TW201407151A - Dual mode multi-ion detector and fabrication method thereof and method for measuring cation sensitivity thereof - Google Patents

Abstract

A dual mode multi-ion detector including a conductive substrate is provided. An electrochromic film is disposed on the conductive substrate, wherein the electrochromic film includes titanium dioxide. The invention also provides a fabrication method thereof and a method for measuring cation sensitivities thereof.

Description

Dual-mode multi-ion sensor, manufacturing method thereof and multi-mode measurement Method for cation sensitivity of heavy ion sensor

The invention relates to a sensor, in particular to a dual mode multi-ion sensor and a method for measuring the cation sensitivity thereof.

The theory of electrochromism (EC) was proposed by JRPlatt in 1961. If a transition metal oxide or a compound generates a redox reaction via an applied voltage, the transition metal oxide or compound will have an electron injection (Injection) or Extraction causes a change in color and transmittance (Transmittance, T%).

At present, electrochromic materials are classified into transition metal oxides, organic compounds and high molecular polymers. The transition metal oxides have low operating voltage, fast reaction speed and long service life, and the operating voltage of organic compounds is low and the reaction speed is fast. However, it is impossible to repeat the cycle many times and the service life is short, and the polymer has the ability to be electrically discolored, but the operating voltage is high, the reaction speed is slow, and it is susceptible to the environmental temperature. Therefore, transition metal oxides are currently the most commonly used electrochromic materials. However, even transition metal oxides may still have some disadvantages, such as being toxic or expensive.

The Republic of China Invention Patent No. I273131 discloses an electrochromic film which produces a color change by a reversible redox reaction of an organic electrochromic conductive layer. The electrochromic film can achieve electrochromic effect by using a single transparent substrate, and can be bonded to the surface of other objects in combination with the application of the adhesive layer.

The Republic of China New Patent Certificate No. M338359 discloses an electrical change The color film device comprises: a transparent substrate layer; a transparent conductive film layer disposed under the polymer transparent material layer to provide negatively charged electrons; and a color changing film disposed on the transparent conductive layer a layer below the thin film layer; and a metal oxide layer disposed under the transparent conductive film layer to provide positively charged ions; the color changing film is provided with negatively charged electrons or The metal oxide layer provides a positively charged ion that changes color.

The Republic of China New Patent Certificate No. M266470 discloses an electrochromic thin film device comprising: a first conductive glass; a second conductive glass opposite thereto; and a second conductive glass formed opposite to the first conductive glass A conductive polymer film layer on the surface. A gas chamber for containing a working gas is disposed between the conductive polymer film layer and the first conductive glass. The electrochromic glass element has the advantages of compact and simple structure, simple operation and low production cost, and solves the problems of complicated structure and high cost of the conventional color-changing glass.

However, the aforementioned Republic of China invention patent certificates Nos. I273131, M338359 and M266470 are packaged in a state in which the electrolyte concentration is fixed, and thus cannot be used to measure the ion concentration of a solution to be tested.

The Republic of China Invention Patent No. M362401 discloses a pH meter which includes a meter body and an inductive element coupled to the meter body for detecting the pH of the liquid. Wherein, there is a color display on the meter body, and the color display shows the pH of the sensing element after detecting the liquid in a different color display manner. In the implementation, the meter body can also be provided with a color display capable of displaying pH and a numerical display for the user to select and use. However, it only uses the color change as a single mode of measurement, so the reliability is low.

The Republic of China Invention Patent Application No. 094138243 discloses a method for preparing a pH sensor, a pH sensor prepared, a system containing the pH sensor, and a measuring method. The above pH sensor is an extended gate ion sensing field effect transistor structure. The method for preparing the above-mentioned pH sensor comprises the steps of: providing an extended gate ion sensing field effect transistor having an extended gate region; forming a nitride on the extended gate region by radio frequency sputtering The titanium layer is used to obtain a pH sensor.

The invention of the invention of sodium ion selective electrode, a sodium ion selective electrode and a sodium ion sensing device, comprising: (a) providing a conductive substrate; (b) forming a wire The conductive substrate extends as an external electrical contact; and (c) forms a sodium ion sensing film on the conductive substrate.

The Republic of China invention patent application No. 092135902 discloses an extended field effect transistor applied to a potassium and sodium ion sensing element, which is based on an extended ion sensing field effect transistor to produce potassium and sodium ion sensing elements, The extended ion sensing field effect transistor extends the signal to intercept the electrode, and is fixed with hydrophilic bi-acrylic aromatic potassium polyurethane polymer mixed negative electrical additive, potassium, sodium ion selection and other substances to make potassium and sodium. Ion sensing electrode. The hydrophilic double-acrylic aromatic potassium urate polymer can be hardened and hydrophilic, and the potassium and sodium ion options are fixed to form a filterless circuit, a single-layer ion selective membrane and a signal-stabilized ion sensing electrode, resulting in When the potassium and sodium concentration values are measured on the sample, the interference between the potassium and sodium ion selective electrodes can be reduced, and the measured value is closer to the true value.

The above-mentioned Republic of China invention patent certificates Nos. 094138243, 098104928 and 092135902 are only measured by voltage changes. A mode with low reliability.

As can be seen from the above, at present, the ion concentration can be measured only in a single mode, and thus the reliability is low.

Therefore, there is a need for an electrochromic material and an ion concentration measurement method which can improve or solve the above problems.

In view of this, an embodiment of the present invention provides a dual mode multiple ion sensor comprising: a conductive substrate; and an electrochromic film disposed on the conductive substrate, wherein the electrochromic film comprises titanium dioxide.

Another embodiment of the present invention provides a method of fabricating a dual mode multiple ion sensor comprising the steps of: providing a conductive substrate; and forming an electrochromic film on the conductive substrate, wherein the electrochromic film comprises titanium dioxide.

Yet another embodiment of the present invention provides a method of measuring a cationic sensitivity of a dual mode multiple ion sensor, comprising the steps of: (a) providing a dual mode multiple ion as described in claim 1 of the patent application; a sensor; (b) immersing the dual mode multiple ion sensor in an electrolyte and subjecting the dual mode multiple ion sensor to a coloring reaction, wherein the electrolyte has a cation concentration; (c) measuring the dual mode Multi-ion sensor's color penetration rate corresponding to a wavelength range; (d) immersing a dual-mode multi-ion sensor in the electrolyte for a decolorization reaction; (e) measuring dual-mode multiple ion sensing a decolorization transmittance in the wavelength range; (f) changing the cation concentration of the electrolyte, and repeating the steps (b) to (e); and (g) measuring according to steps (c) and (f) Measuring the color penetration rate to determine the yang of the dual-mode multi-ion sensor Ion sensibility.

Yet another embodiment of the present invention provides a method of measuring a cationic sensitivity of a dual mode multiple ion sensor, comprising the steps of: (a) providing a dual mode multiple ion as described in claim 1 of the patent application; a sensor; (b) immersing the dual mode multiple ion sensor in an electrolyte and measuring a redox current density of the dual mode multiple ion sensor at a scan voltage, wherein the electrolyte has a cation concentration; (c) changing the cation concentration of the electrolyte, and repeating the step of (b); and (d) determining the redox current density measured according to step (b) and step (c) to determine the dual mode multiple ion sensor A cationic sensitivity.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The composition and use of the disclosed embodiments will be discussed in detail below. It should be understood that the embodiments provide many inventive concepts that have been implemented in a variety of specific embodiments. The specific embodiments discussed herein are for illustrative purposes only and are not limiting of the scope of the disclosure.

1 is a cross-sectional view showing a method of fabricating a dual mode multiple ion sensor 100 in accordance with an embodiment of the present invention. As shown in FIG. 1, a conductive substrate 101 may be provided first, and then an electrochromic film 102 is formed thereon, wherein the electrochromic film 102 includes titanium dioxide, thereby completing the fabrication of the dual mode multiple ion sensor 100. In the present embodiment, the electrochromic film 102 can partially cover (or expose) the conductive substrate 101 thereunder.

The conductive substrate 101 may include a two-layer structure including a conductive film 101a disposed above a transparent substrate 101b. For example, the conductive substrate 101 may include an Indium Tin Oxide/Polyethylene Terephthalate (ITO/PET) conductive substrate, an Indium Tin Oxide/Glass (ITO/Glass) conductive substrate. Or a two-layer structure of a Fluorine-doped Tin Oxide/Polyethylene Terephthalate (FTO/Glass) conductive substrate. In some embodiments, a commercially available flexible indium tin oxide film/plastic conductive substrate can be used as the conductive substrate 101, and it can have a resistance value of 20 Ω.

In some embodiments, the titanium dioxide included in the electrochromic film 102 can be in powder form, such as in the form of a nanopowder. In some embodiments, the particle size range can be from about 3 to 100 nm. For example, P25 (Degussa) can be used as a source of titanium dioxide, but is not limited thereto. Furthermore, the electrochromic film 102 may further comprise a dispersing agent and a surfactant.

The dispersing agent may include ethyl acetylacetone. The surfactant may include polyethylene glycol octylphenyl ether (C ₁₄ H ₂₂ O(C ₂ H ₄ O) _n ). May be used, for example, Triton ^TM X-100 (Dow) as the source of polyethylene glycol octylphenyl ether, and then limited thereto.

In some embodiments, the electrochromic film 102 can be formed on the conductive substrate 101 by first preparing a titania colloid, and then forming a titania colloid on the conductive substrate 101 by any suitable method. In some embodiments, the titanium dioxide colloid can be formed by mixing titanium dioxide (such as titanium dioxide powder), a dispersant solution (such as ethyl acetylacetone solution), and a surfactant (such as polyethylene glycol octyl phenyl ether). Which is dispersed The volume ratio of the solution to the titanium dioxide may be about 0 to 0.3 ml: 1 to 5 ml, and the volume ratio of the surfactant to the titanium dioxide may be about 0 to 0.3 ml: 1 to 5 ml. Adding a dispersant solution can increase the degree of dispersion of the colloid and avoid the occurrence of agglomeration. The adhesion between the electrochromic film 102 and the conductive substrate 101 can be improved by adding a surfactant. Furthermore, the formed titania colloid can be further uniformly mixed, for example, the titania colloid is placed in an ultrasonic oscillator, and then the uniformly mixed titania colloid is allowed to stand to diffuse uniformly. In some embodiments, the standing time It can be about 5~48 hours. In addition, in some embodiments, the electrochromic film 102 can be formed on the conductive substrate 101 by screen printing a titania colloid on the conductive substrate 101. In some embodiments, the distance between a screen for screen printing and the conductive substrate 101 can be from about 0.1 cm to about 0.4 cm, preferably about 0.1 cm. After the screen printing of the titania colloid on the conductive substrate 101, the conductive substrate 101 having the titania colloid may be further baked in an oven to dry-form the titania colloid. In some embodiments, the baking temperature may be 70-150 ° C, and preferably 125 ° C, and the baking time may be 5-30 minutes, and preferably 10 minutes.

2 is a diagram showing an electrochromic device 200 electrically coupled to a dual mode multiple ion sensor 100 (as shown in FIG. 1) in accordance with an embodiment of the present invention. The electrochromic device 200 includes a power supply 201, an electrode 202, and an electrolyte 203. The power supply 201 can use the power supply of the PST-3201 manufactured by Good Will Electronics, but other power supplies having the same function can also be used. Electrode 202 can include a platinum rod. The electrolyte 203 is a solution containing a cation such as a hydrogen ion electrolyte, a sodium ion electrolyte, a potassium ion electrolyte or a lithium ion electrolyte. In one embodiment, the electrolyte 203 can be a hydrogen ion electrolyte (pH=1~13) or a sodium ion electrolyte (1~ ^10-5 M sodium chloride solution).

In some embodiments, the electrical connection between the electrochromic device 200 and the dual mode multiple ion sensor 100 can be achieved by immersing the dual mode multiple ion sensor 100 and the electrode 202 in the electrolyte 203. The dual-mode multi-ion sensor 100 and the electrode 202 are electrically connected (for example, by a wire) to the positive end and the negative end (or the negative end and the positive end) of the power supply 201, respectively. For example, the dual mode multiple ion sensor 100 can be electrically connected to the positive end of the power supply 201, and the electrode 202 can be electrically connected to the negative end of the power supply 201. Alternatively, the dual mode multiple ion sensor 100 can be electrically connected to the negative end of the power supply 201, and the electrode 202 can be electrically connected to the positive end of the power supply 201. The power supply 201 can provide an operating voltage between the dual mode multiple ion sensor 100 and the electrode 202. . In one embodiment, the operating voltage can be approximately 0.5 to 3 volts.

When the power supply 201 provides an operating voltage between the dual mode multiple ion sensor 100 and the electrode 202, the electrochromic film 102 in the dual mode multiple ion sensor 100 will chemically react as shown in the following equation (1), and Causes changes in color and penetration:

Wherein M ⁺ is a cation contained in the electrolytic solution 203, such as H ⁺ , Li ⁺ or Na ⁺ , and the x value is 0 to 1, and the size thereof depends on the amount of electricity supplied to the film. The direction in which equation (1) is performed will depend on whether the dual mode multiple ion sensor 100 is electrically connected to the positive or negative terminal of the power supply 201. Since TiO ₂ is nearly colorless and M _x TiO ₂ is light blue, when the electrochromic film 102 undergoes a chemical reaction of the formula (1), it will produce a color change, so the chemical reaction of the formula (1) is also called For a coloring (reaction to the right) / color removal (reaction to the left) reaction.

When the dual mode multiple ion sensor 100 is electrically connected to the negative end of the power supply 201 (that is, the negative power is applied to the dual mode multiple ion sensor 100, and the electrode 202 is electrically connected to the power supply 201 The electrons and the cations are simultaneously injected into the electrochromic film 102 to perform a coloring reaction. Conversely, when the dual mode multiple ion sensor 100 is electrically connected to the positive end of the power supply 201, the electrodes 202 are electrically connected. To the negative end of the power supply 201, a decoloring reaction will be performed at this time.

Based on the characteristics that the electrochromic film 102 generates color and transmittance changes under the operating voltage, the electrochromic device 200 and an optical detector can be used to obtain the sensation of the cation contained in the electrolyte by the dual mode multi-ion sensor 100. measure. Here, "sensitivity" is defined as an increase in the transmittance of the dual-mode multi-ion sensor 100 caused by an increase in the unit concentration of cations at a fixed room temperature. 3 is a flow chart showing a method 400 of measuring the cation sensitivity of the dual mode multiple ion sensor 100 in accordance with an embodiment of the present invention. First, step 10 is performed to provide a dual mode multiple ion sensor 100 (as shown in Figure 1). Next, in step 20, the dual mode multiple ion sensor 100 is immersed in an electrolyte and the dual mode multiple ion sensor 100 is subjected to a coloring reaction, wherein the electrolyte has a cation concentration. In step 20, the dual mode multiple ion sensor 100 can be electrically connected to the electrochromic device 200 for coloring reaction, wherein the dual mode multiple ion sensor 100 is immersed in the electrolyte 203. In some embodiments, the cation is a hydrogen ion and the hydrogen ion concentration can range from about 10 ^-1 M to 10 ^-5 M, that is, its pH is about 1-5. In other embodiments, a sodium chloride solution can be used as the electrolyte 203, so the cation is sodium ion and the sodium ion concentration can range from about 1 to 10 ^-5 M. In some embodiments, the coloring reaction can be carried out for about 60 to 120 seconds.

After the coloring reaction is completed, step 30 is performed to measure the color penetration (T _color (%)) corresponding to the wavelength range of the dual mode multiple ion sensor 100. The measurement of step 30 can be carried out using an ultraviolet-visible (UV-Vis) optical spectrum analyzer (Optical Spectrum Analyzer). In some embodiments, the above wavelength range is from 300 to 900 nm. In other embodiments, the above wavelength range is from 500 to 900 nm.

Next, in step 40, the dual mode multiple ion sensor 100 is immersed in the electrolyte 203 for a decolorization reaction. Similarly, in step 40, the dual mode multiple ion sensor 100 can be electrically coupled to the electrochromic device 200 for a decolorizing reaction, wherein the dual mode multiple ion sensor 100 is immersed in the electrolyte 203. In some embodiments, the decolorization reaction can be carried out for about 240 to 360 seconds.

After the decoloring reaction is completed, step 50 is performed to measure the decolorization transmittance (T _bleach (%)) corresponding to the wavelength range of the dual mode multi-ion sensor 100. The measurement of step 50 can be performed using an ultraviolet light-visible spectrum analyzer. In some embodiments, the above wavelength range is from 300 to 900 nm. In other embodiments, the above wavelength range is from 500 to 900 nm.

Next, step 60 is performed to change the cation concentration of the electrolyte 203, and steps 20 to 50 are repeated.

Next, step 70 is performed to determine the cation sensitivity of the dual mode multi-ion sensor 100 based on the color penetration measured in steps 30 and 60. For example, cation concentration and dual mode multiple ion sensation can be made The relationship between the color penetration of the detector 100 at a fixed wavelength in the above wavelength range, and the cation sensitivity of the dual mode multiple ion sensor 100 is determined accordingly. In some embodiments, a relationship between the negative logarithm of the cation concentration and the color penetration of the dual mode multiple ion sensor 100 at a fixed wavelength in the above wavelength range can be made and linearized to obtain a dual mode. A cationic sensitivity of the multiple ion sensor 100. Since the color transmittance of the dual-mode multi-ion sensor 100 at different wavelengths is different, it is necessary to measure the color transmittance of the dual-mode multi-ion sensor 100 at a fixed wavelength, and it is preferable to select the coloring wear. The permeability changes more than the average wavelength to get a more accurate sensitivity. In an embodiment, the fixed wavelength may be 800 nm. It should be noted that the reason for obtaining the cation sensitivity of the dual mode multi-ion sensor 100 by step 70 is based on the negative logarithm of the cation concentration and the color penetration of the dual mode multi-ion sensor 100 at a fixed wavelength. The rates are linear with each other.

4 is a diagram showing an electrochemical measurement system 300 electrically coupled to a dual mode multiple ion sensor 100 (as shown in FIG. 1) in accordance with an embodiment of the present invention. The electrochemical measurement system 300 includes a reference electrode 301, an electrode 302, an electrolyte 303, and a Cyclic Voltammogram (CV) 304. The reference electrode 301 can be a silver/silver chloride reference electrode. The electrolyte 303 can be similar to the electrolyte 203. Similarly, the electrolyte 203 may include a solution containing a cation such as a hydrogen ion electrolyte, a sodium ion electrolyte, a potassium ion electrolyte or a lithium ion electrolyte. In one embodiment, the electrolyte 203 can be a hydrogen ion electrolyte (pH=1~13) or a sodium ion electrolyte (1~ ^10-5 M sodium chloride solution). In some embodiments, the cyclic voltammeter 304 can utilize a cyclic voltammeter of SP-150 manufactured by BioLogic, although other cyclic voltammeters of the same function can also be used.

In some embodiments, the electrical connection between the electrochemical measurement system 300 and the dual mode multiple ion sensor 100 can be achieved by: dual mode multiple ion sensor 100, electrode 302 and reference electrode 301 Soaked in the electrolyte 303 and electrically connected (for example by a wire) to the cyclic voltammeter 304. The cyclic voltammeter 304 supplies a scan voltage between the dual mode multiple ion sensor 100 and the reference electrode 301. When the cyclic voltammeter 304 supplies a scan voltage between the dual mode multiple ion sensor 100 and the reference electrode 301, the molecular structure of the electrochromic film 102 is combined with the cations in the electrolyte 303 to cause the electrochromic film 102 to be generated. Redox current. The redox current density of the electrochromic film 102 is related to the material properties of the electrochromic film 102 and the cation concentration of the electrolyte 303, and the peak of the redox current depends on the material properties of the electrochromic film 102, when the peak is at a certain voltage. When high, it means that the electrochromic film 102 has a strong oxidation or reduction reaction for this voltage.

5 is a flow chart showing a method 500 of measuring the cation sensitivity of a dual mode multiple ion sensor in accordance with another embodiment of the present invention. First, step 15 is performed to provide a dual mode multiple ion sensor 100 (as shown in Figure 1).

Next, step 25 is performed to immerse the dual mode multiple ion sensor 100 in an electrolyte and measure the redox current density of the dual mode multiple ion sensor 100 at a scan voltage, wherein the electrolyte has a cationic concentration . In step 25, the dual mode multiple ion sensor 100 can be electrically coupled to the electrochemical measurement system 300 (as shown in FIG. 4) for measurement of redox current density, wherein dual mode multiple ion sensing 100 dip Soaked in the electrolyte 303. In some embodiments, the scan voltage is between -2.5 and +2.5 volts. In the preferred embodiment, the scan voltage is -1 to +1 volts.

Next, step 35 is performed to change the cation concentration of the electrolyte 203, and step 25 is repeated.

Thereafter, step 45 is performed to determine a cationic sensitivity of the dual mode multiple ion sensor 100 based on the redox current density measured in steps 25 and 35. For example, a relationship between the cation concentration and the redox current density of the dual mode multi-ion sensor 100 at a fixed voltage of the dual mode multiple ion sensor 100 within the scan voltage can be determined. The cationic sensitivity of the dual mode multiple ion sensor 100. In some embodiments, a relationship between the negative logarithm of the concentration of the cation and the redox current density of the dual mode multiple ion sensor 100 at a fixed voltage within the scan voltage can be made and linearized to obtain The cationic sensitivity of the dual mode multiple ion sensor 100. In some embodiments, the fixed voltage can be from -1 to -2.5 volts. It should be noted that the reason for obtaining the cation sensitivity of the dual mode multi-ion sensor 100 by step 45 is based on the negative logarithm of the cation concentration of the electrolyte and the dual mode multi-ion sensor 100 at a fixed voltage. The redox current densities are linear with each other.

According to the above embodiment, the cation sensitivity of the dual mode multiple ion sensor 100 can be obtained by the above-described electrochemical mode or optical mode measurement method. Furthermore, after obtaining the cationic sensitivity, the (1) coloring and decolorizing transmittance (optical mode) of the electrolyte having an unknown cation concentration may be further measured; or (2) the redox current, the electrolyte may be obtained. Concentration of cations.

The invention is widely used. For example, the present invention can be applied to detecting the ion concentration of a body fluid in a human body, particularly a hydrogen ion concentration or a pH value. The pH value of body fluids in human body plays an important role in human health. When the pH value is low, the metabolism of cells in the body is slow, which has a serious impact on physiological functions and increases the risk of cancer. After being metabolized, heme cells in the human body produce many inorganic and organic acids, such as carbonic acid, phosphoric acid, sulfuric acid, uric acid, lactic acid, etc., in which sulfuric acid is a strong acid and releases a large amount of hydrogen ions. These metabolically produced inorganic and organic acids can be absorbed by buffer systems in the human body (such as bicarbonate systems, proteins, hydrogen phosphate systems, etc.), especially sulfuric acid, which releases a large amount of hydrogen ions, 99.99% of which are Can be absorbed by these buffer systems. Since these buffer systems all have a weak acid, even if a strong acid is added, the weak acid and its conjugate base can be paired with most of the hydrogen ions released by the strong acid, so that the strong acid is converted into a weak acid, thereby maintaining the stability of the pH. In addition, sodium ions in human body fluids are also important for human health. The primary function of sodium ions is to maintain the balance between water and pH in the body, so that the body fluid maintains a certain osmotic pressure to maintain normal water content. If the electrolyte is unbalanced, the water and pH will lose balance. Finally, various physiological and biochemical reactions that sustain life will cause problems one by one. For example, due to lack of sodium salt, it will produce symptoms such as weakness, lethargy, dehydration and palpitations.

Various embodiments in accordance with the present invention will be described below.

[Embodiment 1] Method of manufacturing dual mode multiple ion sensor

Perform the following steps to make a dual mode multi-ion sensor: (a) add 2.5 ml of deionized water to 3 grams of P25 (Degussa), then add 0.1 ml of ethyl acetylacetone solution and 0.2 ml of Triton ^TM X. -100 (Dow) to form a mixture; (b) placing the above mixture into an ultrasonic oscillator for uniform mixing, and then uniformly mixing the mixture in a cool place for 24 hours to diffuse uniformly to form a a titanium dioxide colloid; (c) printing a titania colloid on a conductive substrate, wherein a distance between a screen and a conductive substrate used for screen printing is 0.1 cm; and (d) placing a conductive substrate having a titania colloid The dual-mode multi-ion sensor was fabricated by baking in an oven at a temperature of about 125 ° C for 10 minutes to form an electrochromic film on the conductive substrate.

[Embodiment 2] Method for measuring hydrogen ion sensation of dual mode multi-ion sensor (optical mode)

The following steps are sequentially performed, wherein three solutions containing different hydrogen ion concentrations are respectively used as the electrolyte, which are electrolyte A (pH=1), electrolyte B (pH=3), and electrolyte C (pH=5). (a) providing the dual mode multi-ion sensor of Embodiment 1 and an electrochromic device electrically connected thereto, wherein the electrochromic device comprises: a platinum rod as an electrode having a cation (hydrogen ion or sodium ion) a concentration of an electrolyte, and a power supply (PST-3201; Goodwill Electronics), in which a dual-mode multi-ion sensor and platinum rod are immersed in the electrolyte, and a dual-mode multi-ion sensor and a platinum rod Electrically connected to the positive and negative terminals (or the negative terminal and the positive terminal) of the power supply by a wire, and the power supply provides an operating voltage between the dual mode multiple ion sensor and the platinum rod; b) electrically connecting the dual-mode multi-ion sensor and the platinum rod to the negative end and the positive end of the power supply respectively, so that the electrochromic film performs a color reaction of 90 seconds, wherein the operating voltage is 2.5 volts; (c) Ultra-violet-visible spectrum analyzer (Labomed) measurement of dual-mode multiple ion sensing In a wavelength range of 300 to 900 nm coloring transmittance _{(T color (%));} (d) the dual mode multi-ion sensor electrode and a platinum rod connected to the power supply interchanged, i.e. the dual mode The multi-ion sensor and the electrode are respectively electrically connected to the positive end and the negative end of the power supply, and the electrochromic film is subjected to a decoloring reaction for about 300 seconds, wherein the operating voltage is also 2.5 volts; and (e) the decolorizing reaction Upon completion, the decolorization transmittance (T _bleach (%)) of the dual mode multi-ion sensor in the wavelength range of 300-900 nm was measured by an ultraviolet-visible spectrum analyzer (Labomed).

Figure 6 is a graph showing the color penetration versus wavelength for a dual mode multiple ion sensor at different hydrogen ion concentrations (expressed in pH) according to Example 2. Figure 7 is a graph showing the hydrogen ion concentration (expressed in pH) versus the dual mode multi-ion sensor at a fixed wavelength (800 nm). In Figure 7, after linearization, the resulting linearity was 0.9934 and the hydrogen ion sensitivity was 1.125 T%/pH.

[Embodiment 3] Method for measuring sodium ion sensitivity of a dual mode multi-ion sensor (optical mode)

This embodiment is the same as Embodiment 2 except that the electrolyte is replaced with an electrolyte having different sodium ion concentrations, which are 1 M, 10 ^-1 M, 10 ^-2 M, 10 ^-3 M, 10 ^-4 M, and 10, respectively. ^-5 M sodium chloride solution. Figure 8 is a graph showing the color penetration versus wavelength for a dual mode multiple ion sensor at different sodium ion concentrations (represented by pNa values) in accordance with Example 3 of the present invention. Figure 9 is a graph showing the relationship between the concentration of sodium ions (expressed in pNa) and the transmittance of a dual mode multiple ion sensor at a fixed wavelength (800 nm). In Figure 9, after linearization, the resulting linearity was 0.9979 and the sodium ion sensitivity was 2.242 T%/pNa.

[Embodiment 4] Method for measuring hydrogen ion sensation of dual mode multi-ion sensor (electrochemical mode)

The following steps are sequentially performed, wherein four solutions containing different hydrogen ion concentrations are respectively used as the electrolyte, which are electrolyte A (pH=1), electrolyte B (pH=3), and electrolyte C (pH=5). And electrolyte D (pH = 7).

(a) providing the dual-mode multi-ion sensor of Embodiment 1 and an electrochemical measurement system electrically connected thereto, wherein the electrochemical measurement system comprises: a reference electrode, a platinum rod as an electrode, and a cation An electrolyte (hydrogen ion or sodium ion) concentration, and a cyclic voltammeter, wherein the dual mode multi-ion sensor, the platinum rod and the reference electrode are immersed in the electrolyte and electrically connected to the cycle by a wire An voltammeter, and the cyclic voltammeter supplies a scan voltage between the dual mode multiple ion sensor and the reference electrode, wherein the scan voltage is -1 to +1 volt; and (b) is measured using an electrochemical measurement system The redox current density of a dual mode multiple ion sensor at a scan voltage.

Figure 10 is a graph showing the redox current density versus scan voltage for a dual mode multiple ion sensor at different hydrogen ion concentrations (expressed in pH) according to Example 4. Figure 11 shows the hydrogen ion concentration (in pH) and the dual-mode multi-ion sensor at a fixed voltage (-0.8 volts) A plot of current density under special conditions. In Fig. 11, after linearization, the obtained linearity was 0.9814, and the sensitivity of hydrogen ions was 0.3655 mA/cm 2 .

[Embodiment 5] Method for measuring sodium ion sensation of dual mode multi-ion sensor (electrochemical mode)

This embodiment is the same as the embodiment 4 except that the electrolyte is replaced with an electrolyte containing different sodium ion concentrations, which are 1 M, 10 ^-1 M, 10 ^-2 M, 10 ^-3 M, 10 ^-4 M and 10, respectively. ^-5 M sodium chloride solution.

Figure 12 is a graph showing the redox current density versus scan voltage for a dual mode multiple ion sensor at different sodium ion concentrations (expressed as pNa values) according to Example 5. Figure 13 is a graph showing the relationship between sodium ion concentration (expressed as pNaa value) and current density at a fixed voltage (-0.87 volts) for a dual mode multiple ion sensor. In Fig. 13, after linearization, the obtained linearity was 0.9556, and the sensitivity of sodium ions was 0.0905 mA/cm 2 .

In summary, the present invention provides a novel dual-mode multi-ion sensor having an electrochromic film comprising titanium dioxide and having the advantages of non-toxicity, chemical stability, acid and alkali resistance, and low cost. The present invention also provides a method for measuring the cationic sensitivity of a dual mode multi-ion sensor in a dual mode (optical mode and electrochemical mode), and after knowing the cationic sensitivity, the electrolysis having an unknown cation concentration can be further measured. The cation concentration of the liquid. Furthermore, the dual mode measurement method of the present invention is more accurate than the method of measuring the sensitivity of a cation only in a single mode.

10, 15, 20, 25, 30, 35, 40, 50, 60 ‧ ‧ methods

100‧‧‧Double mode multi-ion sensor

101‧‧‧Electrical substrate

101a‧‧‧Electrical film

101b‧‧‧Transparent substrate

102‧‧‧Electrochromic film

200‧‧‧Electron-changing device

201‧‧‧Power supply

202, 302‧‧‧ electrodes

203, 303‧‧‧ electrolyte

300‧‧‧Electrochemical Measurement System

301‧‧‧ reference electrode

400, 500‧‧‧ method

1 is a cross-sectional view showing a method of fabricating a dual mode multiple ion sensor according to an embodiment of the present invention.

2 is a diagram showing an electrochromic device electrically coupled to a dual mode multiple ion sensor in accordance with an embodiment of the present invention.

3 is a flow chart showing a method of measuring the cationic sensitivity of a dual mode multiple ion sensor in accordance with an embodiment of the present invention.

4 is a diagram showing an electrochemical measurement system electrically coupled to a dual mode multiple ion sensor in accordance with an embodiment of the present invention.

Figure 5 is a flow chart showing a method of measuring the cationic sensitivity of a dual mode multiple ion sensor in accordance with another embodiment of the present invention.

Figure 6 is a graph showing the color penetration versus wavelength for a dual mode multiple ion sensor at different hydrogen ion concentrations (expressed in pH) according to Example 2.

Figure 7 is a graph showing the relationship between the concentration of hydrogen ions (expressed in pH) and the transmittance of a dual mode multi-ion sensor at a fixed wavelength (800 nm).

Figure 8 is a graph showing the color penetration versus wavelength for a dual mode multiple ion sensor at different sodium ion concentrations (represented by pNa values) in accordance with Example 3 of the present invention.

Figure 9 shows a plot of sodium ion concentration (expressed as pNa) versus permeability of a dual mode multiple ion sensor at a fixed wavelength (800 nm).

Figure 10 shows the different hydrogen ion concentrations according to Example 4 (in The pH value is a plot of the redox current density of the lower dual mode multiple ion sensor versus the scan voltage.

Figure 11 is a graph showing the relationship between the hydrogen ion concentration (in pH) and the current density of a dual mode multi-ion sensor at a fixed voltage (-0.8 volts).

Figure 12 is a graph showing the redox current density versus scan voltage for a dual mode multiple ion sensor at different sodium ion concentrations (expressed as pNa values) according to Example 5.

Figure 13 is a graph showing the relationship between sodium ion concentration (expressed as pNa value) and current density at a fixed voltage (-0.87 volts) for a dual mode multiple ion sensor.

100‧‧‧Double mode multi-ion sensor

101‧‧‧Electrical substrate

101a‧‧‧Electrical film

101b‧‧‧Transparent substrate

102‧‧‧Electrochromic film

Claims (27)

A dual mode multiple ion sensor comprises: a conductive substrate; and an electrochromic film disposed on the conductive substrate, wherein the electrochromic film comprises titanium dioxide. The dual-mode multi-ion sensor of claim 1, wherein the conductive substrate comprises a flexible indium tin oxide film disposed on a plastic conductive substrate. The dual mode multiple ion sensor of claim 2, wherein the conductive substrate has a resistance value of 20 Ω. The dual mode multiple ion sensor of claim 1, wherein the electrochromic film further comprises a dispersing agent and a surfactant. The dual mode multiple ion sensor of claim 4, wherein the surfactant comprises polyethylene glycol octyl phenyl ether. The dual mode multiple ion sensor of claim 4, wherein the dispersing agent comprises ethyl acetylacetone. A method of manufacturing a dual mode multiple ion sensor, comprising the steps of: providing a conductive substrate; and forming an electrochromic film on the conductive substrate, wherein the electrochromic film comprises titanium dioxide. The method of manufacturing the dual-mode multi-ion sensor according to claim 7, wherein the conductive substrate comprises a flexible indium tin oxide disposed on a plastic conductive substrate. The method for manufacturing a dual mode multi-ion sensor according to claim 7, wherein the electrochromic film further comprises a dispersing agent and a surfactant. The method of manufacturing a dual mode multiple ion sensor according to claim 9, wherein the surfactant comprises polyethylene glycol octylphenyl ether. The method of producing a dual mode multiple ion sensor according to claim 9, wherein the dispersing agent comprises ethyl acetylacetone. The method of manufacturing a dual mode multiple ion sensor according to claim 7, wherein the electrochromic film is formed on the conductive substrate by printing a titanium dioxide colloid on the conductive substrate. The method of manufacturing a dual mode multiple ion sensor according to claim 12, wherein the titanium dioxide colloid is formed by mixing titanium dioxide, a dispersant solution, and a surfactant. The method for manufacturing a dual-mode multi-ion ion sensor according to claim 13, wherein a volume ratio of the dispersant solution to the titanium dioxide is about 0 to 0.3 ml: 1 to 5 ml, and the interface activity is The volume ratio of the agent to the titanium dioxide is about 0 to 0.3 ml: 1 to 5 ml. The method for manufacturing a dual mode multiple ion sensor according to claim 13 , further comprising: placing the conductive substrate having the titania colloid in an oven after forming the electrochromic film on the conductive substrate. bake. The method of manufacturing a dual mode multiple ion sensor according to claim 15, wherein the baking is performed at a temperature of 70 to 150 ° C for 5 to 30 minutes. A method for measuring a cationic sensitivity of a dual mode multiple ion sensor, comprising the steps of: (a) providing a dual mode multiple ion sensor as described in claim 1; (b) The dual mode multiple ion sensor is immersed in an electrolyte and the coloring reaction is performed on the dual mode multiple ion sensor, wherein the electrolyte has a cation concentration; (c) measuring the dual mode multiple ion sensor a color penetration rate corresponding to a wavelength range; (d) immersing the dual mode multiple ion sensor in the electrolyte for a decolorization reaction; (e) measuring the dual mode multiple ion sensor at a decolorization transmittance of the wavelength range; (f) a step of changing the cation concentration of the electrolyte, and repeating steps (b) to (e); and (g) according to the step (c) and the step (f) The measured color penetration is determined to determine a cationic sensitivity of the dual mode multiple ion sensor. A method of measuring the cationic sensitivity of a dual mode multiple ion sensor as described in claim 17, wherein the cation comprises hydrogen ions, sodium ions, potassium ions or lithium ions. A method for measuring the cationic sensitivity of a dual mode multi-ion sensor as described in claim 17, wherein an ultraviolet-visible light spectrum analyzer is used to measure the coloring transmittance and the color-removing transmittance. . A method for measuring the cation sensitivity of a dual mode multi-ion sensor as described in claim 17 of the patent application, wherein the dual mode is separately The multi-ion ion sensor applies a positive potential to carry out the coloring reaction of step (b) and applies a negative potential to carry out the decoloring reaction of step (c). The method for measuring the cation sensitivity of a dual mode multi-ion sensor as described in claim 20, wherein the positive potential and the negative potential are 0.5 to 3 volts. The method for measuring the cation sensitivity of the dual mode multi-ion sensor as described in claim 17, wherein the coloring reaction is performed for 60 to 120 seconds, and the decolorization reaction is performed for 240 to 360 seconds. . A method of measuring the cationic sensitivity of a dual mode multi-ion sensor as described in claim 17, wherein the wavelength range is from 300 to 900 nm. A method for measuring a cationic sensitivity of a dual mode multiple ion sensor, comprising the steps of: (a) providing a dual mode multiple ion sensor as described in claim 1; (b) The dual mode multiple ion sensor is immersed in an electrolyte and measures the redox current density of the dual mode multiple ion sensor at a scan voltage, wherein the electrolyte has a cation concentration; (c) changing the electrolysis The cation concentration of the liquid, and repeating the step of (b); and (d) determining the cation of the dual mode multi-ion sensor based on the redox current density measured in the step (b) and the step (c) Sensitivity. A method of measuring the cationic sensitivity of a dual mode multi-ion sensor as described in claim 24, wherein the cation comprises a hydrogen ion, a sodium ion, a potassium ion or a lithium ion. A method of measuring the cation sensitivity of a dual mode multi-ion sensor as described in claim 24, wherein the scan voltage is -2.5 to +2.5 volts. A method of measuring the cationic sensitivity of a dual mode multiple ion sensor as described in claim 24, wherein the scan voltage is provided by a cyclic voltammeter.