Composite electrolyte for detecting organic amine gas and its preparation method, electrochemiluminescence gas sensor and detection method

Abstract

This application relates to the field of sensors, disclosing a composite electrolyte for detecting organic amine gases and its preparation method, an electrochemiluminescence gas sensor, and a detection method. The composite electrolyte for detecting organic amine gases includes an electrochemiluminescence probe and an ionic liquid. The electrochemiluminescence gas sensor for detecting organic amine gases of this application includes a sensor and the aforementioned composite electrolyte; the composite electrolyte is coated on the electrodes of the sensor. The electrochemiluminescence gas sensor for detecting organic amine gases of this application, based on a photoelectric bivariate response mode, can effectively distinguish organic amine gases and achieve ppm-level detection of organic amine gases at room temperature.

Description

Technical Field

[0001] This application relates to the field of sensors, and mainly to composite electrolytes for detecting organic amine gases and their preparation methods, electrochemiluminescence gas sensors and detection methods. Background Technology

[0002] Amines are products formed when one or more hydrogen atoms in an ammonia molecule are replaced by hydrocarbon groups. Amines are widely distributed in the biological world and possess crucial physiological and biological activities. Amine gases are generally considered toxic and are key indicators in areas such as food spoilage and environmental pollution. For example, the spoilage of meat and fish releases biogenic amines (such as putrescine, cadaverine, and trimethylamine), making their detection essential. Besides toxicity, amines are also biomarkers for human diseases. Volatile organic compounds (VOCs) exhaled by some patients are characteristic of certain diseases (e.g., trimethylamine can be used to detect acute heart failure and fatty liver). Amines are also found in amino acids, neurotransmitters, and nucleic acids, and are extremely important for human survival. In pharmacology, many drugs contain amine functional groups. In industry, amines are present in various products, such as fertilizers and disinfectants. Therefore, the development of sensitive amine sensors is essential. However, amine gases usually occur as mixed gases with complex compositions, making selective detection of amine gases a technical challenge.

[0003] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this application is to provide a composite electrolyte for detecting organic amine gas and its preparation method, an electrochemiluminescence gas sensor and detection method. The electrochemiluminescence gas sensor for detecting organic amine gas is a sensor based on photoelectric bivariate response mode, which aims to solve the problem that the selectivity of existing sensors for amine gases needs to be improved.

[0005] The technical solution of this application is as follows:

[0006] A composite electrolyte for detecting organic amine gas, wherein the raw materials include an electrochemiluminescent probe and an ionic liquid;

[0007] The electrochemiluminescent probe has electrochemiluminescent properties, including but not limited to one of Ru(bpy)3Cl2·6H2O and its derivatives, Ru(bpy)3(PF6)2 and its derivatives, and [Ir(ppy)2(bpy)](PF6) and its derivatives;

[0008] The ionic liquid has high ionic conductivity and high organic amine solubility, including but not limited to one of [BMIM][PF6], [BMIM][BF4], [BMIM][BF6], [BMIM][Ac], [EMIM][NTF2], and [EMIM][Gly].

[0009] The electrochemiluminescent probe is used in the ionic liquid at a concentration of 0.1-50 mmol / L.

[0010] The composite electrolyte for detecting organic amine gas is wherein the ionic liquid is [BMIM][PF6], and the electrochemiluminescent probe is Ru(bpy)3Cl2·6H2O or Ru(bpy)3(PF6)2.

[0011] In the embodiments of this application, Ru(bpy)3 is used. 2+ The luminescent signal and the current signal generated by the organic amine gas are used as a photoelectric bivariate response, Ru(bpy)3 2+ A composite electrolyte for detecting organic amine gases, which can generate luminescent signals with various amines, is selected using an ionic liquid [BMIM][PF6] with high solubility for organic amine gases to provide a sensitive current response. The electrochemiluminescent gas sensor for detecting organic amine gases prepared using this composite electrolyte, based on a photoelectric bivariate response mode, can effectively distinguish organic amine gases and achieve ppm-level detection of organic amine gases at room temperature.

[0012] The composite electrolyte for detecting organic amine gas, wherein the electrochemiluminescence probe is at a concentration of 32 mmol / L in the ionic liquid.

[0013] A method for preparing a composite electrolyte for detecting organic amine gas as described above, comprising the following steps:

[0014] The electrochemiluminescence probe was dissolved in an ionic liquid to obtain the composite electrolyte used for detecting organic amine gas.

[0015] An electrochemiluminescence gas sensor for detecting organic amine gas, comprising a sensor and a composite electrolyte for detecting organic amine gas as described above;

[0016] The composite electrolyte used to detect organic amine gas is coated on the electrodes of the sensor.

[0017] The electrochemiluminescence gas sensor for detecting organic amine gas in this application is a novel electrochemiluminescence gas sensor for detecting organic amine gas based on a bivariate response mode of a composite electrolyte for detecting organic amine gas. It uses the luminescence signal of the electrochemiluminescence probe and the current signal generated by the organic amine gas as photoelectric bivariate responses, and proposes a novel bivariate sensor for selective enhancement.

[0018] The electrochemiluminescence gas sensor for detecting organic amine gas is provided with 5-100 μL of the composite electrolyte for detecting organic amine gas per square centimeter of electrode.

[0019] The electrochemiluminescence gas sensor for detecting organic amine gas is provided with 30 μL of the composite electrolyte for detecting organic amine gas per square centimeter of electrode.

[0020] An organic amine gas detection method, wherein the organic amine gas detection method is based on an electrochemiluminescence gas sensor for detecting organic amine gas as described above, and includes the following steps:

[0021] The gas to be tested is brought into contact with the electrochemiluminescence gas sensor used to detect organic amine gas, and current signals and light emission signals are collected.

[0022] Calculate the ratio of the light emission signal to the current signal, and determine the type of gas to be tested based on the ratio.

[0023] The organic amine gas detection method further includes the following steps:

[0024] The method for detecting organic amine gas further includes the following steps:

[0025] Cyclic voltammetry was performed on the electrochemiluminescence gas sensor used for detecting organic amine gas to find the redox peak and redox peak potential of the electrochemiluminescence probe.

[0026] Based on the redox peak potential, a working voltage is applied to the electrochemiluminescence gas sensor for detecting organic amine gas. Different wavelength filters are used to detect the emission wavelength of the electrochemiluminescence gas sensor for detecting organic amine gas. The filter with the strongest response is selected as the filter used to collect the emission signal.

[0027] During the cyclic voltammetry test, the parameters are set as follows:

[0028] The voltage is set to 0~1.6V;

[0029] During the detection of the emission wavelength, a photomultiplier tube is used to collect the emission signal. The parameters of the photomultiplier tube are set as follows:

[0030] The voltage is set to 800-1200V;

[0031] After determining the type of gas to be tested based on the ratio, the organic amine gas detection method further includes the following steps:

[0032] The concentration of the gas to be measured is determined based on the light emission signal or the current signal.

[0033] The method for detecting organic amine gas, wherein when the ionic liquid is [BMIM][PF6], the electrochemiluminescence probe is Ru(bpy)3Cl2·6H2O or Ru(bpy)3(PF6)2, and the concentration of the electrochemiluminescence probe in the ionic liquid is 32 mmol / L, the process of contacting the gas to be tested with the electrochemiluminescence gas sensor for detecting organic amine gas and collecting the current signal and the luminescence signal specifically includes the following steps:

[0034] An operating voltage is applied to the electrochemiluminescence gas sensor for detecting organic amine gas, the gas to be tested is introduced, and the current signal is collected. At the same time, a filter is used to collect the luminescence signal.

[0035] When acquiring the current signal, the parameters are set as follows: apply a working voltage of 1.35V;

[0036] When collecting the light emission signal, a photomultiplier tube is used to collect the light emission signal, and the parameters of the photomultiplier tube are set as follows: the voltage is set to 950V.

[0037] Beneficial effects: The electrochemiluminescence gas sensor for detecting organic amine gas in this application is based on a photoelectric bivariate response mode, which can effectively distinguish organic amine gas and achieve ppm-level detection of organic amine gas at room temperature. Attached Figure Description

[0038] Figure 1 The graph shows the results of cyclic voltammetry tests on two different sensors in Embodiment 1 of this application.

[0039] Figure 2 This is a graph showing the emission signals of the electrochemiluminescence gas sensor used to detect organic amine gas in Example 2 of this application at different wavelengths.

[0040] Figure 3 This is a graph showing the photoelectric bivariate response of the electrochemiluminescence gas sensor used to detect organic amine gas in Example 3 of this application to 10 ppm of tri-n-propylamine.

[0041] Figure 4 This is a graph showing the photoelectric bivariate response of the electrochemiluminescence gas sensor used to detect organic amine gas in Example 4 of this application to 10 ppm of amphetamine.

[0042] Figure 5 This is a graph showing the photoelectric bivariate response of the electrochemiluminescence gas sensor used to detect organic amine gas in Example 5 of this application to 100 ppm of amphetamine. Detailed Implementation

[0043] This application provides a composite electrolyte for detecting organic amine gas, its preparation method, an electrochemiluminescence gas sensor, and a detection method. To make the objectives, technical solutions, and effects of this application clearer and more explicit, the following provides a more detailed description. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0044] To overcome the selectivity limitations of existing sensors and improve sensor reliability, novel gas sensors based on the principle of multivariable response are rapidly developing. Multivariable sensors (also known as intelligent, multi-parameter, high-order, or multidimensional characteristic sensors) provide completely independent multidimensional variable responses from the sensor. The general design criteria for multivariable sensors involve the following aspects: (1) sensing materials with different responses to different gases; (2) multivariable sensors that provide independent outputs and identify these different gas responses; and (3) data analysis that provides quantification of multiple analytes, interference suppression, and drift minimization. Electrochemiluminescence gas sensors, due to their potential bivariate response of both luminescence and current signals, and their inherent high sensitivity, low background signal, low cost, and real-time room temperature monitoring capability, have become ideal tools for the bivariate response and selective detection of amine gases.

[0045] This application provides a composite electrolyte for detecting organic amine gas, comprising an electrochemiluminescence probe and an ionic liquid. In this application, the luminescence signal from the electrochemiluminescence probe and the current signal generated by the organic amine gas are used as a photoelectric bivariate response. The electrochemiluminescence probe can generate gas-sensing luminescence signals with various amines. The composite electrolyte for detecting organic amine gas is an ionic liquid with high solubility for organic amine gas, providing a sensitive current response.

[0046] This application provides a method for preparing a composite electrolyte for detecting organic amine gas, comprising the following steps:

[0047] The electrochemiluminescence probe was dissolved in an ionic liquid to obtain the composite electrolyte used for detecting organic amine gas.

[0048] This application provides an electrochemiluminescence gas sensor for detecting organic amine gas, including a sensor and the aforementioned composite electrolyte for detecting organic amine gas; the composite electrolyte for detecting organic amine gas is coated on the electrodes of the sensor.

[0049] The electrochemiluminescence gas sensor for detecting organic amine gas disclosed in this application is a photoelectric dual-variable mode sensor. It uses a composite electrolyte of ionic liquid (IL) and electrochemiluminescence probe for detecting organic amine gas, and organic amine gas as a co-reactant of the electrochemiluminescence probe. The composite electrolyte for detecting organic amine gas, made of ionic liquid and electrochemiluminescence probe, uniformly covers the working electrode, reference electrode and counter electrode, thus completing the preparation of the electrochemiluminescence gas sensor for detecting organic amine gas.

[0050] This application presents a novel electrochemiluminescence gas sensor for detecting organic amine gases. Based on a bivariate response mode using a composite electrolyte for detecting organic amine gases, this sensor utilizes the luminescence signal from an electrochemiluminescence probe and the current signal generated by the organic amine gas as a photoelectric bivariate response, proposing a novel bivariate sensor for enhanced selectivity. The electrochemiluminescence probe can generate luminescence signals for gas sensing with various amines. The electrolyte is an ionic liquid with high solubility for organic amine gases to provide a sensitive current response. The luminescence signal and the current signal are output independently.

[0051] Specifically, the preparation method of the electrochemiluminescence gas sensor for detecting organic amine gas according to this application includes the following steps:

[0052] The composite electrolyte for detecting organic amine gas was uniformly coated on the electrodes of the sensor to prepare the electrochemiluminescence gas sensor for detecting organic amine gas of this application.

[0053] Specifically, the ionic liquid used as the electrolyte can be an ionic liquid with high solubility for organic amine gases, including but not limited to one of [BMIM][PF6], [BMIM][BF4], [BMIM][BF6], [BMIM][Ac], [EMIM][NTF2], and [EMIM][Gly].

[0054] Specifically, the electrochemiluminescent probe, as the luminescent group, can be a probe molecule with electrochemiluminescent properties, including but not limited to one of Ru(bpy)3Cl2·6H2O and its derivatives, Ru(bpy)3(PF6)2 and its derivatives, [Ir(ppy)2(bpy)](PF6) and its derivatives.

[0055] Specifically, in this application, the concentration of the electrochemiluminescence probe in the ionic liquid is preferably 0.1-50 mmol / L. This range ensures the optimal balance between luminescence intensity and sensitivity, avoids signal noise problems, and optimizes the compatibility of the electrochemiluminescence probe with the ionic liquid and the long-term stability of the system.

[0056] The electrochemiluminescence gas sensor for detecting organic amine gas disclosed in this application utilizes the organic amine gas as a co-reactant, reacting with the luminescence signal generated by the electrochemiluminescence probe. A photomultiplier tube (PMT) collects the luminescence signal, and simultaneously, an electrochemical workstation acquires the current response generated by the organic amine gas as an electrical signal using a constant potential or step potential mode. Specifically, the organic amine gas can be one or more of amphetamine (AP), tri-n-propylamine (TPrA), methamphetamine (MA), dimethylamine, trimethylamine, diethylamine, and triethylamine.

[0057] In the embodiments of this application, the ionic liquid is preferably [BMIM][PF6], the electrochemiluminescence probe is preferably Ru(bpy)3Cl2·6H2O or Ru(bpy)3(PF6)2, and the concentration of the electrochemiluminescence probe in the ionic liquid is preferably 32 mmol / L. In the preferred embodiment, the concentration of the electrochemiluminescence probe is 32 mmol / L, which represents the optimal equilibrium point, further improving the stability and repeatability of the luminescence signal, and is suitable for the field of organic amine gas sensing and detection. In the embodiments of this application, Ru(bpy)3Cl2·6H2O or Ru(bpy)3(PF6)2 is used. 2+ The luminescent signal and the current signal generated by the organic amine gas are used as a photoelectric bivariate response, Ru(bpy)3 2+ It can generate luminescent signals for gas sensing with various amines. The electrolyte is an ionic liquid [BMIM][PF6] with high solubility for organic amine gases to provide a sensitive current response.

[0058] Furthermore, the sensor is an electrochemical sensor, and the electrodes of the sensor include a working electrode, a reference electrode, and a counter electrode. Specifically, the process of uniformly coating the sensors with a composite electrolyte for detecting organic amine gas involves uniformly coating the working electrode, reference electrode, and counter electrode with the composite electrolyte for detecting organic amine gas.

[0059] The amount of composite electrolyte used for detecting organic amine gases is determined based on the electrode area, with 5-100 μL of composite electrolyte per square centimeter of electrode. This dosage range ensures that the composite electrolyte completely covers the working electrode, counter electrode, and reference electrode. Furthermore, since the composite electrolyte is liquid, this dosage avoids leakage problems caused by overflow, thereby improving the signal stability, repeatability, and lifespan of the sensor. In a preferred embodiment, the amount of composite electrolyte used for detecting organic amine gases is 30 μL / cm², which further optimizes the efficiency of the electrochemical reaction and is suitable for industrial-scale production.

[0060] This application also provides a detection method based on the above-mentioned electrochemiluminescence gas sensor for detecting organic amine gas, comprising the following steps:

[0061] (1) Cyclic voltammetry was performed on the electrochemiluminescence gas sensor used to detect organic amine gas to find the redox peak and redox peak potential of the electrochemiluminescence probe;

[0062] (2) Based on the redox peak potential, apply the working voltage to the electrochemiluminescence gas sensor used to detect organic amine gas, use filters of different wavelengths to detect the emission wavelength of the electrochemiluminescence gas sensor used to detect organic amine gas, and select the filter with the strongest response as the filter used to acquire the ECL signal.

[0063] (3) The gas to be tested is brought into contact with the electrochemiluminescence gas sensor used to detect organic amine gas, and the current signal and ECL signal are collected;

[0064] (4) Calculate the ratio of the ECL signal and the current signal, and determine the type of gas to be tested based on the ratio.

[0065] During the detection process, the luminescence signal and the current signal are output independently. The organic amine gas, as a co-reactant, will generate a luminescence signal (i.e., ECL signal) with the electrochemiluminescence probe, which can be collected by a photomultiplier tube (PMT). At the same time, the current response generated by the organic amine gas can be collected by an electrochemical workstation using a constant potential or step potential mode.

[0066] Then, the ratio of the light emission signal to the current signal of various amine gases is processed. The ratio of the photoelectric dual response signals of different gases is different, thereby enabling selective identification of amine gases.

[0067] Specifically, in step (1), when performing the cyclic voltammetry test, the key parameters can be set as follows: the voltage can be set to 0~1.6V; other parameters can be set as follows: the scan rate can be set to 50-500mV / s, and the sampling interval can be set to 0.01-0.1V. The parameter settings consider the balance between response baseline, sampling accuracy, and efficiency. In the embodiment of this application, the parameters are set as follows: the voltage is set to 0~1.6V, the scan rate is set to 100mV / s, and the sampling interval is set to 0.05V. Under these parameter conditions, the test results are the best.

[0068] In step (2), the photomultiplier tube (PMT) collects the emission signal. The key parameters of the PMT can be set as follows: voltage set to 800-1200V; other parameters can be set as follows: sampling interval set to 0.01-1s. In the embodiment of this application, the parameters of the PMT are set as follows: voltage set to 950V, sampling interval set to 0.5s.

[0069] Step (3) specifically includes the following steps:

[0070] Nitrogen was selected as the background gas, and the test was conducted at room temperature. The working voltage was applied to the electrochemiluminescence gas sensor used to detect organic amine gas, the background gas was introduced, and after the luminescence signal tended to stabilize, the gas to be tested was introduced, the current signal was collected, and the ECL signal was collected at the same time using a filter.

[0071] In step (3), during the test, the working voltage is applied to the electrochemiluminescence gas sensor used to detect organic amine gas according to the redox peak potential value in step (1), and the filter used is the filter with the strongest response in step (2).

[0072] In step (3), the flow rates of both the background gas and the gas to be tested are 100 mL / min.

[0073] In step (3), the key parameter for acquiring the current signal can be set to: applied operating voltage; other parameter settings can be: sampling interval can be set to 0.01-0.1V; the key parameter for the PMT can be set to: voltage set to 800-1200V; other parameter settings can be: sampling interval set to 0.01-1s. In the embodiment of this application, the parameters for acquiring the current signal are set to: sampling interval set to 0.5s, and the parameters for the PMT are set to: voltage set to 950V, sampling interval set to 0.5s.

[0074] In this application, the type of gas to be tested can be more accurately determined by comparing ratios. Using two independent two-dimensional response signals—current signal and emission signal—allows for more accurate determination of the gas type and concentration, essentially meaning two X variables jointly determine one Y. Although, in the current Example 4, the emission signals of tri-n-propylamine and amphetamine at the same concentration differ significantly, their emission signals are roughly similar at lower concentrations of tri-n-propylamine and higher concentrations of amphetamine. Therefore, if only the emission signal is collected, it will be impossible to determine the type of organic amine gas.

[0075] In this application, the sensor employing a photoelectric dual-variable response mode ensures that even in the aforementioned situations, the sensor has another variable—the current signal—to pinpoint the type of gas to be measured. In a preferred embodiment, for the detection of tripropylamine and amphetamine, even if their emission signals are similar at specific concentrations, they can still be clearly distinguished by the emission / current ratio, significantly improving the sensor's reliability and practicality.

[0076] Based on the electrochemiluminescence gas sensor for detecting organic amine gases in this application, a method for determining the type of gas based on the ratio of luminescence signal to current signal is proposed. This method collects the luminescence signal and current signal generated by the electrochemiluminescence gas sensor for detecting organic amine gases during operation, calculates the ratio between the two, and achieves selective identification of different organic amine gases, thereby performing qualitative and quantitative analysis of the gas to be tested.

[0077] For gas detection, theoretically, this ratio remains relatively stable for the same gas. For example, the ratio for tripropylamine is approximately 16729, and the ratio for amphetamine is approximately 5401.3. Therefore, the ratio method is mainly used to improve the selectivity of sensors and distinguish gas types, rather than for quantitative determination of gas concentration.

[0078] For gas concentration detection, this application can achieve it through independent emission or current signals. Specifically, the emission intensity or current magnitude has a linear relationship with the gas concentration within a certain range, and quantitative analysis can be performed by establishing a standard curve. Furthermore, a dual-signal fusion algorithm can be combined to further improve the accuracy and anti-interference capability of concentration detection.

[0079] The electrochemiluminescence gas sensor for detecting organic amine gases provided in this application is not only suitable for detecting a single organic amine gas, but can also achieve simultaneous identification of multiple organic amine gases through a signal decoupling algorithm. Specifically, when multiple organic amine gases coexist, the total luminescence signal and total current signal collected by the electrochemiluminescence gas sensor for detecting organic amine gases can be expressed as a linear superposition of the contributions of each gas. By establishing a multivariate equation system and combining it with a machine learning algorithm, the type and concentration of each gas can be deduced.

[0080] Compared with traditional methods that rely solely on emission signals, the proposed solution has the following advantages:

[0081] 1. Improve the accuracy of gas type identification and avoid misjudgment caused by similar luminescence signals of different gases at specific concentrations;

[0082] 2. Enhance the sensor's anti-interference capability and counteract the impact of environmental factors on a single signal;

[0083] 3. Expand the detection range and improve response linearity;

[0084] 4. Enables multivariate detection, laying the foundation for subsequent intelligent recognition.

[0085] The present application will be further described below through specific embodiments.

[0086] Example 1

[0087] This embodiment fabricated a sensor based on IL electrolyte and a sensor based on IL / Ru(bpy)3. 2+ Electrolyte sensor.

[0088] (1) The specific fabrication steps of the IL-based electrolyte sensor are as follows:

[0089] Measure 10 μL of pure ionic liquid [BMIM][PF6] and uniformly cover the working electrode, reference electrode, and counter electrode to complete the fabrication of the IL-based electrolyte sensor. 30 μL of IL electrolyte is used per square centimeter of electrode.

[0090] (2) Based on IL / Ru(bpy)3 2+ The specific fabrication steps for the electrolyte sensor are as follows:

[0091] The preparation of the composite electrolyte for detecting organic amine gas is completed by dissolving Ru(bpy)3Cl2·6H2O in the ionic liquid [BMIM][PF6]. The concentration of Ru(bpy)3Cl2·6H2O in [BMIM][PF6] is 32 mmol / L.

[0092] Take 10 μL of the prepared composite electrolyte for detecting organic amine gas and evenly cover the working electrode, reference electrode, and counter electrode to complete the IL / Ru(bpy)3-based detection. 2+ Fabrication of an electrolyte sensor. Specifically, 30 μL of IL / Ru(bpy)3 was used per square centimeter of electrode. 2+ Electrolytes.

[0093] In this embodiment, the sensor based on IL electrolyte and the sensor based on IL / Ru(bpy)3 are discussed. 2+The electrolyte sensors were subjected to cyclic voltammetry tests to search for Ru(bpy)3. 2+ With Ru(bpy)3 3+ The redox peaks and redox potentials were observed. The testing procedure is as follows:

[0094] Nitrogen was selected as the background gas, and the test was conducted at room temperature. The background gas was introduced at a flow rate of 100 mL / min. After purging the impurity gases in the gas chamber and gas path, the cyclic voltammetry test was started. No test gas was input during the test. The cyclic voltammetry test parameters were: voltage set to 0~1.6V, scan rate set to 100mV / s, and sampling interval set to 0.05V.

[0095] Test results are as follows Figure 1 As shown (where IL is an IL-based electrolyte sensor, IL / Ru(bpy)3), 2+ For IL / Ru(bpy)3 2+ The electrolyte sensor observed a pair of distinct redox peaks at 1.35V and 1.4V, and the close peak potentials indicate that the reaction is highly reversible.

[0096] Example 2

[0097] This embodiment prepares an electrochemiluminescence gas sensor (hereinafter referred to as "sensor") for detecting organic amine gas. The specific steps are as follows:

[0098] The preparation of the composite electrolyte for detecting organic amine gas is completed by dissolving Ru(bpy)3Cl2·6H2O in the ionic liquid [BMIM][PF6]. The concentration of Ru(bpy)3Cl2·6H2O in [BMIM][PF6] is 32 mmol / L.

[0099] Measure 10 μL of the prepared composite electrolyte for detecting organic amine gas and evenly cover the working electrode, reference electrode, and counter electrode to complete the sensor fabrication. Specifically, 30 μL of IL / Ru(bpy)3 is used per square centimeter of electrode. 2+ Electrolytes.

[0100] The emission wavelength of the sensor in Example 2 was tested, and the test process is as follows:

[0101] The sensor parameters are set as follows: apply a working voltage of 1.35V and set the sampling interval to 0.5s; the PMT parameters are set as follows: voltage of 950V and sampling interval of 0.5s.

[0102] Nitrogen was selected as the background gas, and the test was conducted at room temperature. After the background gas was introduced and the emission signal stabilized, the test gas—10 ppm of TPRA—was introduced. The flow rates of both the background gas and the test gas were 100 mL / min. Different filters were used for detection, and the emission signals of different wavelengths of the filters were recorded. The filters used were 380 nm, 425 nm, 520 nm, 555 nm, 575 nm, 590 nm, and 620 nm.

[0103] Test results are as follows Figure 2 As shown, the response is strongest at 620nm. In subsequent embodiments, a 620nm filter is used for ECL signal acquisition.

[0104] Example 3

[0105] The sensor in this embodiment is prepared using the same method as in Embodiment 2. This embodiment uses a bivariate response detection method for the luminescence and current signals of tri-n-propylamine gas.

[0106] The testing process is as follows:

[0107] The sensor parameters are set as follows: apply a working voltage of 1.35V and set the sampling interval to 0.5s; the PMT parameters are set as follows: voltage of 950V and sampling interval of 0.5s.

[0108] Nitrogen was selected as the background gas, and the test was conducted at room temperature. After the background gas was introduced and the emission signal stabilized, the test gas, 10 ppm of tri-n-propylamine (TPrA), was introduced. The flow rates of both the background gas and the test gas were 100 mL / min. ECL signal acquisition was performed using a 620 nm filter, and the emission signal and current signal were recorded simultaneously.

[0109] In this embodiment, Ru(bpy)3 2+ As the luminescent agent in electrochemiluminescence, tri-n-propylamine gas acts as a co-reactant, generating a luminescent signal. Under potentiometric catalysis, tri-n-propylamine produces a current signal. The test results are as follows: Figure 3 As shown in the figure (the upper figure is the result of the emission signal, and the lower figure is the result of the current signal), the results show that the sensor prepared in this embodiment can achieve photoelectric bivariate response detection of tri-n-propylamine gas at the ppm level.

[0110] Example 4

[0111] The sensor in this embodiment is prepared using the same method as in Example 2. This embodiment uses a bivariate response detection of the luminous and electrical signals of amphetamine gas.

[0112] The testing process is as follows:

[0113] The sensor parameters are set as follows: apply a working voltage of 1.35V and set the sampling interval to 0.5s; the PMT parameters are set as follows: voltage of 950V and sampling interval of 0.5s.

[0114] Nitrogen was selected as the background gas, and the test was conducted at room temperature. After the background gas was introduced and the emission signal stabilized, the test gas, 10 ppm of amphetamine (AP), was introduced. The flow rates of both the background gas and the test gas were 100 mL / min. ECL signal was acquired using a 620 nm filter, and the emission signal and current signal were recorded simultaneously.

[0115] In this embodiment, Ru(bpy)3 2+ As the luminescent agent in electrochemiluminescence, amphetamine gas acts as a co-reactant, generating a luminescent signal, while amphetamine produces a current signal under potentiometric catalysis. The test results are as follows... Figure 4 As shown in the figure (the upper figure is the result of the emission signal, and the lower figure is the result of the current signal), the results show that the sensor prepared in this embodiment can achieve photoelectric bivariate response detection of amphetamine gas at the ppm level.

[0116] Example 5

[0117] The sensor in this embodiment is prepared using the same method as in Example 2. This embodiment uses a bivariate response detection of the luminous and electrical signals of amphetamine gas.

[0118] The testing process is as follows:

[0119] The sensor parameters are set as follows: apply a working voltage of 1.35V and set the sampling interval to 0.5s; the PMT parameters are set as follows: voltage of 950V and sampling interval of 0.5s.

[0120] Nitrogen was selected as the background gas, and the test was conducted at room temperature. After the background gas was introduced and the emission signal stabilized, the test gas, 100 ppm of amphetamine (AP), was introduced. The flow rates of both the background gas and the test gas were 100 mL / min. ECL signal was acquired using a 620 nm filter, and the emission signal and current signal were recorded simultaneously.

[0121] In this embodiment, Ru(bpy)3 2+ As the luminescent agent in electrochemiluminescence, amphetamine gas acts as a co-reactant, generating a luminescent signal, while amphetamine produces a current signal under potentiometric catalysis. The test results are as follows... Figure 5 As shown in the figure (the upper figure is the result of the emission signal, and the lower figure is the result of the current signal), the results show that the sensor prepared in this embodiment can achieve photoelectric bivariate response detection of amphetamine gas at the ppm level.

[0122] Example 6

[0123] This embodiment proposes a selective identification method based on sensor-based photoelectric bivariate signals (luminescence signal and current signal) to distinguish and detect organic amine gas.

[0124] In this embodiment, the photoelectric bivariate signals of tripropylamine and amphetamine measured by the sensors in Examples 3, 4, and 5 were processed by ratio analysis. Selective identification of organic amine gases was performed based on the difference in the ratio of the photoelectric bivariate signals, and the results are shown in Table 1. The results show that, at the same gas concentration, the ratio of the luminous signal to the current signal of tripropylamine (16729.5) is much greater than that of amphetamine (5401.3). When the concentration of amphetamine is 100 ppm, the luminous signal is roughly similar to that of tripropylamine at 10 ppm, making gas differentiation impossible. However, the ratio of the luminous signal to the current signal of amphetamine at 100 ppm (5917.8) remains relatively stable and is much smaller than that of tripropylamine (16729.5), allowing for gas differentiation. Furthermore, the gas concentration of the same gas can be tested using the response values ​​of the luminous and current signals. The sensor based on this application can achieve differentiated detection of tripropylamine and amphetamine gases, and the selectivity of the sensor can be improved based on the photoelectric bivariate response.

[0125] Table 1

[0126]

[0127] In summary, the electrochemiluminescence gas sensor for detecting organic amine gas based on the above-mentioned method has the following advantages:

[0128] 1. A selective identification method based on photoelectric dual-variable signals (luminescence signal and current signal) can effectively distinguish and detect organic amine gases;

[0129] 2. A detection method for an electrochemiluminescence gas sensor based on photoelectric dual-variable mode for detecting organic amine gas was developed, achieving ppm-level detection of organic amine gas at room temperature.

[0130] It should be understood that the application of this application is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of this application.

Claims

1. A method for detecting organic amine gas, characterized in that, The detection method for organic amine gas is based on an electrochemiluminescence gas sensor for detecting organic amine gas, and includes the following steps: The gas to be tested is brought into contact with the electrochemiluminescence gas sensor used to detect organic amine gas, and current signals and light emission signals are collected. Calculate the ratio of the light emission signal to the current signal, and determine the type of gas to be tested based on the ratio; The electrochemiluminescence gas sensor for detecting organic amine gas includes a sensor and a composite electrolyte for detecting organic amine gas. The composite electrolyte used for detecting organic amine gas is coated on the electrodes of the sensor; The composite electrolyte used for detecting organic amine gas comprises an electrochemiluminescent probe and an ionic liquid as raw materials. The electrochemiluminescent probe includes one of Ru(bpy)3Cl2·6H2O and its derivatives, Ru(bpy)3(PF6)2 and its derivatives, and [Ir(ppy)2(bpy)](PF6) and its derivatives; The ionic liquid includes one of [BMIM][PF6], [BMIM][BF4], [BMIM][BF6], [BMIM][Ac], [EMIM][NTF2], and [EMIM][Gly]. The concentration of the electrochemiluminescent probe in the ionic liquid is 0.1-50 mmol / L.

2. The detection method for detecting organic amine gas according to claim 1, characterized in that, The ionic liquid is [BMIM][PF6], and the electrochemiluminescent probe is Ru(bpy)3Cl2·6H2O or Ru(bpy)3(PF6)2.

3. The detection method for detecting organic amine gas according to claim 1, characterized in that, The concentration of the electrochemiluminescent probe in the ionic liquid is 32 mmol / L.

4. The detection method for detecting organic amine gas according to claim 1, characterized in that, The method for preparing the composite electrolyte for detecting organic amine gas includes the following steps: The electrochemiluminescence probe was dissolved in an ionic liquid to obtain the composite electrolyte used for detecting organic amine gas.

5. The detection method for detecting organic amine gas according to claim 1, characterized in that, The electrode is provided with 5-100 μL of the composite electrolyte for detecting organic amine gas per square centimeter.

6. The detection method for detecting organic amine gas according to claim 1, characterized in that, The electrode is provided with 30 μL of the composite electrolyte for detecting organic amine gas per square centimeter.

7. The detection method for detecting organic amine gas according to claim 1, characterized in that, The detection method for detecting organic amine gas further includes the following steps: Cyclic voltammetry was performed on the electrochemiluminescence gas sensor used to detect organic amine gas to find the redox peak and redox peak potential of the electrochemiluminescence probe. Based on the redox peak potential, a working voltage is applied to the electrochemiluminescence gas sensor for detecting organic amine gas. Different wavelength filters are used to detect the emission wavelength of the electrochemiluminescence gas sensor for detecting organic amine gas. The filter with the strongest response is selected as the filter used to collect the emission signal. During the cyclic voltammetry test, the parameters are set as follows: The voltage is set to 0~1.6V; During the detection of the emission wavelength, a photomultiplier tube is used to collect the emission signal. The parameters of the photomultiplier tube are set as follows: The voltage is set to 800-1200V; After determining the type of gas to be tested based on the ratio, the method for detecting organic amine gas further includes the following steps: The concentration of the gas to be measured is determined based on the light emission signal or the current signal.

8. The detection method for detecting organic amine gas according to claim 1, characterized in that, When the ionic liquid is [BMIM][PF6], and the electrochemiluminescence probe is Ru(bpy)3Cl2·6H2O or Ru(bpy)3(PF6)2, and the concentration of the ionic liquid is 32 mmol / L, the process of contacting the gas to be tested with the electrochemiluminescence gas sensor for detecting organic amine gas and collecting the current signal and the luminescence signal specifically includes the following steps: An operating voltage is applied to the electrochemiluminescence gas sensor for detecting organic amine gas, the gas to be tested is introduced, and the current signal is collected. At the same time, a filter is used to collect the luminescence signal. When acquiring the current signal, the parameters are set as follows: apply a working voltage of 1.35V; When collecting the light emission signal, a photomultiplier tube is used to collect the light emission signal, and the parameters of the photomultiplier tube are set as follows: the voltage is set to 950V.

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