CN116609411B - Method for improving slope sensitivity of solid contact type ion selective electrode and application thereof - Google Patents
Method for improving slope sensitivity of solid contact type ion selective electrode and application thereof Download PDFInfo
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Abstract
The invention relates to the field of electrochemical sensors, in particular to a method for improving slope sensitivity of a solid contact type ion selective electrode and application thereof. The photo-thermal nano material is used as a solid contact conducting layer of the solid contact ion selective electrode, the pulsed near infrared laser is used for irradiating the solid contact ion selective electrode, the temperature change and the transient current are regulated, the potential response slope is improved, and the high-sensitivity slope response of the electrode is realized. Compared with the traditional potential measurement under the zero-current condition, the method disclosed by the invention has the advantages that the electrode temperature is increased by regulating and controlling the solid contact conductive layer through the pulse near infrared laser, the slope sensitivity is improved by utilizing the generated transient current, the limit of the traditional Nernst slope is broken through, and the method is more beneficial to the high-sensitivity and high-precision measurement of the ion concentration.
Description
Technical Field
The invention relates to the field of electrochemical sensors, in particular to a method for improving slope sensitivity of a solid contact type ion selective electrode and application thereof.
Background
The solid contact ion selective electrode is generally composed of a conductive substrate, a solid contact conductive layer and an ion selective sensitive film. Wherein the solid contact conductive layer plays a role of ion-electron conduction for stabilizing the electrode potential response; ion selective sensitive membranes are used to identify ions. Solid contactThe detection principle of the ion selective electrode is that the relation between the response potential of the sensitive film and the activity of the ion to be detected accords with the Nernst equation, the response slope is + -RT/nF, and R is the molar gas constant (8.314J. Mol) -1 ·K -1 ) T is the thermodynamic temperature and F is the Faraday constant (96486.7℃ Mol -1 ) N is the charge number of the ion to be measured. Therefore, the slope sensitivity of the solid contact type ion selective electrode is closely related to the temperature, and the improvement of the temperature of the electrode is beneficial to improving the slope sensitivity, namely the high-sensitivity and high-precision detection of ions to be detected is more beneficial.
There are two ways to increase the electrode temperature reported at present: firstly, heating and heating the solution to be tested and an electrochemical system integrally; and secondly, only the surface or the nearby area of the electrode is heated. The former needs to design a special detection pool, the device is complex, and the whole system has a slower heating process; the latter only heats the electrode or the adjacent solution, and can rapidly raise the temperature of the electrode without affecting the overall temperature of the solution to be measured. Among them, the beam heating method is an important non-constant temperature heating method. However, the laser heating method reported at present basically adopts laser with ultraviolet or visible light wavelengths, and long-term irradiation of the light with the wavelengths to the ion-selective sensitive film can cause photolysis of sensitive film components such as an ionophore, an ion exchanger, a plasticizer and the like to generate various byproducts, so that the performances of electrode selectivity, linear range, detection limit, service life and the like are affected. Therefore, development of a gentle laser irradiation method and effective increase in electrode temperature are very necessary for realizing high-sensitivity potential measurement of ion-selective electrodes.
Compared with ultraviolet light (50-80 kcal/mol), near infrared laser presents a low-energy excited state (about 35 kcal/mol), and is widely applied in the field of biomedical imaging, but research and application in the field of solid contact type ion selective electrodes have not been carried out, particularly, the temperature of the electrodes is raised by irradiation of the electrodes with near infrared laser, and the generated transient current is utilized to regulate the response of ions on an ion selective sensitive film, so that improvement of the slope sensitivity of potential response has not been reported.
Disclosure of Invention
The invention aims to provide a method for improving slope sensitivity of a solid contact type ion-selective electrode and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for improving slope sensitivity of solid contact ion selective electrode uses photo-thermal nano material as solid contact conductive layer of solid contact ion selective electrode, uses pulse near infrared laser to irradiate solid contact ion selective electrode, adjusts temperature change and generates transient current, improves potential response slope, and realizes high sensitivity slope response of electrode.
Further, a pulsed near infrared laser is utilized to pass through the ion selective sensitive membrane to reach the solid contact conductive layer; by means of the light-heat conversion effect, the temperature of the solid contact conducting layer after absorbing near infrared laser is increased, the surface temperature of the ion selective sensitive film is increased through the thermal diffusion effect, and meanwhile transient current generated by illumination is utilized to regulate and control the diffusion of ions to be detected into the ion selective sensitive film, so that a pulse potential value is obtained; and according to the relation between the pulse potential value and the ion activity logarithm, a response slope is obtained, and high-sensitivity and high-precision detection of ions is realized.
The pulsed near infrared laser is a laser of wavelength 808nm emitted by a near infrared laser; the pulse near infrared laser irradiates the solid contact ion selective electrode with a spot diameter of 1-10 mm and an irradiation time of 1-60 s.
The transient current is generated instantaneously when the pulse near-infrared laser irradiates the solid contact type ion selective electrode and is used for regulating and controlling the diffusion of ions to be detected into the ion selective sensitive film to obtain a pulse potential value; wherein the transient current density is 0.1-10A/m 2 。
The solid contact conductive layer is made of a material with photo-thermal effect, good conductivity and double-electric-layer capacitance and capable of conducting ions and electrons.
The solid contact conductive layer is made of mesoporous carbon, graphene, carbon nano tube or nano gold.
The device adopted by the method comprises a solid contact type ion selective electrode, a reference electrode, a near infrared laser, a potentiometer and a quartz sample cell; and near infrared laser emitted by the near infrared laser irradiates the solid contact type ion selective electrode through the quartz sample cell and the solution to be detected.
Use of the method for increasing the slope sensitivity of a solid contact ion-selective electrode in potentiometric detection.
A potential detection method, regard photo-thermal nano material as solid contact conductive layer of the solid contact ion selective electrode, utilize pulse near infrared laser to illuminate to the electrode, after the solid contact conductive layer absorbs near infrared laser, heat the ion selective sensitive membrane through the heat transfer, form a thin thermostatical layer between ion selective sensitive membrane and solution to be measured; and regulating and controlling the diffusion of the ions to be detected into the ion selective sensitive film by utilizing transient current generated by illumination to obtain a pulse potential value, and realizing quantitative detection of the ions to be detected according to the logarithmic relation between the pulse potential value and the ion activity.
The structure of the solid contact type ion selective electrode is a conductive matrix, a solid contact conductive layer and an ion selective sensitive film in sequence; the conductive matrix is a glassy carbon electrode, a gold electrode, a screen printing electrode or an ITO (indium tin oxide) electrode; the solid contact conductive layer is mesoporous carbon, graphene, a carbon nanotube or nano gold; the ion-selective sensitive membrane consists of a polymer membrane matrix, a plasticizer, an ionophore and an ion exchanger.
The invention has the following advantages:
(1) Compared with the traditional solid contact type ion selective electrode, the solid contact conductive layer provided by the invention has the ion-electron conduction effect, and the potential response performance of the electrode is improved by the characteristic that the solid contact conductive layer can absorb near infrared laser to generate heat.
(2) Compared with the traditional potential response, the potential response regulated by the pulse near infrared laser breaks through the limit of a Nernst equation, the response slope is obviously improved, and the high-sensitivity and high-precision measurement of the ion concentration is facilitated.
(3) Compared with the continuous near infrared laser illumination which only causes the electrode temperature to be increased, the pulse near infrared laser illumination provided by the invention not only plays a role in increasing the ion selective electrode temperature, but also further regulates and controls the diffusion of ions from a solution phase to be detected to an ion selective sensitive film phase by means of transient current generated by illumination, thereby increasing the potential response slope.
Drawings
Fig. 1 is a block diagram of a solid contact type calcium ion selective electrode according to an embodiment of the present invention.
Fig. 2 is a device diagram of a method for detecting a potential of a solid contact type ion selective electrode according to an embodiment of the present invention.
Fig. 3 is a graph showing a change in electrode temperature caused by irradiation of a near infrared laser on a solid contact type calcium ion selective electrode according to an embodiment of the present invention.
Fig. 4 is a graph showing the potential response of a solid contact type calcium ion selective electrode irradiated by a pulsed near infrared laser according to an embodiment of the present invention.
Fig. 5 is a graph showing a calibration curve of a solid contact type calcium ion selective electrode with or without pulsed near infrared laser irradiation according to an embodiment of the present invention, and an illustration is a graph showing a slope.
Fig. 6 is a graph comparing calibration curves of solid contact type calcium ion selective electrodes when pulse near infrared laser irradiation is performed at different contents of solid contact conductive layers of photo-thermal nano materials according to the embodiment of the invention, and the inset graph is a graph comparing slope.
Fig. 7 is a graph showing the potential response of a solid contact type ion selective electrode irradiated by a pulsed near infrared laser and a continuous near infrared laser according to an embodiment of the present invention, and the graph is a graph showing slope contrast.
Fig. 8 is a diagram illustrating a case where a pulsed near infrared laser irradiates a solid contact type ion selective electrode to generate a transient current according to an embodiment of the present invention.
In the figure, a 1-conductive matrix, a 2-photo-thermal nano material solid contact conductive layer, a 3-calcium ion selective sensitive film, a 4-solid contact calcium ion selective electrode, a 5-reference electrode, a 6-near infrared laser, 7-808-nm near infrared laser, an 8-potentiometer and a 9-quartz sample cell.
Detailed Description
The present invention is described in further detail below in conjunction with the detailed description, but does not limit the scope and application of the present invention. The materials, reagents and equipment used in the examples below, not specifically described, are conventional in the art and are commercially available to those skilled in the art.
The invention constructs the solid contact type ion selective electrode by taking the photo-thermal nano material as the solid contact conductive layer, irradiates the solid contact type ion selective electrode by using the pulse near infrared laser, improves the temperature of the electrode, and simultaneously improves the potential response slope by using transient current generated by illumination, thereby realizing high-sensitivity and high-precision detection of ions. Further, a pulsed near infrared laser is utilized to pass through the ion selective sensitive membrane to reach the solid contact conductive layer; by means of the light-heat conversion effect, the temperature of the solid contact conducting layer after absorbing near infrared laser is increased, the surface temperature of the ion selective sensitive film is increased through the thermal diffusion effect, and meanwhile transient current generated by illumination is utilized to regulate and control the diffusion of ions to be detected into the ion selective sensitive film, so that the improvement of potential response slope is realized.
Example 1
The preparation of the solid contact type calcium ion selective electrode 4 specifically comprises the following steps:
(1) Polishing an L-shaped glassy carbon electrode with the diameter of 3mm to a mirror surface with the surface of the electrode being bright by adopting 0.05 mu m alumina, and sequentially ultrasonically cleaning the electrode in ultrapure water, ethanol and ultrapure water for later use;
(2) Preparing a dispersion liquid containing 10 mg/mL disordered mesoporous carbon by adopting tetrahydrofuran, dripping 10 mu L of the dispersion liquid on the glassy carbon electrode in the step (1), and preparing the disordered mesoporous carbon modified glassy carbon electrode (namely, the disordered mesoporous carbon is taken as a photo-thermal nanomaterial) after the tetrahydrofuran is volatilized;
(3) 4.32 mg calcium ionophore II, 4.14 mg sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, 57.24 mg polyvinyl chloride and 110 μl of 2-nitrophenyl octyl ether are dissolved in 2 mL tetrahydrofuran to obtain a solution of calcium ion selective sensitive membrane 3;
(4) 200 mu L of the calcium ion selective sensitive film 3 solution prepared in the step (3) is dripped on the electrode in the step (2), and after drying in a constant temperature and humidity box, the solid contact type calcium ion selective electrode 4 (see figure 1) is prepared, and the electrode is arranged at the temperature of 1.0x10 -3 M CaCl 2 The solution was activated overnight for use.
Example 2
The construction of a device diagram for regulating and controlling potential response of a solid contact type ion selective electrode by near infrared laser comprises the following steps:
(1) Placing the solid contact type calcium ion selective electrode 4 in the step (4) in the example 1 serving as a working electrode and Ag/AgCl (3M KCl) serving as a reference electrode 5 in a quartz sample cell 9 filled with 0.5M NaCl solution, and connecting the working electrode and the reference electrode 5 with a CHI 660C electrochemical workstation respectively through leads;
(2) Placing a near infrared laser 6 (808 nm infrared laser MDL series) on one side of a quartz sample cell 9, and adjusting the distance between the near infrared laser 6 and the quartz sample cell 9 to enable 808nm near infrared laser 7 to form a light spot with the diameter of 3mm on a working electrode in the step (1) (see figure 2);
(3) The working power of the near infrared laser 6 is adjusted to 1.8W, the near infrared laser 6 is turned on, so that a laser spot irradiates the working electrode, and the temperature rise of the lower electrode with different laser irradiation time (0 s, 30 s, 60 s, 120 s, 240 s and 360 s) is recorded by a thermal infrared imager.
As a result, as shown in fig. 3, when the near-infrared laser irradiates 10 s, the temperature of the solid contact type calcium ion selective electrode 4 increases suddenly; the electrode temperature rise rate then gradually decreases and the temperature approaches equilibrium after 360 a s a. The result shows that the near infrared laser can effectively raise the temperature of the solid contact type calcium ion selective electrode 4, and provides a basis for the subsequent realization of high-temperature potential measurement.
Example 3
The measurement of the potential response of the pulsed near-infrared laser regulated solid contact ion selective electrode specifically comprises the following steps:
(1) The apparatus of example 2 was constructed using the solid contact type calcium ion selective electrode 4 prepared in example 1;
(2) A0.5M NaCl solution is placed in a quartz sample cell 9 as a background electrolyte, and CaCl is added dropwise into the sample cell 2 The concentration of the solution is 10 -3 M, measuring electrode potential response by adopting an open circuit potential technology of the CHI 660C electrochemical workstation; then, the working power of the near infrared laser 6 is adjusted to be 1.8W, a laser source is turned on, the electrode is immediately turned off after being irradiated by laser for 5 seconds, and the potential response of the electrode is measured in the process;
(3) According to the method of the step (2), the concentration is 3×10 in turn -3 、5×10 -3 、7×10 -3 、10 -2 M CaCl 2 The potential response of the electrodes without and with laser irradiation was measured. As a result of measurement, as shown in fig. 4, the potential without laser irradiation exhibited a steady-state response, while the potential with pulsed laser irradiation exhibited an impulse peak response.
By plotting the steady-state potential response and the calcium ion activity, the pulse peak potential value and the calcium ion activity respectively, as shown in fig. 5, the electrode potential under the laser irradiation and the electrode potential under the pulsed laser irradiation are both linear responses, and the response slopes are 27.1±0.6 mV/dec and 34.8±1.1 mV/dec in order (see the inset of fig. 5). This result shows that the use of pulsed laser effectively improves the response slope sensitivity of the solid-contact ion-selective electrode.
Example 4
The measurement of the potential response of the solid contact ion selective electrode regulated by the pulse near infrared laser under the condition of different contents of the photo-thermal material comprises the following steps:
(1) The procedure of example 1 was used to prepare a solid contact ion-selective electrode, except that 20 μl of 10 mg/mL disordered mesoporous carbon dispersion was applied dropwise to the glassy carbon electrode, as in example 1, to prepare a solid contact ion-selective electrode;
(2) The procedure (2) of example 3 was employed, in turn at a concentration of 10 -3 、3×10 -3 、10 -2 M CaCl 2 The electrode potential response under the irradiation of the pulsed laser was measured, and a corresponding calibration curve was obtained (see fig. 6). The electrode slope for 20. Mu.L of disordered mesoporous carbon was greater (38.1.+ -. 0.9 mV/dec) than for 10. Mu.L of disordered mesoporous carbon (34.8.+ -. 1.1 mV/dec).
The results show that the disordered mesoporous carbon content as the solid contact conductive layer has obvious influence on the slope sensitivity of the pulsed near infrared laser-controlled solid contact ion-selective electrode. The larger the content, the higher the slope sensitivity.
Example 5
The measurement of the potential response of the continuous near infrared laser regulated solid contact ion selective electrode specifically comprises the following steps:
(1) Preparing a solid contact ion selective electrode according to the procedure of example 4, and constructing an assay device using the procedure of example 3;
(2) A0.5M NaCl solution is placed in a quartz sample cell 9 as a background electrolyte, and CaCl is added dropwise into the sample cell 2 The concentration of the solution is 10 -3 M, measuring electrode potential response by adopting an open circuit potential technology of the CHI 660C electrochemical workstation; then, the working power of the near infrared laser 6 is adjusted to be 1.8 and W, a laser light source is turned on to continuously irradiate the electrode, and the potential response of the electrode is measured in the process;
(3) After the electrode potential in the step 2 is stabilized, caCl in the sample cell is sequentially changed 2 The solution concentrations were 3X 10 respectively -3 、10 -2 M, the potential response of the electrode under continuous laser irradiation is measured simultaneously. After the measurement is completed, the laser light source is turned off.
As a result of measurement, as shown in FIG. 7, the potential response gradient under continuous laser irradiation was 35.6.+ -. 0.4. 0.4 mV/dec. In comparison with the response slope under pulsed laser irradiation obtained in example 4, although the time of pulsed laser irradiation was shorter, the obtained response slope was larger than that under continuous laser irradiation. This result provides the experimental basis for the present invention.
Example 6
The measurement of transient current generated by pulsed near-infrared laser illumination solid contact type ion selective electrode specifically comprises the following steps:
(1) Constructing the device in the embodiment 4, adding a platinum wire as a counter electrode, and constructing a three-electrode system; the quartz sample cell 9 is placed with 3 multiplied by 10 -3 M CaCl 2 And 0.5M NaCl solution;
(2) Obtaining an open circuit potential value E by adopting an open circuit potential technology of the CHI 660C electrochemical workstation, setting a voltage value of a timing current technology as E, and measuring a current-time curve;
(3) The working power of the laser source is adjusted to be 1.8 and w, the light source is turned off after the near infrared laser source irradiates the working electrode for 5 seconds, and meanwhile, the current-time curve is measured.
As a result, as shown in fig. 8, the irradiation of the pulsed laser light produced a photocurrent of about 0.7 μa, and after the laser light was turned off, the current was gradually restored to the state before the irradiation of the light. This result indicates that the generation of transient current is an important factor in raising the slope of the potential response.
Example 7
The application of the pulse near infrared laser to regulate the potential response of the solid contact ion selective electrode specifically comprises the following steps:
(1) Collecting actual seawater sample (longitude: 121 DEG 26'21' ', latitude 37 DEG 31'16 ''), taking back to laboratory, and filtering with 0.22 μm filter membrane;
(2) The device of example 2 was set up using the solid contact type calcium ion selective electrode 4 prepared in example 1, and a 50 ml actual seawater sample was placed in the quartz sample cell 9. Determination of electrode potential response E using open circuit potential technique of CHI 660C electrochemical workstation 0 The method comprises the steps of carrying out a first treatment on the surface of the Then, the operating power of the near infrared laser 6 was adjusted to 1.8 and W, the laser light source was turned on, the electrode was immediately turned off after irradiating with laser light for 5 seconds, and the potential response of the electrode was measured simultaneously in this process (E 0 ′）；
(3) Adding 2.5. 2.5M calcium chloride solution 0.2. 0.2 ml into the actual seawater sample, and obtaining an open circuit potential E by adopting the method of the step (2) 1 And pulse near infrared illumination potential E 1 ′；
(4) Repeating the steps3) Twice, obtain E 2 、E 2 ' and E 3 、E 3 ′；
(5) According to E obtained 0 、E 0 ′、E 1 、E 1 ′、E 2 、E 2 ′、E 3 、E 3 The method adopts a standard addition method calculation method to obtain the calcium ion concentration of 6.72+/-0.22M in the actual seawater sample measured by the open circuit potential (namely, no illumination), the measurement precision is 3.3 percent, the calcium ion concentration of 6.91+/-0.09M in the actual seawater sample measured by the pulse near infrared illumination potential, and the measurement precision is 1.3 percent.
The result shows that the precision of the result of measuring the calcium ions is obviously improved due to the improvement of the slope of the solid contact type ion selective electrode by the pulse near infrared illumination.
Claims (7)
1. A method for improving slope sensitivity of a solid contact ion-selective electrode, which is characterized by comprising the following steps: the photo-thermal nano material is used as a solid contact conducting layer of the solid contact type ion selective electrode, the pulsed near infrared laser is used for irradiating the solid contact type ion selective electrode, the temperature change and the transient current are regulated, the potential response slope is improved, and the high-sensitivity slope response of the electrode is realized;
the photo-thermal nano material is disordered mesoporous carbon.
2. The method for increasing the slope sensitivity of a solid contact ion-selective electrode according to claim 1, wherein: using a pulsed near infrared laser to pass through the ion selective sensitive membrane to reach the solid contact conducting layer; by means of the light-heat conversion effect, the temperature of the solid contact conducting layer after absorbing near infrared laser is increased, the surface temperature of the ion selective sensitive film is increased through the thermal diffusion effect, and meanwhile transient current generated by illumination is utilized to regulate and control the diffusion of ions to be detected into the ion selective sensitive film, so that a pulse potential value is obtained; and according to the relation between the pulse potential value and the ion activity logarithm, a response slope is obtained, and high-sensitivity and high-precision detection of ions is realized.
3. A method of increasing the slope sensitivity of a solid contact ion-selective electrode according to claim 1 or 2, wherein: the pulsed near infrared laser is a laser of wavelength 808nm emitted by a near infrared laser; the pulse near infrared laser irradiates the solid contact ion selective electrode with a spot diameter of 1-10 mm and an irradiation time of 1-60 s.
4. The method for increasing the slope sensitivity of a solid contact ion-selective electrode according to claim 2, wherein: the transient current is generated instantaneously when the pulse near-infrared laser irradiates the solid contact type ion selective electrode and is used for regulating and controlling the diffusion of ions to be detected into the ion selective sensitive film to obtain a pulse potential value; wherein the transient current density is 0.1-10A/m 2 。
5. A method of increasing the slope sensitivity of a solid contact ion-selective electrode according to claim 1 or 2, wherein: the solid contact conductive layer is made of a material with photo-thermal effect, good conductivity and double-electric-layer capacitance and capable of conducting ions and electrons.
6. An apparatus for use in a method of increasing the slope sensitivity of a solid contact ion-selective electrode according to claim 1, wherein: the device comprises a solid contact type ion selective electrode, a reference electrode, a near infrared laser, a potentiometer and a quartz sample cell; and near infrared laser emitted by the near infrared laser irradiates the solid contact type ion selective electrode through the quartz sample cell and the solution to be detected.
7. The method for increasing the slope sensitivity of a solid contact ion-selective electrode according to claim 1, wherein: the structure of the solid contact type ion selective electrode is a conductive matrix, a solid contact conductive layer and an ion selective sensitive film in sequence; the conductive matrix is a glassy carbon electrode, a gold electrode, a screen printing electrode or an indium tin oxide electrode; the ion-selective sensitive membrane consists of a polymer membrane matrix, a plasticizer, an ionophore and an ion exchanger.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU972381A1 (en) * | 1979-01-05 | 1982-11-07 | Северо-Кавказский Филиал Всесоюзного Научно-Исследовательского И Конструкторского Института "Цветметавтоматика" | Pulse automatic polarograph |
| US6632349B1 (en) * | 1996-11-15 | 2003-10-14 | Lifescan, Inc. | Hemoglobin sensor |
| CN109187688A (en) * | 2018-12-05 | 2019-01-11 | 中国科学院烟台海岸带研究所 | A kind of light-operated polymer sensitive membrane electrochemical detection method and its device |
| CN110470722A (en) * | 2019-08-23 | 2019-11-19 | 中国科学院烟台海岸带研究所 | A kind of method and device thereof carrying out potential change detection using PhotoelectrochemicalMethod Method |
| WO2020222149A1 (en) * | 2019-05-02 | 2020-11-05 | Epitronic Holdings Pte. Ltd. | Microelectronic sensor with bolometric or pyroelectric detector for sensing electrical signals in sub-terahertz and terahertz frequency ranges |
| CN113514525A (en) * | 2020-04-09 | 2021-10-19 | 中国科学院烟台海岸带研究所 | Method for measuring nitrate ions by using solid contact type ion selective electrode |
| CN113588753A (en) * | 2021-07-09 | 2021-11-02 | 中国科学院烟台海岸带研究所 | Ion selective electrode current detection method |
| WO2021237974A1 (en) * | 2020-05-26 | 2021-12-02 | 江苏大学 | Volt-ampere electronic tongue-based device and method for rapid testing of physical and chemical indicators of soybean sauce |
| CN114544728A (en) * | 2020-11-25 | 2022-05-27 | 中国科学院烟台海岸带研究所 | Thin-layer polymer film ion selective electrode based on pulse constant current control and detection method |
| CN114577873A (en) * | 2022-02-25 | 2022-06-03 | 南京农业大学 | Water body heavy metal ion detection and recovery electrode, preparation method and detection and recovery method |
| CN114646681A (en) * | 2022-05-23 | 2022-06-21 | 中国科学院烟台海岸带研究所 | Visual detection method of solid contact type ion selective electrode |
| CN114910535A (en) * | 2022-04-24 | 2022-08-16 | 江苏大学 | Method for high-sensitivity and rapid detection of alpha-hydroxy sanshool based on cell electrochemical taste sensor |
-
2023
- 2023-07-20 CN CN202310892710.9A patent/CN116609411B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU972381A1 (en) * | 1979-01-05 | 1982-11-07 | Северо-Кавказский Филиал Всесоюзного Научно-Исследовательского И Конструкторского Института "Цветметавтоматика" | Pulse automatic polarograph |
| US6632349B1 (en) * | 1996-11-15 | 2003-10-14 | Lifescan, Inc. | Hemoglobin sensor |
| CN109187688A (en) * | 2018-12-05 | 2019-01-11 | 中国科学院烟台海岸带研究所 | A kind of light-operated polymer sensitive membrane electrochemical detection method and its device |
| WO2020222149A1 (en) * | 2019-05-02 | 2020-11-05 | Epitronic Holdings Pte. Ltd. | Microelectronic sensor with bolometric or pyroelectric detector for sensing electrical signals in sub-terahertz and terahertz frequency ranges |
| CN110470722A (en) * | 2019-08-23 | 2019-11-19 | 中国科学院烟台海岸带研究所 | A kind of method and device thereof carrying out potential change detection using PhotoelectrochemicalMethod Method |
| CN113514525A (en) * | 2020-04-09 | 2021-10-19 | 中国科学院烟台海岸带研究所 | Method for measuring nitrate ions by using solid contact type ion selective electrode |
| WO2021237974A1 (en) * | 2020-05-26 | 2021-12-02 | 江苏大学 | Volt-ampere electronic tongue-based device and method for rapid testing of physical and chemical indicators of soybean sauce |
| CN114544728A (en) * | 2020-11-25 | 2022-05-27 | 中国科学院烟台海岸带研究所 | Thin-layer polymer film ion selective electrode based on pulse constant current control and detection method |
| CN113588753A (en) * | 2021-07-09 | 2021-11-02 | 中国科学院烟台海岸带研究所 | Ion selective electrode current detection method |
| CN114577873A (en) * | 2022-02-25 | 2022-06-03 | 南京农业大学 | Water body heavy metal ion detection and recovery electrode, preparation method and detection and recovery method |
| CN114910535A (en) * | 2022-04-24 | 2022-08-16 | 江苏大学 | Method for high-sensitivity and rapid detection of alpha-hydroxy sanshool based on cell electrochemical taste sensor |
| CN114646681A (en) * | 2022-05-23 | 2022-06-21 | 中国科学院烟台海岸带研究所 | Visual detection method of solid contact type ion selective electrode |
Non-Patent Citations (4)
| Title |
|---|
| Engineered Cellulose Nanofiber Membranes with Ultrathin Low-Dimensional Carbon Material Layers for Photothermal-Enhanced Osmotic Energy Conversion;Qixing Luo et al.;ACS Applied Materials & Interfaces;第14卷(第11期);13223–13230 * |
| Nanoparticle enhanced salinity-gradient osmotic energy conversion under photothermal effect;Qinlong Ren et al.;Energy Conversion and Management;第251卷;115032 * |
| 固体接触式聚合物敏感膜电位型传感器检测海水中碳酸根;梅博杰;梁荣宁;秦伟;;分析试验室(11);全文 * |
| 基于氧空位的光热协同水分解制氢机理研究;吴启亮;中国博士学位论文全文数据库工程科技Ⅰ辑(第1期);B015-6 * |
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