CN115236148A - Salinity detection sensor suitable for coastal zone sediment environment and detection method thereof - Google Patents
Salinity detection sensor suitable for coastal zone sediment environment and detection method thereof Download PDFInfo
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
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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
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Abstract
The invention relates to detection of salt content in environment, in particular to a salinity detection sensor suitable for a horizontal plane and a vertical section of a coastal zone sediment and a detection method thereof. The sensor comprises a cation electrode, an anion electrode and a thin-layer sample introduction device, wherein the thin-layer sample introduction device is arranged between the anion electrode and the cation electrode; wherein, the thin layer sample injection device is a material capable of spontaneously absorbing a sample. The potential salinity sensor has the advantages of low cost, high sensitivity, quick response time, small required sample amount, simple operation and the like. The sensor is expected to be used as a novel salinity meter.
Description
Technical Field
The invention relates to detection of salt content in environment, in particular to a salinity detection sensor suitable for a horizontal plane and a vertical section of coastal zone sediment and a detection method thereof.
Background
A large amount of salt is stored in seawater, the salt content (salinity) in different environments has different distributions, and the salinity has important significance for environmental monitoring and ecological processes. Salinity refers to the ratio of total dissolved solids in a sample to the weight of the sample, usually expressed in grams contained per kilogram of sample. Salinity is used to represent the mass fraction of salt species in seawater. The average salinity of oceans in the world is 35 per thousand. Salinity also plays an extremely important role in coastal zone environments. Salinity is a controlling factor in distributing contaminants between the sediment and pore water, and increasing salinity can facilitate the deposition of dissolved materials from the aqueous phase into the sediment. Salinity also affects the bioavailability of organic and inorganic contaminants in the sediment, which in turn affects biotoxicity. Salinity is also the most important factor in controlling biodistribution in coastal zones, and differences in salinity in sediments affect biodistribution.
The salinity sensors on the market are mainly optical refraction sensors and conductivity sensors. However, the above two sensors are not suitable for salinity sensors in coastal zone sediment environments. On the one hand, the complex interference of the matrix in the sediment environment with the measurement, and on the other hand, the smaller sample volume in the sediment environment is not suitable for the immediate detection. And further, a proper salinity sensor for the coastal zone sediment environment needs to be designed aiming at the two difficulties of salinity detection of the sediment environment.
Disclosure of Invention
The invention aims to provide a salinity detection sensor suitable for a coastal zone sediment environment and a detection method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a salinity test sensor adapted for coastal zone sediment environments, comprising: the sensor comprises a cation electrode, an anion electrode and a thin-layer sample introduction device, wherein the thin-layer sample introduction device is arranged between the anion electrode and the cation electrode; wherein, the thin layer sample injection device is a material capable of spontaneously absorbing a sample.
And the corresponding positions of the top ends of the cation electrode and the anion electrode are respectively coated with the response materials of the corresponding electrodes.
The cation response material in the cation electrode is copper ferricyanide (CuHCF) and manganese oxide complex (MnO) 2 、Na x Mn y O z (x, y, z may be the same or different and are selected from 1-5)), vanadium oxide complex (Na) x V y O z (x，y, z may be the same or different and are selected from 1-5)), cobalt oxide (Co) 3 O 4 ) Titanium oxide complex (Na) x Ti y O z (x, y, z may be the same or different and are selected from 1-5)), a titanium phosphate complex (NaTi) 2 (PO 4 ) 3 ) Vanadium phosphate complex (Na) 3 V 2 (PO 4 ) 3 ) Iron phosphate complex (Na) 2 FeP 2 O 7 ) Prussian blue (PW);
the anion response material in the anion electrode is silver (Ag), silver chloride (AgCl), silver-silver chloride (Ag/AgCl), bismuth (Bi), bismuth oxychloride (BiOCl) and polypyrrole (PPy).
The cation electrode is a sodium electrode, a potassium electrode, a magnesium electrode or a calcium electrode, the anion electrode is a chlorine electrode, the thin-layer sample injection device is paper, a filter membrane, cloth, a porous stone plate, sponge, porous glass, porous ceramic, functionalized paper (for example, a catalyst, an enzyme and an adsorbent are loaded on the paper to change the property of the solution to be detected), and the like.
A preparation method of a salinity detection sensor suitable for coastal zone sediment environments comprises the following steps:
1) Preparing an electrode substrate: cutting the conductive substrate into a T shape, wherein the T-shaped vertical edge is positioned in the middle of the transverse edge or is eccentrically arranged with the middle of the transverse edge; coating the surface of one side of the T-shaped transverse edge with a corresponding electrode material;
or cutting the conductive substrate into a 'one' shape;
2) Preparation of cation electrode and anion electrode: taking the prepared electrode matrixes as a cation electrode matrix and an anion electrode matrix respectively, coating response materials of the electrodes at the intersection of the transverse edge and the vertical edge of the T-shaped matrixes of the cation electrode matrix and the anion electrode matrix, wherein the coating width of the response materials is the same as that of the vertical edge;
or, respectively coating the response materials of the electrodes on the conductive substrates cut into the shape of a straight line;
then calcining at 120 ℃ for 30min to respectively obtain a cation electrode and an anion electrode of the salinity sensor; placing the two calcined electrodes in an overlapping manner to enable the longitudinal parts of the electrodes to be overlapped;
3) Preparing a sensor: arranging a material which can spontaneously suck a sample and is used as a thin layer sample feeding device between the electrodes overlapped in the step 2).
The surface of the cation electrode and the surface of the anion electrode facing the thin layer sample introduction device are non-conductive surfaces; the cross edge and the vertical edge of the base body on the conductive surfaces of the cation electrode and the anion electrode are coated with the response material of the electrodes, and the coating width of the response material is the same as that of the vertical edge.
The conductive substrate is indium tin oxide glass (ITO), tin fluorine oxide (FTO), zinc aluminum oxide (AZO), iron plate/sheet, aluminum plate/sheet, copper plate/sheet, steel plate/sheet, titanium plate/sheet, silver plate/sheet, gold plate/sheet and glassy carbon;
the method for detecting the salinity of the coastal zone sediment environment by using the sensor comprises the steps of inserting the sensor into a coastal zone sediment to be detected, enabling a sample to be contacted with the sample through a material capable of spontaneously sucking the sample in a thin-layer sample injection device, enabling cations in the sample to act with a cation electrode, enabling anions in the sample to act with an anion electrode to respectively generate potential response, and calculating according to potential response signals to further obtain the salinity of the sample.
The potential value of the cation electrode in the sensor is increased along with the increase of salinity, the potential value of the anion electrode is reduced along with the increase of salinity, the sample salinity is obtained through calculation of the generated potential value, and the formula (formula 1) is calculated according to the potential response signal
Wherein A and B are constants obtained by calibrating the potential salinity sensor; c Na 、C k 、C ca 、C Mg 、 C Cl Is Na + 、K + 、Ca 2+ 、Mg 2+ 、Cl - Molarity at salinity of 35 °; t is the sample temperature.
When detecting coastal zone sediment, a plurality of sensors can be connected in series or in parallel to perform potential superposition, so that the resolution of the sensors is improved, and the salinity detection precision is further improved.
The sensor can amplify signals through multistage series connection, and the salinity detection resolution is improved. The specific principle is that in the design of the circuit, the series circuit is the superposition of the same potential of each electrode current, and the parallel circuit is the superposition of the same current of each electrode potential. According to the invention, potential superposition can be carried out by using a multi-stage series circuit design through potential detection, so that the resolution of the sensor is improved, and the resolution of superposed n electrodes is improved by n times. The sensor can also carry out current superposition through a multi-stage parallel circuit.
When the coastal zone sediment is detected, the potential sensor is connected with the electrochromic material in parallel, and the potential response drives the potential change of the electrochromic material, so that the color change is caused to carry out visual display of the potential response.
Furthermore, the sensor of the present invention can be read out by colorimetric analysis, thereby simplifying the potentiometer, and can be read out by naked eyes, a colorimetric card, a smart phone, and the like. The electrode is connected with the electrochromic material in parallel according to a specific principle, the potential change of the electrode can cause the color change of the electrochromic material, and then the color change is read visually. The sensors of the present invention can be coupled to a variety of electrochromic materials, for example: polyaniline and its derivative (PANI), tungsten trioxide and its derivative (WO) 3 ) Prussian blue and its derivative (PW), vanadium pentoxide and its derivative (V) 2 O 5 ) Polythiophene and its derivatives (PT), polyethylenedioxythiophene (PEDOT), polypyrrole and its derivatives (PPs), viologen and its derivatives, and the like.
Principle of detection
When the object to be detected contains salts, the potential is increased due to the action of the cations in the sample to be detected and the cation electrode of the sensor, the potential is decreased due to the action of the anions in the sample to be detected and the anion electrode of the sensor, potential response is generated, the salinity of the object to be detected can be obtained through calculation of a potentiometer reading formula, meanwhile, the cation electrode in the sensor is a positive electrode, and the anion electrode is a negative electrode, so that the total potential signal is amplified twice compared with a single electrode, and the resolution of the sensor is improved.
The sensor of the present invention can maintain a stable response in the pH range of 4 to 10. The sensor can be used for on-site detection in coastal zone sediment environment, pretreatment is not needed, and accurate salinity can be obtained through correction (ion correction and temperature correction) of corresponding mathematical algorithm.
The invention has the advantages that:
the integrated paper-based potential salinity sensor is not influenced by environmental turbidity, the detected concentration (activity) is directly related to salinity, so that the size of an electrode can be reduced, the amount of a sample to be detected is reduced, and meanwhile, the paper base is introduced to serve as a thin-layer sample, so that the amount of the sample to be detected can be reduced, and the paper base plays a certain sample pretreatment role to improve the anti-interference capability of the sensor; the potential salinity sensor provided by the invention can be used for detecting the salinity of the horizontal plane and the vertical section of the sediment in the coastal zone, and specifically comprises the following steps:
1. the invention realizes the direct detection of the salinity in the coastal zone sediment environment, provides a brand-new potential salinity detection method, and improves the limitations of the traditional indirect detection methods such as conductivity, optical refraction and the like. And is expected to be further expanded and applied in the aspects of detecting various ion concentrations and the like in the environment of seawater/coastal zone sediments.
2. According to the invention, the paper base is added into the sensor, so that the sample amount is effectively reduced, the anti-interference capability of the sensor is improved, and the in-situ salinity detection of the horizontal plane and the vertical section of the coastal zone sediment is realized.
3. The invention has the advantages of low cost, simple structure and simple and convenient operation. The sensor consists of three parts in total, and only the potential value needs to be read. The total cost of not including potentiometers is less than 6RMB and this is the cost calculated for laboratory ordering, with further cost reductions expected after commercial large-scale ordering and optimization.
4. The salinity test method provided by the invention is suitable for detecting the salinity of the coastal zone sediment environment, and can be further extended to the salinity test of various complex matrixes, such as blood plasma, various tissues and the like.
Drawings
FIG. 1 is a schematic diagram of the design and assembly of a vertical-section potential salinity sensor in an embodiment of the present invention.
FIG. 2 is a schematic diagram of the design and assembly of the planar potential salinity sensor according to the embodiment of the present invention.
Fig. 3 shows the potential response (fig. a) and the calibration curve (fig. B) of the cation electrode and the anion electrode according to the embodiment of the present invention.
FIG. 4 is the potential response (FIG. A) and the calibration curve (FIG. B) of the potential salinity sensor at 1-100 deg. according to the embodiment of the present invention.
Fig. 5 shows the potential response (fig. a) and the calibration curve (fig. B) of the potential salinity sensor of the embodiment of the present invention at 19, 19.5, 20, 38, 39, 40, 76, 78, 80, 94, 97, 100 °, and fig. C is a partially enlarged view of the calibration curve.
FIG. 6 shows K in an embodiment of the present invention + (A-a)、Na + (A-b)、Ca 2+ (A-c)、Mg 2+ (A-d)、 SO 4 2- (C-a) and Cl - (C-b) potential response diagram and K + 、Mg 2+ 、Ca 2+ The selectivity coefficient of (a).
FIG. 7 is the potential response (B) of the cation electrode in the NaCl solution (a) and the simulated seawater and the potential response (A) of the anion electrode in the NaCl solution (d) and the simulated seawater (c) and the calibration curve (B) in the example of the present invention.
FIG. 8 shows the potential variation of the potential salinity sensor in simulated seawater with different pH values according to the embodiment of the present invention.
FIG. 9 is a graph showing the change of potential of the potential salinity sensor at different temperatures (graph A) and the slope (graph B) and intercept (graph C) of the calibration curve with the change of temperature according to the embodiment of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The following examples were conducted in accordance with conventional methods and conditions, and experimental methods without specifying specific conditions were used.
The integrated paper-based potential salinity sensor is not influenced by environmental turbidity, so that the size of an electrode can be reduced, the amount of a sample to be detected can be reduced, and meanwhile, the paper base is used as a sample passage, so that the amount of the sample to be detected can be reduced, and the paper base plays a certain sample pretreatment role to improve the anti-interference capability of the sensor; in addition, because the seawater is composed of various ions and the matrix is complex, the salinity in the seawater sediment can be quickly detected by referring to the formula 1 during the actual seawater salinity detection.
Using the sensor of the invention wherein the cation (Na) + 、K + 、Mg 2+ And Ca 2+ ) And anions (Cl) - ) Potential responses are generated at the cation electrode and the anion electrode respectively, the principle is based on a Nernst equation, and the Nernst equation is corrected through ions and temperature so as to realize salinity detection.
During testing, the paper base in the sensor is used as a sample passage, and a sample solution is introduced into the sensor, so that the electrode of the sensor generates potential change. During measurement, an electrochemical system is used for recording the potential change between the positive electrode and the negative electrode on the salinity sensor.
The sensor is formed by performing sandwich-like assembly on a cation electrode, an anion electrode and a paper base, wherein the cation electrode is connected with the positive electrode of a potentiometer, and the anion electrode is connected with the negative electrode of the potentiometer. The positive electrode may be connected to an anionic electrode, the negative electrode may be connected to a cationic electrode, and the potential of the potentiometer is negative when the potentiometer is connected to the positive electrode.
Example 1
The salinity detection sensor suitable for the coastal zone sediment environment comprises a cation electrode, an anion electrode and a thin layer sample feeding device, wherein the thin layer sample feeding device is arranged between the anion electrode and the cation electrode, and the salinity detection sensor is suitable for the coastal zone sediment environment and comprises a cation electrode, an anion electrode and a thin layer sample feeding device, and the thin layer sample feeding device is arranged between the anion electrode and the cation electrode; wherein, the thin layer sample injection device is a material capable of spontaneously absorbing a sample.
The base material of the thin layer sample injection device is filter paper (with various sizes and thicknesses), a filter membrane and cloth strips, and the core of the base material is capable of spontaneously sucking a sample. In the examples, filter paper was used.
And the corresponding positions of the top ends of the cation electrode and the anion electrode are respectively coated with the response materials of the corresponding electrodes.
Example 2
Preparing a horizontal surface potential salinity sensor:
1. and (4) preparing a cation electrode.
1) Electrode material-Cu 3 [Fe(CN) 6 ] 2 ·nH 2 O (CuHCF) preparation: adding 0.1M CuSO 4 ·5H 2 O and 0.05M K 3 Fe(CN) 6 After stirring at room temperature, 50mL of ultrapure water was added and mixed to form a cloudy brown solution. And (3) carrying out ultrasonic treatment for 30min, standing for 12h, washing the obtained precipitate for three times, drying the precipitate at 70 ℃ for 24h, and grinding the obtained CuHCF into fine powder.
Grinding the obtained CuHCF fine powder with carbon slurry (600 μ L, shengtianfeng technology) and dilute lotion (300 μ L, shengtianfeng technology) to obtain the cationic electrode material.
2) Preparing a cation electrode matrix: cutting an ITO glass plate of 1X 5cm by taking the ITO glass plate as a matrix, covering a PTFE adhesive tape on the conductive surface, and reserving 1X 1cm 2 Leaving 1 x 0.5cm at one end 2 Position (1 x 0.5 cm) 2 Is connected with the positive pole of the potentiometer);
3) Preparation of a cation electrode: 60mg of the obtained cation electrode material was uniformly coated on the reserved 1X 1cm of the substrate 2 A position. Then calcining at 120 ℃ for 30min to prepare the electrode.
2. And (4) preparing an anion electrode.
1) Electrode material: selecting a commercial Ag/AgCl slurry,
2) Preparing an anion electrode matrix: cutting an ITO glass plate of 1X 5cm by taking the ITO glass plate as a matrix, covering a PTFE adhesive tape on the conductive surface, and reserving 1X 1cm 2 Leaving 1 x 0.5cm at one end 2 Position (1 x 0.5 cm) 2 Is connected with the negative pole of the potentiometer);
3) Preparation of an anion electrode: 60mg of Ag/AgCl slurry was uniformly applied to the reserved 1 x 1cm of the substrate 2 Location. Then calcining at 120 ℃ for 30min to prepare the electrode.
3. And (5) assembling the horizontal plane potential salinity sensor.
Referring to fig. 2, the sensor is similar to a sandwich, the cation electrode and the anion electrode are separated from two sides, and the sandwich is a thin layer sample introduction device (paper) fixed by a clamp.
Preparing a vertical section potential salinity sensor:
1. and (4) preparing a cation electrode.
1) Preparation of electrode material-CuHCF: the electrode material is consistent with the level potential salinity sensor.
2) Preparing a cation electrode matrix: with an ITO glass plate as a substrate, as shown in FIG. 9, 1X 5cm was cut 2 (position A) and 11 x 1cm 2 (B site) ITO glass plate, one conductive side was covered with PTFE tape. The ITO was then immersed in concentrated hydrochloric acid to eliminate the indium tin oxide at B, where the resistance was measured with a multimeter to ensure complete elimination. Cutting the tape at position A into 1X 1cm 2 And 1 × 0.5cm 2 Two regions (fig. 1). 1 × 1cm 2 The zone for coating with electrode material, 1 × 0.5cm 2 The region is connected to a potentiometer. The electrode calcination process is consistent with that of a planar potential sensor. Position B with 2 strips of PTFE tape (11X 0.2 cm) 2 ) Covering to ensure waterproof performance (fig. 1).
3) Preparation of a cation electrode: 60mg of the above-obtained cationic electrode material was uniformly applied to 1X 1cm of the A matrix 2 A position. Then calcined at 120 ℃ for 30min to prepare the electrode.
2. And preparing an anion electrode.
1) Electrode material: selecting a commercial Ag/AgCl slurry,
2) Preparation of an anion electrode matrix: the preparation process is consistent with that of the cation electrode of the vertical profile potential salinity sensor;
3) Preparation of an anion electrode: 60mg of Ag/AgCl slurry was uniformly applied to the reserved 1X 1cm of the substrate 2 Location. Then calcined at 120 ℃ for 30min to prepare the electrode.
3. And (4) assembling the vertical profile potential salinity sensor.
Referring to fig. 1, the sensor is similar to a sandwich, the cation electrode and the anion electrode are separated from two sides, and the sandwich is a thin layer sample introduction device (paper) fixed by a clamp. The actual measurement requires waterproofing treatment using a sealing film. The B site is inserted into the deposit and can be measured over a depth range of 1-10 cm.
Example 3
The salinity detection sensor suitable for the coastal zone sediment environment comprises a cation electrode, an anion electrode and a thin layer sample injection device, wherein the thin layer sample injection device is arranged between the cation electrode and the anion electrode; wherein, the thin layer sample injection device is a material capable of spontaneously absorbing a sample.
And the corresponding positions of the top ends of the cation electrode and the anion electrode are respectively coated with the response materials of the corresponding electrodes.
The cation electrode and the anion electrode were subjected to a potential test in advance.
Respectively assembling a cation electrode and an Ag/AgCl (3M KCl) reference electrode, assembling an anion electrode and the Ag/AgCl (3M KCl) reference electrode, and immersing the electrodes into a detection pool, wherein the detection pool is filled with NaCl solution. The potential change was recorded by a potentiometer.
Preparation of a level sensor:
1) Preparing an electrode substrate: cutting the conductive substrate into a T shape, coating corresponding electrode materials on the transverse part of the substrate, and positioning the longitudinal part of the substrate at the middle position of the transverse part or deviating from the middle position and leaning against any end of the transverse part;
or cutting the conductive substrate into a 'one' shape;
2) Preparation of cation electrode and anion electrode: taking the prepared electrode matrix as a cation electrode matrix and an anion electrode matrix respectively, and coating response materials of the electrodes on the transverse and longitudinal intersection of the matrix respectively by taking the longitudinal part as a conductive surface wider than the transverse part;
or, respectively coating the response materials of the electrodes on the conductive substrates cut into the shape of a straight line;
then calcining at 120 ℃ for 30min to respectively obtain a cation electrode and an anion electrode of the salinity sensor; placing the two calcined electrodes in an overlapping manner to enable the positions of the response materials of the coated electrodes to be mutually and correspondingly overlapped;
3) Preparing a sensor: a material which can spontaneously suck a sample and is used as a sample passage is arranged between the electrodes overlapped in the step 2).
The surface of the cation electrode and the surface of the anion electrode facing the sample path are non-conductive surfaces;
as can be seen from FIG. 3A, the potential of the cation electrode increases with increasing salinity, and the potential of the anion electrode decreases with increasing salinity. From the calibration graph 3B, it is found that the potential response slopes of the cation electrode and the anion electrode are 52 and 52.2mV, respectively, close to the nernst response.
Example 4
The difference from example 3 is that the potential test is performed after the cation electrode and the anion electrode are assembled (level potential salinity sensor), i.e. a reference electrode is not used, and the potential test comprises the cation electrode, the anion electrode and a thin layer sample feeding device (paper). The positive electrode of the potentiometer is connected with the positive ion electrode, and the negative electrode of the potentiometer is connected with the negative ion electrode.
NaCl solutions with different salinity of 1 degree, 5 degrees, 10 degrees, 50 degrees and 100 degrees are respectively prepared, 1mL of NaCl solutions with different salinity are respectively sucked into a culture dish, the paper base part of the potential salinity sensor is contacted with the solutions, and then a stable reading is recorded through a potentiometer. The real-time response curve and the calibration curve are shown in FIG. 4.
The real-time response curve is shown in FIG. 4A, the calibration curve is shown in FIG. 4B, and as can be seen from FIG. 4, the potential value gradually increases with the increase in NaCl concentration. The response slope was 105.1mV, which is very close to the slope stack of the cation and anion electrodes, indicating that the potential salinity sensor can detect both cation and anion concentrations (activity).
Example 5
The difference from example 4 is that the resolution test of the potential salinity sensor was performed using the level sensor prepared as described in example 2 for detecting solutions of NaCl of different salinity.
The NaCl solutions with different salinity are prepared into 19, 19.5, 20, 38, 39, 40, 76, 78, 80, 94, 97 and 100 degrees of NaCl solutions with different salinity respectively, then 1mL of NaCl solutions with different salinity is sucked into a culture dish respectively, the paper base part of the potential salinity sensor is contacted with the solutions, and then a stable reading is recorded through a potentiometer. The real-time response curve and the calibration curve are shown in FIG. 5.
The real-time response curve is shown in fig. 5A, the calibration curve is shown in fig. 5B, and fig. 5C is a partially enlarged view of the calibration curve. It can be seen from fig. 5 that the potential salinity sensors can distinguish solutions of NaCl of different salinity. Therefore, the resolutions of the potential salinity sensor in the intervals of 1-20 degrees, 21-40 degrees, 41-80 degrees and 81-100 degrees are respectively 0.5 degrees, 1 degree, 2 degrees and 3 degrees.
Example 6
Example 5 was different in that the selectivity of the positive and negative ion electrodes in the device was tested by replacing the solution to be tested.
The positive electrode of the potentiometer in the assembled detection device is respectively connected with a cation/anion electrode, the negative electrode of the potentiometer is connected with an Ag/AgCl (3M KCl) reference electrode to assemble different detection devices, the electrodes are inserted into detection cells containing different samples with different concentrations to test the selectivity coefficients of the cation electrode and the anion electrode in the device, wherein the samples are NaCl and MgCl 2 、CaCl 2 KCl and MgSO 4 Solutions were prepared separately for 10 samples -5 、10 -4 、10 -3 、10 -2 、10 -1 And 1M series concentrations.
Cationic electrode and Ag/AgCl (3M KCl) immersion in NaCl, mgCl 2 、CaCl 2 Performing open-circuit potential test on KCl; anionic electrode and Ag/AgCl (3M KCl) immersion in NaCl and MgSO 4 An open circuit potential test was performed. The selectivity coefficient was calculated from the potential obtained by the cation electrode and the anion electrode, respectively, and calculated with reference to the following equation.
In the formula, E I And E J Potential response values, z, of the ions to be measured and the interfering ions, respectively I And z J The charge numbers of the ions to be measured and the interfering ions, a I And a J The activity of the ions to be detected and the activity of the interfering ions are respectively, F is a Faraday constant, and R is an ideal gas constant.
From FIGS. 6A-B, it can be seen that Na + To K + 、Ca 2+ And Mg 2+ Has selectivity coefficients of 0.27, -0.24 and-0.97, respectively, so that the cation electrode is actually opposite to Na + 、K + 、Ca 2+ And Mg 2+ There is a potential response. As shown in fig. 6C, the pair of anion electrodes SO 4 2- Almost no response, so the selectivity coefficient cannot be calculated, and the anionic electrode is only sensitive to Cl - There is a corresponding.
Example 7
The apparatus assembled in example 5 above was used to separate NaCl solutions of different salinity from simulated seawater.
The salinity of the simulated seawater is 35 degrees, the ratio is NaCl: mgCl 2 ：MgSO 4 ：CaCl 2 : KCl =0.42M:0.06M:0.03M: 0.12M:0.11M, and concentrating and diluting according to the proportion under other salinity.
NaCl solutions with different salinity and simulated seawater with different salinity of 1 degree, 5 degrees, 10 degrees and 50 degrees are respectively configured, the assembled cation electrode and anion electrode are respectively immersed into a detection pool together with an Ag/AgCl (3M KCl) reference electrode, and the detection pool is respectively filled with the NaCl solutions with different salinity or the simulated seawater. The stable reading is then recorded by a potentiometer.
The real-time response curve is shown in fig. 7A, the correction curve is shown in fig. 7B, and it can be seen from fig. 7 that the cation/anion electrode has a potential difference value when detecting the simulated seawater and the NaCl solution with the same salinity, the potential value of the cation electrode is higher, and the potential value of the anion electrode is lower when detecting the NaCl solution. It can be seen from fig. 7B that the potential difference between the cation electrode and the anion electrode is 5.6mV and 0.9mV, because the simulated seawater is composed of a plurality of salts, different salts have different relative masses, and ions of different valences have different potential responses.
In this example, the sodium electrode is referred to as Na + 、K + 、Ca 2+ And Mg 2+ All have potential response, chlorine electrode is connected with Cl - There is a potential response. Will K + 、Ca 2+ And Mg 2+ The ion concentration is converted to NaCl concentration, simulating seawater at 35 deg. (NaCl: mgCl) 2 ：MgSO 4 ：CaCl 2 : KCl =0.42M:0.06M:0.03M: 0.12M: 0.11M) and NaCl solution.
Cation electrode calculation:
anion electrode calculation:
in the formula, E 1 And E 2 Initial potential values, C, for the cation and anion electrodes, respectively Na -C Cl Is Na + -Cl - Molarity at salinity of 35 °. R is an ideal gas constant, T is temperature, n is the electron transfer number in the electrode reaction, and F is a Faraday constant.
The theoretical potential difference values (35 ℃ NaCl solution and simulated seawater) of the cation electrode and the anion electrode are respectively 5.5mV and 1mV through calculation according to the formula. Whereas the difference was actually measured to be 5.6mV and 0.9mV from FIGS. 7A-B, respectively. This is very close to theory, indicating that the potential response equation described above is in line with the reality.
Example 8
The difference from example 3 is that the samples are NaCl solutions of different pH.
NaCl (35 ℃) solutions at pH 2 to 12 were prepared, 1mL of each solution was aspirated into a petri dish, the paper-based portion of the potential salinity sensor was contacted with the solution, and then a stable reading was recorded by a potentiometer.
The potential response is shown in figure 8. It can be seen from fig. 8 that the salinity acquired by the potential salinity sensor in the range of pH 4-10 hardly changes, and the salinity has less deviation in the range of pH 2-10, and the potential salinity sensor can directly detect without being influenced by the pH of the sediment considering the actual coastal zone sediment environment.
Example 9
The difference from the embodiment 3 is that the response of the potential salinity sensor is changed at different temperatures. The water bath adjusts the temperature of the sample to simulate the temperature change when detecting the salinity of the sediment in the coastal zone on site.
Preparing 1, 5, 10 and 50-degree simulated seawater solutions respectively, putting the sample solution into a water bath (5 ℃), detecting the sample by a potential salinity sensor, and reading out readings by a potentiometer. Then adjusting the temperature of the water bath kettle to 15 ℃, 25 and 35 ℃, and repeating the detection process.
The potential correction curve at each temperature is shown in fig. 9A, the slope change of the potential correction curve at each temperature is shown in fig. 9B, and the intercept change of the potential correction curve at each temperature is shown in fig. 9C. As can be seen from FIG. 9, the slope of the potential response curve varies with temperature by 0.35 mV/deg.C, and the intercept varies by 1.38 mV/deg.C.
Example 10
The device comprises a potential salinity sensor, a potentiometer, a temperature measuring gun, a conductivity salinity meter and an optical refraction salinity meter. The positive electrode of the potentiometer is connected with the sodium electrode, the negative electrode of the potentiometer is connected with the chlorine electrode, the potentiometer records potential change, and the temperature measuring gun records the surface temperature of the electrode. The test was carried out using a level sensor prepared as described in example 2, where the sample solution was real seawater samples of varying salinity, the samples being taken from the strolling river in the smoke counter city of Shandong province.
1. Potential salinity sensor for measuring real seawater salinity
The real seawater samples are respectively marked as 1-6, 1mL of solution is respectively sucked into a culture dish, the paper base part of the potential salinity sensor is contacted with the solution, and then a stable reading is recorded through a potentiometer. And then reading the temperature of the surface of the sensor through a temperature gun, and obtaining the salinity through algorithm correction.
2. Conductivity salinity meter for measuring true seawater salinity
And respectively immersing the conductivity salinity meter into No. 1-6 real seawater samples, and recording readings of the conductivity salinity meter after the readings are stable.
3. Optical refraction salinity meter for measuring real seawater salinity
Respectively sucking No. 1-6 real seawater samples through a suction pipe, dripping the samples onto an optical refraction salinity meter, and reading out readings of the optical refraction salinity meter through an ocular lens.
The salinity value measured by the potential salinity sensor is very close to the value obtained by the conductivity salinity meter, and the data read by the optical refraction salinity meter has certain deviation. At present, the conductivity salinity meter is the gold standard for salinity measurement, so that the potential salinity sensor has certain reliability in salinity measurement.
TABLE 1 optical refraction salinity meter, conductivity salinity meter and electric potential salinity sensor for measuring real seawater
Example 11
The difference from example 3 is that here the salinity (electrochromism) is read visually in order to eliminate the potentiometer.
Manufacturing a PANI electrochromic device: polyaniline (PANI) is electrodeposited on an ITO electrode according to the existing mode, then a gel electrolyte layer is covered, and then a layer of ITO electrode is covered to form the PANI electrochromic device, and the color of the device can change along with the change of an external potential.
The potential salinity sensor described in the above embodiments was connected to a PANI electrochromic device. 1, 5, 10, 50 and 100 degrees of simulated seawater solution are respectively configured, the potential salinity sensor is contacted with a sample, the color of the PANI device can be changed into yellow and purple along with the increase of salinity, and the salinity is read.
Example 12
The difference from example 3 is that here the salinity (electrochromism) is read visually in order to eliminate the potentiometer.
WO 3 Electric fieldManufacturing a color-changing device: electrodeposition of tungsten trioxide on ITO electrodes (WO) 3 ) Then covering with gel electrolyte layer and then with ITO electrode to form WO 3 The color of the electrochromic device can change along with the change of the external potential.
The potential salinity sensor is connected with WO 3 The electrochromic device is connected. Respectively preparing 1, 5, 10, 50 and 100 deg. simulated seawater solution, contacting potential salinity sensor with sample, and measuring the salinity by WO 3 The device color turns blue as the salinity increases, and the salinity is read.
Example 13
The difference from example 3 is that here, in order to eliminate the potentiometer, a visual readout of the salinity (electrochromism) is carried out.
And manufacturing a PEDOT electrochromic device. And (3) electrodepositing polyethylene dioxythiophene (PEDOT) on the ITO electrode, then covering the gel electrolyte layer, and then covering a layer of ITO electrode to form the PEDOT electrochromic device, wherein the color of the device can change along with the change of the external potential.
The potential salinity sensor described in the above example was connected to a PEDOT electrochromic device. 1, 5, 10, 50 and 100 degrees of simulated seawater solution are respectively configured, the potential salinity sensor is contacted with a sample, the color of the PEDOT device changes to blue along with the increase of salinity, and the salinity is read.
Example 14
The difference from example 3 is that here the salinity (electrochromism) is read visually in order to eliminate the potentiometer.
Manufacturing a PW electrochromic device: and (3) electrodepositing Prussian blue (PW) on the ITO electrode, then covering the gel electrolyte layer, and then covering a layer of ITO electrode to form a PW electrochromic device, wherein the color of the device can change along with the change of the external potential.
The potential salinity sensor described in the above embodiment was connected to a PW electrochromic device. 1, 5, 10, 50 and 100-degree simulated seawater solutions are respectively configured, a potential salinity sensor is in contact with a sample, the color of the PEDOT device can be whitened along with the rise of salinity, and the salinity can be read.
Example 15
The difference from the embodiment 3 is that the potential salinity sensor array is formed, and the electrodes are connected in series in a multi-stage mode to perform potential superposition so as to improve the resolution. The device comprises a plurality of potential salinity sensors and potentiometers.
Taking the horizontal sensor described in example 2 as an example, a plurality of cation electrodes and anion electrodes were designed, and a potential salinity sensor array was constructed by assembling 10 sets of electrodes in a series circuit configuration with one cation electrode and anion electrode as a set of electrodes. Compared with the potential salinity sensor, the potential response of the potential salinity sensor array is 10 times that of the potential salinity sensor, and the salinity resolution can be improved.
Example 16
The difference from the embodiment 15 is that the current salinity sensor array is provided, and the electrodes are connected in parallel in a multi-stage mode to perform current superposition so as to improve the resolution. The device comprises a plurality of current salinity sensors and an ammeter.
Taking the horizontal sensor described in example 2 as an example, the current of the cation electrode and the anion electrode also changes in response when detecting salinity. A plurality of cation electrodes and anion electrodes are designed, one cation electrode and anion electrode are used as a group of electrodes, and 10 groups of electrodes are assembled according to the design of a parallel circuit to form the current salinity sensor array. Compared with the current salinity sensor, the potential response of the current salinity sensor array is 10 times of the current signal amplification, and the salinity resolution can be improved.
Example 17
The apparatus comprises a level sensor, a potentiometer and a temperature measuring gun as described in example 2. The positive electrode of the potentiometer is connected with the positive ion electrode, the negative electrode of the potentiometer is connected with the negative ion electrode, potential change is recorded through the potentiometer, and the temperature of the surface of the electrode is recorded through the temperature measuring gun. Here the sample is a dew on the surface of lotus leaves.
And (3) contacting the potential salinity sensor with dew on the surface of the lotus leaf, recording after the readout is stable, and calculating the salinity by a formula.
Example 18
The difference from example 17 is that the sample here is a bead on the surface of a seaside building.
And (3) contacting the potential salinity sensor with the surface water beads of the seaside building, recording after the readings are stable, and calculating the salinity by a formula.
Example 19
The difference from example 17 is that the sample here is a bead of a leaf of a seaside tree.
And (3) contacting the potential salinity sensor with the leaves and water drops of the seaside trees, recording after the readings are stable, and calculating the salinity by a formula.
Example 20
A vertical sensor was prepared as described in example 2 and the potential measurements were performed after the cation electrode and anion electrode were assembled (vertical profile potential salinity sensor), i.e. without the use of a reference electrode, including a cation electrode, an anion electrode and a thin layer sample injection device (paper). The positive electrode of the potentiometer is connected with the positive ion electrode, and the negative electrode of the potentiometer is connected with the negative ion electrode. The sample was estuary sediment.
And vertically inserting the profile potential salinity sensor into the sediment, recording after the readout is stable, and calculating the salinity according to a formula 1.
Claims (10)
1. A salinity detection sensor suitable for coastal zone sediment environment, characterized by: the sensor comprises a cation electrode, an anion electrode and a thin-layer sample introduction device, wherein the thin-layer sample introduction device is arranged between the anion electrode and the cation electrode; wherein, the thin layer sample introduction device is a material capable of spontaneously absorbing a sample.
2. The salinity test sensor adapted for coastal zone sediment environment of claim 1, wherein: and the corresponding positions of the top ends of the cation electrode and the anion electrode are respectively coated with the response materials of the corresponding electrodes.
3. The salinity test sensor adapted for coastal zone sediment environment of claim 2, wherein: the cation response material in the cation electrode is copper hexacyanoferrate (Cu) 3 [Fe(CN) 6 ] 2 ·nH 2 O)、Manganese oxide complex (MnO) 2 、Na x Mn y O z (x, y, z may be the same or different and are selected from 1-5)), vanadium oxide complex (Na) x V y O z (x, y, z may be the same or different and are selected from 1-5)), cobalt oxide (Co 3 O 4 ) Titanium oxide complex (Na) x Ti y O z (x, y, z may be the same or different and are selected from 1-5)), a titanium phosphate complex (NaTi) 2 (PO 4 ) 3 ) Vanadium phosphate complex (Na) 3 V 2 (PO 4 ) 3 ) Iron phosphate complex (Na) 2 FeP 2 O 7 ) Prussian blue (PW);
the anion response material in the anion electrode is silver (Ag), silver chloride (AgCl), silver-silver chloride (Ag/AgCl), bismuth (Bi), bismuth oxychloride (BiOCl) and polypyrrole (PPy).
4. The salinity test sensor adapted for coastal zone sediment environment of claim 1, wherein: the thin layer sample injection device is paper, a filter membrane, cloth, a porous stone plate, sponge, a porous stone plate, porous glass, porous ceramic or functionalized paper.
5. A method for preparing a salinity detecting sensor suitable for coastal zone sediment environment according to claim 1, which is characterized in that:
1) Preparing an electrode substrate: cutting the conductive substrate into a T shape, wherein the T-shaped vertical edge is positioned in the middle of the transverse edge or is eccentrically arranged with the middle of the transverse edge; coating the surface of one side of the T-shaped transverse edge with a corresponding electrode material;
or cutting the conductive substrate into a 'one' shape;
2) Preparation of cation electrode and anion electrode: taking the prepared electrode matrixes as a cation electrode matrix and an anion electrode matrix respectively, coating response materials of the electrodes at the intersection of the transverse edge and the vertical edge of the T-shaped matrixes of the cation electrode matrix and the anion electrode matrix, wherein the coating width of the response materials is the same as that of the vertical edge;
or, respectively coating the response materials of the electrodes on the conductive substrates cut into the shape of a straight line;
then calcining at 120 ℃ for 30min to respectively obtain a cation electrode and an anion electrode of the salinity sensor; placing the two calcined electrodes in an overlapping manner to enable the longitudinal parts of the electrodes to be overlapped;
3) Preparing a sensor: and 3) arranging a material which can spontaneously suck a sample and is used as a thin layer sample introduction device between the overlapped electrodes in the step 2).
6. A method for preparing a salinity test sensor suitable for coastal zone sediment environment according to claim 5, which is characterized in that: the surface of the cation electrode and the surface of the anion electrode facing the thin layer sample injection device are non-conductive surfaces; the cross edge and the vertical edge of the base body on the conductive surfaces of the cation electrode and the anion electrode are coated with the response material of the electrodes, and the coating width of the response material is the same as that of the vertical edge.
7. A method for detecting salinity of coastal zone sediment environment using the sensor of claim 1, wherein: inserting the sensor of claim 1 into coastal zone sediment to be detected, allowing the sample to contact with the sample through a material capable of spontaneously sucking the sample in a thin-layer sample feeding device, allowing cations in the sample to act on a cation electrode, allowing anions in the sample to act on an anion electrode to generate potential response, and calculating the salinity of the sample according to the potential response signal.
8. A method of salinity according to claim 7, wherein: the potential value of the cation electrode in the sensor is increased along with the increase of salinity, the potential value of the anion electrode is reduced along with the increase of salinity, the sample salinity is obtained through calculation of the generated potential value, and the formula (formula 1) is calculated according to the potential response signal
Wherein A and B are constants and are obtained by calibrating the potential salinity sensor;C Na 、C k 、C ca 、C Mg 、C Cl is Na + 、K + 、Ca 2+ 、Mg 2+ 、Cl - Molarity at salinity of 35 °; t is the sample temperature.
9. A method of salinity according to claim 7, wherein: when detecting coastal zone sediment, a plurality of sensors as claimed in claim 1 can be connected in series or in parallel to perform potential superposition, so that the resolution of the sensors is improved, and the salinity detection precision is further improved.
10. A method of salinity according to any of claims 7 to 9, wherein: when the coastal zone sediment is detected, the potential sensor is connected with the electrochromic material in parallel, and the potential response drives the potential change of the electrochromic material, so that the color change is caused to carry out visual display of the potential response.
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