226244B (en) | For detecting the electrochemical sensor and its preparation method and application of lead ion and/or cadmium ion | |
| Frag et al. | Preparation, characterization and electrochemical application of CuNiO nanoparticles supported on graphite for potentiometric determination of copper ions in spiked water samples | |
| CN112345604A (en) | Nano bismuth-polypyrrole composite electrode, preparation method thereof and application of nano bismuth-polypyrrole composite electrode in heavy metal ion detection | |
| Zeng et al. | Application of flower-like SnS 2 nanoparticles for direct electrochemistry of hemoglobin and its electrocatalysis | |
| Chen et al. | A novel and sensitive electrochemical sensor based on nanoporous gold for determination of As (III) | |
| Xu et al. | Conductive metal organic framework for ion-selective membrane-free solid-contact potentiometric Cu2+ sensing | |
| Li et al. | Fusiform-like metal-organic framework for enantioselective discrimination of tryptophan enantiomers | |
| Qi et al. | Electrochemical sensor for Cd2+ detection based on carbon fiber paper sequentially modified with CoMOF, AuNPs, and glutathione | |
| CN107991364A (en) | A kind of solid ionic electrodes selective and its preparation and application | |
| See et al. | Highly Sensitive Aluminium (III) ion sensor based on a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode | |
| Fu et al. | Simple preparation and highly selective detection of silver ions using an electrochemical sensor based on sulfur-doped graphene and a 3, 3′, 5, 5′-tetramethylbenzidine composite modified electrode | |
| Li et al. | Bimetallic NiCo metal-organic framework-derived hierarchical spinel NiCo2O4 microflowers for efficient non-enzymatic glucose sensing | |
| CN114538530B (en) | Basic cobalt carbonate nano material for electrochemical sensor and preparation method and application thereof | |
| CN115356388A (en) | Zinc-cobalt sulfide bimetallic organic framework material, preparation method thereof and application thereof in electrochemical detection of glucose | |
| Dewi et al. | Development and characterization of solid Cu/CuSO4 reference electrodes | |
| Zen et al. | Elimination of the Copper‐Zinc Interference at Mercury Film Electrodes by a Nafion/Clay Modified Layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |