CN115184435A - Method for detecting ions in different medium water bodies by all-solid-state polymer film ion selective electrode based on MXene conducting layer - Google Patents
Method for detecting ions in different medium water bodies by all-solid-state polymer film ion selective electrode based on MXene conducting layer Download PDFInfo
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- 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
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Abstract
The invention relates to the technical field of ion selective electrodes, in particular to a MXene conducting layer-based all-solid-state polymer film ion selective electrode for detecting ions in different medium water bodies. The invention utilizes the electrostatic action to lead NH with positive charge 2 -MWCNTs and negatively charged MXene are complexed as ion-electron conducting layer of the all solid polymer membrane ion selective electrode and the polymer sensitive membrane is adhered on the conducting layer. By using NH in the invention 2 The MWCNTs and MXene are compounded, so that the hydrophobicity of MXene can be obviously increased, and the response stability is improved; the MXene interlayer distance is enlarged, and the accumulation of MXene nanosheets is inhibited; simultaneous NH 2 The MWCNTs promote the connection of MXene sheets and accelerate electron transfer. The conductive layer is used as a conductive layer, is suitable for the thermodynamic response and the kinetic response of the ion selective electrode, and can realize the detection application of ions in different medium water bodies.
Description
Technical Field
The invention relates to the technical field of ion selective electrodes, in particular to a method for detecting ions in different medium water bodies by an all-solid-state polymer film ion selective electrode based on an MXene conducting layer.
Background
The electrochemical sensor is a device for detecting based on the electrochemical property of an object to be detected and converting the chemical quantity of the object to be detected into electric quantity, has the advantages of simple operation, convenient carrying, continuous and rapid detection of analytes and the like, and is widely applied to the fields of life science, food safety, medical inspection, environmental monitoring and the like. At present, electrochemical sensors are rapidly developed in the directions of miniaturization, integration, intellectualization and the like, and various electrochemical sensors are continuously emerged and applied to environmental monitoring. Potentiometric polymer membrane ion-selective electrodes are an important branch of electrochemical sensors. In recent years, polymer membrane ion selective electrodes have been used for detection in seawater. Taking calcium ion as an example, the current method is mainly based on the traditional calcium ion selective electrode (Ca) 2+ ISE) testing of the open circuit potential. Conventional Ca 2+ The response of the ISE follows the Nernst equation with a response slope of about 30mV/dec, in which case a potential change of 1mV would cause an error of 8%, and thus the sensitivity would be to be improved; the polymer film calcium ion selective electrode based on pulse constant current control is successfully used for high-sensitivity detection of calcium ions in seawater, but the method is still influenced by background electrolyte. Because the components of the environmental water body are complex and the matrix effect is different, the development of an all-solid-state polymer membrane ion selective electrode which is not interfered by the matrix effect is urgently needed to realize the stable detection of the ion concentration in different environmental water bodies.
The ion-electron conducting layer is an important component for developing stable all-solid-state polymer membrane ion-selective electrodes, and the performance of the ion-electron conducting layer influences the long-term stability and reproducibility of the all-solid-state polymer membrane ion-selective electrodes. Commonly used ion-electron conducting layer materials are nanomaterials. The MXene two-dimensional nano material has large specific surface area and high conductivity, can provide large double-layer capacitance, and has good application prospect. However, the MXene material has strong hydrophilicity, and is inevitably influenced by a water layer in the detection process, so that the MXene material is not favorable for the stability of electrode response; moreover, MXene two-dimensional nanosheets are prone to stacking and aggregation, which leads to reduction of electrochemical performance of the all-solid-state polymer membrane ion-selective electrode.
Disclosure of Invention
In view of the above, the present invention provides a method for detecting ions in different medium water bodies by using an MXene conductive layer-based all-solid-state polymer film ion-selective electrode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a detection method of ions in different medium water bodies by an all-solid-state polymer film ion selective electrode based on an MXene conducting layer, wherein the all-solid-state polymer film ion selective electrode is composed of NH with positive charges 2 -the composite formed by MWCNTs and negatively charged MXene is an ion-electron conducting layer; a polymer sensitive film is adhered to the ion-electron conducting layer;
the polymer sensitive film is a thermodynamically responsive polymer sensitive film or a kinetically responsive polymer sensitive film.
Preferably, NH in said composite material 2 The content of MWCNTs is 5-40 wt%.
Preferably, the preparation method of the composite material comprises the following steps:
reacting NH 2 Dropwise adding the MWCNTs aqueous dispersion into MXene aqueous dispersion, and performing ultrasonic dispersion to obtain the composite material.
Preferably, the concentration of the MXene aqueous dispersion is 0.2-1 mg/mL.
Preferably, the NH is 2 The concentration of the MWCNTs aqueous dispersion is 0.1-1 mg/mL.
Preferably, the preparation method of the all-solid-state polymer membrane ion-selective electrode comprises the following steps:
grinding the composite material and dispersing the ground composite material in water to obtain a composite material dispersion liquid;
dripping the composite material dispersion liquid on a glassy carbon electrode, and naturally airing in a drying cabinet to form the ion-electron conducting layer;
and coating a polymer sensitive membrane on the ion-electron conducting layer to obtain the all-solid-state polymer membrane ion selective electrode.
Preferably, the concentration of the composite material dispersion liquid is 1-3 mg/mL; the volume of the composite material dispersion liquid dropped on the glassy carbon electrode is 5-20 mu L.
Preferably, the thermodynamically responsive polymer-sensitive membrane consists of an ionophore, an ion exchanger, a polymer base material and a plasticizer; the kinetically-responsive polymeric sensing membrane is composed of an ionophore, an inert lipophilic salt, a polymeric base material, and a plasticizer.
Preferably, the ionophore independently comprises a cationic carrier or an anionic carrier; the cationic carriers independently comprise calcium ionophores, potassium ionophores, sodium ionophores, or copper ionophores; the anion carrier independently comprises a nitrate ionophore or a carbonate ionophore.
Preferably, the different medium water body comprises tap water, drinking water, lake water, river water or sea water.
The invention provides a detection method of ions in water bodies with different media by an all-solid-state polymer film ion selective electrode based on an MXene conducting layer, wherein the all-solid-state polymer film ion selective electrode adopts NH with positive charges 2 -the composite formed by MWCNTs and negatively charged MXene is an ion-electron conducting layer; a polymer sensitive film is adhered on the ion-electron conducting layer; the polymer sensitive film is a thermodynamically responsive polymer sensitive film or a kinetically responsive polymer sensitive film.
The invention has the advantages that:
1. the invention utilizes the electrostatic action to carry NH with positive charge 2 The MWCNTs and MXene with negative charges are compounded, the hydrophobicity of the obtained composite material is remarkably increased on the basis of keeping the advantages of the original MXene, the generation of a water layer is effectively prevented, and the response stability of the all-solid-state polymer membrane ion selective electrode is improved.
2. NH in the composite material of the invention 2 The MWCNTs are inserted among the MXene sheet layers, so that the interlayer spacing of the MXene is enlarged, the accumulation of the MXene sheet layers is effectively inhibited, the MWCNTs promote the connection of the MXene sheet layers, and the electricity can be acceleratedAnd (4) transferring the son.
3. The composite material is used as the ion-electron conducting layer, can support the thermodynamic response and the kinetic response of the all-solid-state polymer membrane ion selective electrode, and is a universal ion-electron conducting layer material of the all-solid-state ion selective electrode with good development prospect.
4. The all-solid-state polymer membrane ion selective electrode taking the transition time as the output signal can be used for detecting different ions in different medium backgrounds. The detection signal is not interfered by the background electrolyte.
Drawings
FIG. 1 shows multi-layer MXene (a), few-layer or single-layer MXene (b), and NH provided in example 1 2 MWCNTs (c) and NH 2 -microscopic electron microscopy of MWCNTs/MXene composite (d);
FIG. 2 shows different NH's provided in example 1 2 NH of MWCNTs content 2 -X-ray diffraction pattern of MWCNTs/MXene composite material;
FIG. 3 shows different NH's as provided in example 1 2 NH-MWCNTs content 2 -test pattern of contact angle of MWCNTs/MXene composite;
FIG. 4 shows a few or a single layer of MXene, NH as provided in example 1 2 MWCNTs and NH 2 -cyclic voltammetry test plots of MWCNTs/MXene composite as conducting layer;
FIG. 5 shows a few or a single MXene, NH layer provided in example 1 of the present invention 2 MWCNTs and NH 2 -electrochemical impedance mapping of the conductive layer with MWCNTs/MXene composite;
FIG. 6 is a graph of the potential response of the all-solid-state polymer membrane calcium ion selective electrode based on thermodynamic response provided in example 2;
FIG. 7 is a potential response diagram of the calcium ion selective electrode based on the full-solid polymer membrane with the potential as the output signal, provided in example 3;
fig. 8 is a response curve of the calcium ion selective electrode based on the all-solid-state polymer membrane with the transition time as the output signal provided in example 4.
Detailed Description
The invention provides a detection method of ions in different medium water bodies by an all-solid-state polymer film ion selective electrode based on an MXene conducting layer;
the all-solid-state polymer membrane ion selective electrode is charged with NH with positive charge 2 -MWCNTs and negatively charged MXene form a composite that is an ion-electron conducting layer; a polymer sensitive film is adhered to the ion-electron conducting layer;
the polymer sensitive film is a thermodynamically responsive polymer sensitive film or a kinetically responsive polymer sensitive film.
In the present invention, NH is contained in the composite material 2 The content of MWCNTs is preferably 5 to 40wt%.
In the present invention, the preparation method of the composite material preferably comprises the following steps:
reacting NH 2 Dropwise adding the MWCNTs aqueous dispersion into MXene aqueous dispersion, and performing ultrasonic dispersion to obtain the composite material.
In the present invention, the concentration of the MXene aqueous dispersion is preferably 0.2 to 1mg/mL. In the invention, the preparation method of MXene in the MXene aqueous dispersion liquid is preferably a mild acid etching method; the mild acid etching method preferably comprises the steps of: 2.0g LiF was mixed with 30mL HCl solution (6 mol/L) and stirred until completely dissolved. Then 3.0g Ti was slowly added 3 AlC 2 And (3) powder, heating the mixed solution in a water bath at 40 ℃ and continuously stirring for 48 hours, and etching the Al layer. After the reaction was completed, the mixed solution was repeatedly washed and centrifuged (3500 rpm) until the pH of the supernatant became approximately neutral. Subsequently, the product was collected and lyophilized for 48h to give multilamellar MXene. 0.5g of multi-layer MXene is dispersed in 200mL of ultrapure water, ar is introduced, ultrasonic treatment is carried out for 2h, then centrifugation is carried out for 1h at 3500rpm, and an upper layer solution is collected and freeze-dried to obtain the MXene.
In the present invention, the NH 2 The concentration of the aqueous MWCNTs dispersion is preferably 0.1 to 1mg/mL. In the present invention, the NH 2 The process for the preparation of aqueous MWCNTs dispersions preferably comprises the following steps: reacting NH 2 -MWCNTs dispersed in water, cetyl trimethyl addedAmmonium bromide, and ultrasonic treatment to obtain the NH 2 -aqueous MWCNTs dispersions.
In the present invention, the time for the ultrasonic dispersion is preferably 1h.
After the ultrasonic dispersion, the invention preferably further comprises the steps of carrying out centrifugal washing on the obtained system, and carrying out freeze drying on the obtained precipitate.
In the present invention, the method for preparing the all-solid-state polymer membrane ion-selective electrode preferably comprises the steps of:
grinding the composite material and dispersing the ground composite material in water to obtain a composite material dispersion liquid;
dripping the composite material dispersion liquid on a glassy carbon electrode, and naturally airing in a drying cabinet to form the ion-electron conducting layer;
and coating a polymer sensitive membrane on the ion-electron conducting layer to obtain the all-solid-state polymer membrane ion selective electrode.
The composite material is ground and then dispersed in water to obtain the composite material dispersion liquid. In the present invention, the concentration of the composite material dispersion is preferably 1 to 3mg/mL.
After the composite material dispersion liquid is obtained, the composite material dispersion liquid is dripped on a glassy carbon electrode and is naturally dried in a drying cabinet to form the ion-electron conducting layer. In the present invention, the volume of the composite material dispersion liquid dropped on the glassy carbon electrode is preferably 5 to 20 μ L. In the present invention, the drying mode is preferably natural drying in a drying cabinet.
After the ion-electron conduction layer is formed, the invention coats a polymer sensitive film on the ion-electron conduction layer to obtain the all-solid-state polymer film ion selective electrode.
In the present invention, the polymer-sensitive film includes a thermodynamically responsive polymer-sensitive film or a kinetically responsive polymer-sensitive film.
In the present invention, the thermodynamically responsive polymer-sensitive membrane is preferably composed of an ionophore, an ion exchanger, a polymer base material and a plasticizer. In the present invention, the ionophore preferably includes a cationic species or an anionic species. In the present invention, the cationic carrier preferably includes calcium ionophore, potassium ionophore, sodium ionophore or copper ionophore. In the present invention, the anionic carrier preferably comprises a nitrate ionophore or a carbonate ionophore. In the present invention, the ion exchanger preferably comprises sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate. In the present invention, the polymeric base material preferably comprises PVC. In the present invention, the plasticizer preferably includes o-nitrophenyloctyl ether. In the invention, the thermodynamically responsive polymer sensitive film consists of the following components in percentage by mass: 0.4-1.2 wt% of ion carrier, 0.4-1.2 wt% of ion exchanger, and the mass ratio of polymer base material to plasticizer is preferably 1:2.
in the present invention, the kinetically responsive polymeric sensing membrane is preferably composed of an ionophore, an inert lipophilic salt, a polymeric base material and a plasticizer. In the present invention, the types of the ionophore, the polymeric base material and the plasticizer are preferably consistent with the above technical solutions, and are not described herein again. In the present invention, the inert lipophilic salt preferably comprises the inert lipophilic salt tetrakis (dodecyl) -tetrakis (4-chlorophenyl) borate. In the invention, the dynamic response polymer sensitive film consists of the following components in percentage by mass: 0.4-1 wt% of ion carrier, 1-10 wt% of inert lipophilic salt, and the mass ratio of polymer base material to plasticizer is preferably 1:2.
in the present invention, the different medium water body preferably includes tap water, drinking water, lake water, river water or sea water.
In the present invention, the ions in the different medium water body preferably include cations or anions. In the present invention, the cation preferably includes calcium ion, potassium ion, sodium ion, or copper ion, and more preferably calcium ion. In the present invention, the anion includes a carbonate ion or a nitrate ion.
In the present invention, the detection method is specifically preferably:
and detecting by taking the all-solid-state polymer film ion selective electrode as a working electrode, taking Ag/AgCl as a reference electrode and taking a platinum wire electrode as an auxiliary electrode.
The following will describe the method for detecting ions in different medium water bodies by using an all-solid-state polymer membrane ion selective electrode based on an MXene conductive layer according to the present invention in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the all-solid-state polymer membrane calcium ion selective electrode comprises the following specific steps:
(1) Preparation of MXene
MXene is prepared by adopting a mild acid etching method: 2.0g LiF was mixed with 30mL HCl solution (6 mol/L) and stirred until completely dissolved. Then 3.0g Ti was slowly added 3 AlC 2 And (3) powder, heating the mixed solution in a water bath at 40 ℃ and continuously stirring for 48 hours, and etching the Al layer. After the reaction was completed, the mixed solution was repeatedly washed and centrifuged (3500 rpm) until the pH of the supernatant was close to neutral. Subsequently, the product was collected and lyophilized for 48h to give multilamellar MXene. The microscopic electron micrograph of the resulting multilayered MXene is shown as a in fig. 1.
0.5g of multi-layer MXene was dispersed in 200mL of ultrapure water, subjected to ultrasonic treatment for 2h by introducing Ar, and then centrifuged at 3500rpm for 1h, and the upper solution was collected to obtain a small layer or a single layer of MXene after freeze-drying. The microscopic electron micrograph of the resulting few-layer or monolayer MXene is shown in fig. 1 b.
(2)NH 2 Preparation of-MWCNTs/MXene composite material
a) Weighing 10mg of few-layer or single-layer MXene nanosheets, dissolving in 20mL of water, and performing ultrasonic treatment for 0.5h to obtain 0.5mg/mL of MXene dispersion for later use.
b) 10mg of NH are weighed 2 -MWCNTs(NH 2 Microscopic Electron microscopy of MWCNTs as shown in FIG. 1, c)) was dissolved in 20mL of water, 0.1wt% cetyltrimethylammonium bromide was added, and sonication was performed for 1h, yielding 0.5mg/mL NH 2 MWCNTs dispersions.
c) Taking NH of different volumes 2 Dropwise adding the MWCNTs dispersion liquid into 20mL of MXene dispersion liquid under the ultrasonic condition, and continuing to perform ultrasonic treatment for 1h; centrifuging and washing after the ultrasonic treatment is finished, removing unreacted MXene in the supernatant, and continuously washing the precipitate with ultrapure water 3Then freeze-drying overnight to obtain NH 2 -composite of MWCNTs and MXene, NH for short 2 -MWCNTs/MXene composite material. Obtained NH 2 The microscopic electron micrograph of the MWCNTs/MXene composite is shown as d in FIG. 1. As can be seen from d of fig. 1: NH (NH) 2 The MWCNTs are uniformly interpenetrated in the MXene lamella, so that the original lamella structure of MXene is maintained, and agglomeration of MXene is prevented.
Different NH is added 2 NH of MWCNTs content 2 The MWCNTs/MXene composite was subjected to X-ray diffraction tests (results see FIG. 2) and contact angle characterization (results see FIG. 3). As can be seen from FIGS. 2 and 3, with NH 2 The content of MWCNTs is increased, the MXene interlamellar spacing is enlarged continuously, and the hydrophobicity is enhanced sequentially.
(3) Preparation of Polymer sensitive Membrane
a) Preparing a sensitive film based on thermodynamic response: 360mg of a mixture of PVC, o-nitrophenyloctyl ether (o-NPOE), calcium ionophore (ETH 129) and sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate. Weighing 32.66wt% of PVC particles, 65.32wt% of o-nitrophenyloctyl ether, 1.00wt% of calcium ionophore and 1.02wt% of sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, transferring into 3.6mL of tetrahydrofuran, and stirring uniformly to obtain the calcium ion sensitive membrane solution.
b) Sensitive membrane preparation based on kinetic response: 60mg of PVC, 120mg of o-NPOE, 18mg of inert lipophilic salt tetradodecyl-tetrakis (4-chlorophenyl) ammonium borate (ETH 500) and 1.81mg of ETH 129 are weighed and dissolved in 2mL of tetrahydrofuran, and the calcium ion sensitive membrane solution can be obtained after uniform stirring.
(4) Preparing an all-solid-state polymer membrane calcium ion selective electrode:
a) Taking 2mg of the above NH 2 MWCNTs, few-layer or single-layer MXene and NH synthesized 2 Respectively dispersing the MWCNTs/MXene composite material in 1mL of water to prepare 2mg/mL of dispersion liquid. And (3) dripping 10 mu L of the dispersion liquid on a glassy carbon electrode (the diameter of the electrode is 3 mm), continuously dripping 10 mu L of the dispersion liquid on the glassy carbon electrode after water is evaporated, and obtaining uniform ion-electron conducting layers of different materials on the surface of the glassy carbon electrode.
Using cyclic voltammetry to measure in few or single layersMXene、NH 2 MWCNTs and NH 2 -MWCNTs/MXene composite as cyclic voltammogram of the conductive layer, results see FIG. 4. As can be seen from fig. 4: NH 2 The capacitance of the MWCNTs/MXene composite is significantly greater than that of few or single layers of MXene and NH 2 MWCNTs, description of NH 2 The MWCNTs/MXene composite material can promote the stability of potential response.
Testing with few or single layers of MXene, NH 2 -MWCNTs and NH 2 The MWCNTs/MXene composite is the electrochemical impedance of the conductive layer, the results are shown in FIG. 5. As can be seen from FIG. 5, NH 2 The electron transfer rate of the MWCNTs/MXene composite material is obviously faster than that of a few layers or a single layer of MXene and NH 2 -MWCNTs. Thus, NH 2 The MWCNTs/MXene composite material is beneficial to shortening the response time.
And (3) dripping 100 mu L of the polymer calcium ion sensitive membrane solution prepared by a) and b) in the step (3) on the glassy carbon electrode dropwise added with the conducting layer material, volatilizing in a drying cabinet overnight, and obtaining the all-solid-state polymer membrane calcium ion selective electrode based on thermodynamic response and kinetic response.
Example 2
The calcium ion selective electrode based on the all-solid-state polymer membrane with thermodynamic response obtained in the above is used 10 times before - 3 M CaCl 2 The solution was activated overnight. Adopting a two-electrode system, taking an activated all-solid-state polymer film calcium ion selective electrode as a working electrode and Ag/AgCl as a reference electrode, and inserting the two electrodes into a CaCl containing a series of different concentrations 2 In the solution, a potential signal response is generated, and the result is shown in fig. 6, wherein A is a real-time potential change response graph and B is a calibration curve graph in fig. 6. As can be seen from FIG. 6, in NH 2 All-solid-state polymer membrane calcium ion selective electrode based on thermodynamic response and with MWCNTs/MXene composite as conductive layer has stable potential response even at high concentration and potential of 10 -1 ～10 -5 Nernst response was exhibited in the mol/L range, and finally 6.3X 10 could be detected -7 M calcium ion.
Example 3
(1) Calcium ion in 0.5M NaCl background solutionAnd (3) sub-detection: the kinetic response-based all-solid polymer membrane calcium ion-selective electrode obtained above was activated overnight in a 0.1M NaCl solution prior to use. Adopting a three-electrode system, taking the activated all-solid-state polymer film calcium ion selective electrode as a working electrode, ag/AgCl as a reference electrode, a platinum wire electrode as an auxiliary electrode, and inserting the three electrodes into a system without CaCl 2 In 0.5M NaCl background solution, firstly, measuring open-circuit potential under the condition of zero current, and determining the open-circuit potential as the baseline potential of the working electrode; then according to a designed detection program, applying a cathode constant current with the pulse size of 4 muA for 2s to enable ions to be detected in the solution to be efficiently gathered on a polymer sensitive membrane of the working electrode, and finally according to the detection program design, applying an open-circuit potential for 120s to enable the working electrode to spontaneously return to the initial baseline potential; the potential change signal obtained when constant current is applied is the initial potential.
By gradually adding high-concentration CaCl into the solution to be measured 2 The calcium ions were detected according to the step (1) in the present embodiment, and the difference between the generated series of potential response values and the initial potential in the step (1) was used for the quantitative analysis of calcium ions, and the results are shown in fig. 7. As can be seen in FIG. 7, the kinetic response based all-solid-state polymer membrane calcium ion selective electrode is shown at 10 -4 ～10 -3 The calcium ion detection method has the advantages that the calcium ion detection method has a super-Nernst response within the concentration range of mol/L calcium ions, the response slope is about 100mV/dec, and compared with the traditional potential analysis method, the detection method can effectively improve the sensitivity of the electrode on the detection of the calcium ions in the high-concentration background electrolyte.
(2) Detection of calcium ions in 0.01M NaCl background solution: the initial potential value of the 0.01M NaCl background solution was measured in the same manner as in step (1) of this example. Calcium ions were detected by the same method as in step (2) of this example, and the difference between the generated series of potential response values and the initial potential was used for quantitative analysis of calcium ions, and the results are shown in FIG. 7. As can be seen in FIG. 7, the kinetic response based all-solid-state polymer membrane calcium ion selective electrode is shown at 10 -5 ～10 -4 The calcium ion has a super-Nernst response in a mol/L calcium ion range, and the response slope is 150mV/dec. Thus, using chronopotentiometric techniques with potential as output signal, is subject to the electrolyte of the background solutionInfluence, the super-nernst response is presented in different detection ranges, and the sensitive detection of the calcium ion concentration in different water bodies is difficult to realize.
Example 4
(1) Detection of calcium ions in 0.5M NaCl background solution: the kinetic response-based all-solid-state polymer membrane calcium ion-selective electrode obtained above was activated in a 0.1M NaCl solution for 24 hours before use. Adopting a three-electrode system, taking an activated all-solid-state polymer film calcium ion selective electrode as a working electrode, ag/AgCl as a reference electrode and a platinum wire electrode as an auxiliary electrode, and inserting the three electrodes into a reactor containing 1mM CaCl 2 In the 0.5M NaCl solution, firstly, measuring the open-circuit potential under the condition of zero current, and determining the open-circuit potential as the baseline potential of the working electrode; then according to a designed detection program, applying a cathode constant current with the pulse size of 4 muA for 5-15 s to ensure that ions to be detected in the solution are all gathered on the polymer sensitive membrane of the working electrode until calcium ions on the surface of the polymer sensitive membrane are all consumed; as the pulsed current is continuously applied, calcium ions are depleted at the polymer-sensitive membrane surface and the concentration of calcium ions in the solution is insufficient to sustain the applied ion flux, at which point the background ions are extracted along with the calcium ions into the membrane phase to maintain the applied ion flux. Since the chronometric potential varies with the pulse time, when the primary ions are depleted at the surface of the polymer sensitive membrane, the potential variation with time presents an inflection point, and the time corresponding to the inflection point is called as the transition time (τ). And finally, applying 100-300 s of open circuit potential according to the detection program design to ensure that the working electrode spontaneously returns to the initial baseline potential. By gradually adding high-concentration CaCl into the solution to be measured 2 And detecting the transition time of different calcium ion concentrations.
The time at which calcium ions are depleted at the surface of the polymer sensing membrane is called the transition time and is represented by the change of the transient slope of the potential with time. Adding CaCl of different concentrations 2 And (3) deriving the potential value of the solution with time to obtain the transition time of the calcium ions with different concentrations, taking the first derivative of the potential value with time as a vertical coordinate, and taking the time of the vertical coordinate peak value corresponding to the horizontal coordinate as the transition time. According to the Sand equation, with transition time obtained when constant current is appliedThe square root is the quantitative signal for calcium ion concentration detection, and the results are shown in A and B in FIG. 8.
(2) 0.01 detection of calcium ions in M NaCl background solution: the concentration of calcium ions in the 0.01M NaCl background solution was measured in the same manner as in the step (1) of this example, and the results are shown in FIGS. 8C and D. As shown in fig. 8, the transition time of B is consistent with D, which indicates that the effect of different background electrolytes on the transition time is almost negligible, i.e. the method can be used for detecting calcium ions in different background media.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A detection method of ions in different medium water bodies by an all-solid-state polymer film ion selective electrode based on an MXene conduction layer is characterized in that:
the all-solid-state polymer membrane ion selective electrode is charged with NH with positive charge 2 -the composite formed by MWCNTs and negatively charged MXene is an ion-electron conducting layer; a polymer sensitive film is adhered on the ion-electron conducting layer;
the polymer sensitive film is a thermodynamically responsive polymer sensitive film or a kinetically responsive polymer sensitive film.
2. The detection method according to claim 1, wherein NH is present in the composite material 2 The content of MWCNTs is 5-40 wt%.
3. The detection method according to claim 1 or 2, characterized in that the preparation method of the composite material comprises the following steps:
reacting NH 2 Dropwise adding the MWCNTs aqueous dispersion into MXene aqueous dispersion, and performing ultrasonic dispersion to obtain the composite material.
4. The detection method according to claim 3, wherein the concentration of the MXene aqueous dispersion is 0.2 to 1mg/mL.
5. The detection method according to claim 3, wherein the NH is 2 The concentration of the MWCNTs aqueous dispersion is 0.1-1 mg/mL.
6. The detection method according to claim 1, wherein the preparation method of the all-solid-state polymer membrane ion-selective electrode comprises the following steps:
grinding the composite material and dispersing the ground composite material in water to obtain a composite material dispersion liquid;
dripping the composite material dispersion liquid on a glassy carbon electrode, and naturally airing in a drying cabinet to form the ion-electron conducting layer;
and coating a polymer sensitive membrane on the ion-electron conducting layer to obtain the all-solid-state polymer membrane ion selective electrode.
7. The detection method according to claim 6, wherein the concentration of the composite dispersion is 1 to 3mg/mL; the volume of the composite material dispersion liquid dropped on the glassy carbon electrode is 5-20 mu L.
8. The detection method according to claim 1 or 6, wherein the thermodynamically responsive polymer-sensitive membrane consists of an ionophore, an ion exchanger, a polymer base material and a plasticizer; the kinetically responsive polymeric sensing membrane is comprised of an ionophore, an inert lipophilic salt, a polymeric base material and a plasticizer.
9. The detection method according to claim 8, wherein the ionophore independently comprises a cationic species or an anionic species; the cationic carriers independently comprise calcium ionophores, potassium ionophores, sodium ionophores, or copper ionophores; the anion carrier independently comprises a nitrate ionophore or a carbonate ionophore.
10. The detection method according to claim 1, wherein the different medium water body comprises tap water, drinking water, lake water, river water, or sea water.
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