Preparation method of electrochemical sensing gloves for detecting chemical agent markers

Abstract

This paper discloses a method for preparing an electrochemical sensing glove based on screen-printed electrodes (SPEs) modified with Cu-BTC and Au@Cu-BTC materials. A layered Cu-BTC MOF material with a large specific surface area, strong surface reactivity, and strong electron transfer ability was prepared for the hydrolysis products of nerve agents, ethyl methyl phosphate (EMPA) and isopropyl methyl phosphate (IMPA), which have high chemical stability and limited electrochemical activity. Gold nanoparticles (Au NPs) obtained by plasma reduction were loaded on the layered Cu-BTC material to prepare the Au@Cu-BTC material. The strong affinity of the Au-S bond formed between the Au@Cu-BTC material and thiodiglycol (TDG), a hydrolysis product of mustard gas, was utilized to construct an electrochemical sensing glove for efficiently detecting TDG. The detection device is simple to operate, convenient, time-saving, and low-cost, and can be used for online detection in the field.

Description

Technical Field

[0001] The present invention relates to the technical field of detection of chemical agent markers, and in particular to a method for preparing an electrochemical sensing glove for detecting chemical agent markers. Background Art

[0002] Chemical warfare agents (CWAs) are characterized by their high toxicity, rapid onset, and potential for systemic poisoning. The threat posed by CWAs to international peace and security has raised serious concerns due to their rapid action, potent toxicity, and widespread destructive potential. Typical chemical warfare agents fall into two categories: nerve agents, including sarin (GB), soman (GD), and VX, and mustard gas (HD). HD nerve gas, for example, hydrolyzes in aqueous environments to form ethyl methyl phosphate (EMPA) and isopropyl methyl phosphate (IMPA). Mustard gas (HD), a toxic blistering agent, can produce thiodiglycol (TDG). Compounds such as EMPA, IMPA, or TDG are considered environmental markers that can be used to track the intentional or accidental use of chemical warfare agents.

[0003] Developing a simple, rapid, and accurate method for detecting trace levels of chemical warfare agents in the environment is crucial. Over the past few decades, a variety of methods have been established for chemical warfare agent detection, such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), mass spectrometry imaging, and surface-enhanced Raman spectroscopy. However, expensive instrumentation or specialized personnel have limited their application. Therefore, developing cost-effective, user-friendly, and practical field detection methods to identify chemical warfare agents in real-world environments is urgent for both military and civilian applications.

[0004] Electrochemical detection is used to determine the electrochemical activity and reaction characteristics of substances on the electrode surface, and the detection of substances is achieved by observing changes in current, voltage or impedance. Electrochemical technology has attracted much attention due to its advantages such as high sensitivity, good selectivity, simple operation and low cost. Electrochemical detection can achieve real-time detection on site. The hydrolysis products of CWAs have high chemical stability and are difficult to participate in electrochemical redox reactions. Therefore, they usually exhibit limited electrochemical activity, which often leads to low selectivity, low sensitivity and reproducibility. The application of modified electrodes solves this problem. However, electrode modification still faces challenges such as high material cost, complex preparation process and insufficient stability. Therefore, people have been studying catalytic materials that can provide good sensing performance and sensitivity of electrochemical sensors. Summary of the Invention

[0005] To address these issues, the present invention synthesized Cu-BTC and Au@Cu-BTC electrode-modified materials with high sensitivity and selectivity for CWAs hydrolysis products (EMPA, IMPA, and TDG). These materials served as the core for constructing a screen-printed electrode (SPE) electrochemical sensing glove, enabling rapid and sensitive detection of CWAs markers. Compared to traditional technologies, this detection method is simpler and faster, with low sensitivity, and can be used for field testing.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] Step 1: Preparation of Cu-BTC and Au@Cu-BTC electrode modification materials

[0008] (1) Preparation of Cu-BTC

[0009] Copper nitrate trihydrate (Cu(NO₃)₂·3H₂O) was weighed and dissolved in ethanol. Acetic acid and trimethylamine were then added sequentially and stirred thoroughly. Trimellitic acid (H₃BTC) was then added to the solution, stirred thoroughly, and transferred to a Teflon-lined autoclave. After continuous heating and holding for a period of time, the mixture was cooled to room temperature, centrifuged, and washed several times with ethanol.

[0010] (2) Preparation of gold nanoparticles (AuNPs)

[0011] To produce an aqueous solution of AuNPs, a mixture of tetrachloroauric acid (HAuCl4) and sodium citrate is treated with an alternating current-driven low-temperature plasma. The plasma jet is positioned above the solution. A needle-ring electrode structure serves as the high-voltage electrode. A copper strip wrapped around the surface of a quartz tube serves as the ground electrode. After a period of plasma treatment, the solution gradually changes color from light yellow to pink, indicating the production of Au nanoparticles.

[0012] (3) Preparation of Au@Cu-BTC

[0013] Cu-BTC and polyvinylpyrrolidone (PVP) were dissolved in an ethanol solution, and the prepared AuNPs were added while stirring. The mixture was vigorously stirred at room temperature. The sample was then centrifuged and washed to prepare Au@Cu-BTC.

[0014] Step 2: Preparation of SPE based on Cu-BTC and Au@Cu-BTC

[0015] (1) The screen-printed electrode was immersed in sulfuric acid solution and subjected to cyclic voltammetry scanning. It was then washed with ultrapure water and dried to obtain an activated screen-printed electrode.

[0016] (2) Cu-BTC and Au@Cu-BTC suspensions were added to the surface of the above electrodes and dried at room temperature to obtain Cu-BTC / SPE and Au@Cu-BTC / SPE electrodes.

[0017] Step 3: Preparation of SPE electrochemical sensing gloves

[0018] The Cu-BTC / SPE and Au@Cu-BTC / SPE electrodes obtained in step 2 were combined with protective gloves to prepare sensing gloves. The Cu-BTC / SPE was loaded onto the index finger to form an IF / Cu-BTC / SPE for EMPA detection. The Cu-BTC / SPE was loaded onto the middle finger to form an MF / Cu-BTC / SPE for IMPA detection. The Au@Cu-BTC / SPE was loaded onto the ring finger to form an RF / Au@Cu-BTC / SPE for TDG detection.

[0019] Step 4: SPE electrochemical sensing gloves performance test

[0020] (1) Phosphate buffered saline (PBS) and different concentrations of EMPA, IMPA, and TDG solutions were added dropwise onto the surface of the screen-printed electrode prepared in step 2.

[0021] (2) Cyclic voltammetry is used to activate and stabilize the electrode.

[0022] (3) The screen-printed electrode with PBS buffer added was subjected to differential pulse voltammetry (DPV) measurement, and its response current was recorded as I0.

[0023] (4) Measure the DPV current change of the screen-printed electrode after adding different concentrations of EMPA, and record the current response. Finally, plot a standard curve with the current change as the y-axis and the EMPA concentration as the x-axis, using a sweep voltage of -0.6 to 0.6 V, and calculate the limit of detection (LOD).

[0024] (5) Measure the DPV current change of the screen-printed electrode after adding different concentrations of IMPA, and record the current response. Finally, plot a standard curve with the current change as the ordinate and the IMPA concentration as the abscissa, and calculate the limit of detection (LOD).

[0025] (6) Measure the DPV current change of the screen-printed electrode after adding different concentrations of TDG, and record the current response. Finally, draw a standard curve with the current change as the ordinate and the TDG concentration as the abscissa, and calculate the detection limit (LOD).

[0026] As a further embodiment of the present invention, the volume of the ethanol solution in step 1 can be selected in the range of 100 to 120 mL, the mass of copper nitrate trihydrate is preferably in the range of 1.0 g to 4.35 g, the volume of acetic acid is preferably in the range of 6 to 10 mL, the volume of trimethylamine is preferably in the range of 5.0 to 10 mL, and the mass of trimesic acid is preferably in the range of 2.10 to 4.50 g.

[0027] As a further solution of the present invention: the stirring time in step 1 is preferably 0.5h,

[0028] As a further solution of the present invention: the heating temperature in step 1 is preferably 100° C., and the insulation time is preferably in the range of 12 to 24 hours.

[0029] As a further embodiment of the present invention, in step 1, the mixture ratio of HAuCl4 and sodium citrate is 1:5 to 1:10. The plasma jet is positioned 1 to 3 cm above the solution. The high-voltage electrode hollow stainless steel tube has an inner diameter of 1.5 mm, a wall thickness of 0.1 mm, and a length of 150 mm. The copper strip has a width of 10 mm and a thickness of 180 μm. The plasma treatment time is 30 to 90 seconds.

[0030] As a further embodiment of the present invention, the Cu-BTC and polyvinylpyrrolidone in step 1 are mixed in a ratio of 1:10, dissolved in 50-100 mL of ethanol, and 0.1-1 g of AuNPs are added. The mixture is vigorously stirred for 1-2 h.

[0031] As a further solution of the present invention: in step 1, the centrifugal speed is 8000-10000 rpm, and the time is 5-10 minutes.

[0032] As a further solution of the present invention: the mass fraction of the sulfuric acid solution in step 2 is 1% to 5%, and the cyclic voltammetry scanning voltage is -1V to 1V.

[0033] As a further solution of the present invention: 1 to 100 μL of 5 mg / mL Cu-BTC and Au@Cu-BTC suspension is added in step 2.

[0034] As a further solution of the present invention: the pH value of the phosphate buffered saline solution in step 3 is 6, and the concentrations of the EMPA, IMPA and TDG solutions are 1 ng / mL to 100 μg / mL.

[0035] As a further solution of the present invention: in step 3, the scanning voltage range of the cyclic voltammetry is -1V to 1V, the scanning speed is 20mV / s to 50mV / s, and the number of scanning circles is 5 to 10 circles.

[0036] As a further solution of the present invention: in step 3, the scanning voltage of the differential pulse voltammetry is -0.6 to 0.6 V, and the scanning rate is 0.005 V s -1 , pulse amplitude is 0.05V, sampling width is 0.05s, pulse period is 0.5s, sensitivity is 1.0×10 -3 AV -1 .

[0037] The beneficial effects of the present invention are:

[0038] 1. The Cu-BTC layered metal organic framework material constructed by the present invention has the characteristics of large specific surface area, strong surface reaction activity, strong electron transfer ability, easy functionalization and composite, etc., which can effectively improve and enhance the performance of electrochemical sensors and effectively improve their electronic properties and conductivity. The Cu-BTC material can be modified by changing the Cu 2+ and organic ligands to adjust its physical and chemical properties, making it multifunctional. Cu has excellent conductivity, which is conducive to the transmission of electrical signals. 2+ Cu-BTC has a strong affinity for P=O and is used for electrochemical sensing of organophosphorus compounds, improving the sensitivity of electrochemical detection and enabling rapid and reliable detection of EMPA and IMPA.

[0039] 2. Combining AuNPs and Cu-BTC MOF materials to modify the surface of the screen-printed electrode can not only improve the conductivity of the electrode surface, enhance electron transfer, and effectively amplify the detection signal, but also Au can form an Au-S bond with the S element in TDG, realizing the electrochemical detection of TDG.

[0040] 3. Combining the modified screen-printed electrodes with protective gloves can achieve integrated protection and detection, enabling rapid, convenient, sensitive and low-cost detection of nerve agent hydrolysis products EMPA and IMPA and mustard gas hydrolysis product TDG in complex environments containing chemical agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 Schematic diagram of electrochemical sensing gloves based on Cu-BTC / SPE and Au@Cu-BTC / SPE

[0042] Figure 2 Schematic diagram of the preparation process of electrochemical detection system based on Cu-BTC / SPE and Au@Cu-BTC / SPE

[0043] Figure 3 (A) SEM images of Cu-BTC, (B) Au@Cu-BTC, (C) TEM images of AuNPs

[0044] Figure 4 (A) DPV response curve of the electrochemical sensor based on IF / Cu-BTC / SPE for detection of EMPA solutions with different concentrations, (B) fitting curve between DPV current response and EMPA concentration.

[0045] Figure 5 (A) DPV response curve of the electrochemical sensor based on MF / Cu-BTC / SPE for detection of IMPA solutions with different concentrations, (B) fitting curve between DPV current response and IMPA concentration.

[0046] Figure 6 (A) DPV response curve of the electrochemical sensor based on RF / Au@Cu-BTC / SPE for detection of TDG solutions with different concentrations, (B) fitting curve between DPV current response and TDG concentration.

[0047] In the figure, 1. protective gloves; 2. screen-printed (SPE) electrode; 6. adapter; 3. counter electrode (3); 4. working electrode; 5. reference electrode; 41. Cu-BTC material; 42. Au@Cu-BTC material; 7. wire; 8. protective layer. DETAILED DESCRIPTION

[0048] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0049] The present invention adopts an electrochemical sensing glove based on Cu-BTC / SPE and Au@Cu-BTC / SPE, such as Figure 1 As shown, it includes a protective glove (1), a screen-printed (SPE) electrode (2), and an adapter (6). The SPE electrode is composed of a counter electrode (3), a working electrode (4), and a reference electrode (5). The working electrode (4) is modified with two metal organic framework materials, Cu-BTC material (41) and Au@Cu-BTC material (42). The adapter (6) leads out three wires (7) at equal distances, which are respectively connected to the three electrodes of the SPE. A protective layer (8) is attached to the lead wires (7).

[0050] Figure 2The figure shows a schematic flow chart of the electrochemical detection system based on Cu-BTC / SPE and Au@Cu-BTC / SPE. First, the Cu-BTC material was prepared by solvothermal synthesis. Then, tetrachloroauric acid was reduced using plasma technology to obtain gold nanoparticles. Finally, the gold nanoparticles were mixed with Cu-BTC to form the Au@Cu-BTC material. The working electrodes (WE) attached to the index and middle fingers of the glove were then modified with 10.0 μL of a 5 mg / mL homogenous solution of Cu-BTC. The index finger was designated IF / Cu-BTC for EMPA detection. The middle finger was designated MF / Cu-BTC in IMPA. 10.0 μL of a 5 mg / mL homogenous solution of Au@Cu-BTC was dropped onto the ring finger WE to detect TDG, which was designated RF / Au@Cu-BTC. The electrochemical signals of the hydrolysis products at different concentrations were measured by DPV, enabling rapid and convenient detection.

[0051] The implementation steps are as follows:

[0052] 1. Preparation of Cu-BTC and Au@Cu-BTC electrode modified materials

[0053] (1) 4.35 g of zinc nitrate trihydrate, 6.2 mL of acetic acid, and 5.0 mL of trimethylamine were added to 12 mL of ethanol in sequence. After stirring for 1 h, 2.10 g of trimesic acid was added to the solution. The mixture was stirred for 2 h to form a homogeneous solution, which was then transferred to a polytetrafluoroethylene-lined autoclave. The mixture was heated at 120°C for 24 h, cooled naturally to room temperature, centrifuged, and washed with ethanol 3 to 5 times. Figure 3 (A) is a SEM image of Cu-BTC. The Cu-BTC material has nanoscale particle size, a relatively smooth surface, and a layered porous structure. This layered porous structure facilitates the transmission of electrical signals, increases the peak current response, and improves detection sensitivity, demonstrating the successful preparation of the Cu-BTC material.

[0054] (2) A mixed aqueous solution of tetrachloroauric acid (1.214 mM) and sodium citrate (34 mM) was treated with a low-temperature plasma driven by alternating current. The plasma jet was placed 1 cm above the solution. The plasma jet used a typical needle-ring electrode structure: a hollow stainless steel tube (inner diameter 1.5 mm, wall thickness 0.1 mm, length 150 mm) as a high-voltage electrode. A copper strip with a width of 10 mm and a thickness of 180 μm was wrapped around the surface of the quartz tube as a ground electrode. After 30 seconds, the color of the solution gradually changed from light yellow to pink, and AuNPs were produced. Figure 3 (B) is the TEM image of AuNPs, which are evenly distributed without clustering, which is conducive to their uniform dispersion in Cu-BTC.

[0055] (3) 1 g of Cu-BTC and 5 g of PVP were dissolved in an ethanol solution and sonicated for 30 min. The prepared AuNPs (0.1 g) were then added during the stirring process. The mixture was vigorously stirred at room temperature for 2 h. The sample was then centrifuged at 8000 rpm for 5 min and washed three times with ethanol. Finally, it was dried at 60°C for 12 h to obtain Au@Cu-BTC. Figure 3 (C) is the SEM image of Au@Cu-BTC material. Due to the use of PVP, Cu-BTC presents a cohesive layered structure, and uniformly dispersed spherical AuNPs are observed, indicating that the Au@Cu-BTC material is successfully prepared.

[0056] 2. Preparation of SPE based on Cu-BTC and Au@Cu-BTC

[0057] (1) Immerse the screen-printed electrode in a 1% to 5% sulfuric acid solution and perform cyclic voltammetry scanning at a scanning voltage of -1 V to 1 V. Then rinse with ultrapure water and dry to obtain an activated screen-printed electrode.

[0058] (2) Add 10 μL of 5 mg / mL Cu-BTC and Au@Cu-BTC suspensions to the surface of the above electrodes and dry them at room temperature to obtain Cu-BTC / SPE and Au@Cu-BTC / SPE electrodes.

[0059] Step 3: Preparation of SPE electrochemical sensing gloves

[0060] The Cu-BTC / SPE and Au@Cu-BTC / SPE electrodes from step 2 were combined with protective gloves, including: the index finger with IF / Cu-BTC / SPE for EMPA detection, the middle finger with MF / Cu-BTC / SPE for IMPA detection, and the ring finger with RF / Au@Cu-BTC / SPE for TDG detection.

[0061] Step 4: SPE electrochemical sensing gloves performance test

[0062] (1) Phosphate buffered saline (PBS) with a pH of 6 and EMPA, IMPA, and TDG solutions with a concentration of 1 ng / mL to 100 μg / mL were added dropwise onto the surface of the screen-printed electrode prepared in step 2.

[0063] (2) Cyclic voltammetry is used to activate and stabilize the electrode, with a scanning voltage range of -1V to 1V, a scanning speed of 20mV / s to 50mV / s, and a scanning number of 5 to 10 circles.

[0064] (3) The screen-printed electrode with PBS buffer added was subjected to differential pulse voltammetry (DPV) measurement, and its response current was recorded as I0. The scanning voltage was -0.6 to 0.6 V, and the scanning rate was 0.005 V s -1 , pulse amplitude is 0.05V, sampling width is 0.05s, pulse period is 0.5s, sensitivity is 1.0×10 -3 AV -1 .

[0065] (4) Measure the DPV current change of the screen-printed electrode with different concentrations of EMPA added, and record the current response as follows Figure 4 Finally, the standard curve was drawn with the current change as the ordinate and the EMPA concentration as the abscissa, and the scanning voltage was -0.6 to 0.6 V, and the detection limit (LOD) was calculated as shown in the figure below. Figure 4 (B) shown.

[0066] (5) Measure the DPV current change of the screen-printed electrode with different concentrations of IMPA added, and record the current response, such as Figure 5 Finally, the standard curve was drawn with the current change as the ordinate and the IMPA concentration as the abscissa, and the detection limit (LOD) was calculated, as shown in Figure 5 (B) shown.

[0067] (6) Measure the DPV current change of the screen-printed electrode with different concentrations of TDG added, and record the current response, such as Figure 6 Finally, the standard curve was drawn with the current change as the ordinate and the TDG concentration as the abscissa, and the detection limit (LOD) was calculated, as shown in Figure 6 (B) shown.

[0068] 4. Detection of EMPA in actual water samples

[0069] Three water samples with different concentrations were selected: 1 ng / mL (sample 1), 10 ng / mL (sample 2), and 100 ng / mL (sample 3). 60 μL of each sample was dripped onto the IF / Cu-BTC / SPE. Differential pulse voltammetry (DPV) was used on an electrochemical workstation to measure the EMPA solutions at different concentrations. The corresponding response currents were recorded. Based on the working curve Y = 35.23 log C + 276.7 obtained in Step 3, the EMPA concentration in each water sample was calculated. The test results are shown in Table 1.

[0070] Table 1 Detection of EMPA in real samples using IF / Cu-BTC sensor (n=3).

[0071]

[0072]

[0073] 5. Detection of IMPA in actual water samples

[0074] Three water samples with different concentrations were selected: 1 ng / mL (sample 1), 10 ng / mL (sample 2), and 100 ng / mL (sample 3). 60 μL of each water sample was dripped onto the MF / Cu-BTC / SPE. Differential pulse voltammetry (DPV) was used on an electrochemical workstation to measure the IMPA solutions of varying concentrations, and the corresponding response currents were recorded. Based on the working curve obtained in Step 3 (Y = 59.27 log C + 514.39), the IMPA concentration in each water sample was calculated. The test results are shown in Table 2.

[0075] Table 2 Detection of IMPA in actual samples by MF / Cu-BTC sensor (n=3).

[0076]

[0077] 5. Detection of TDG in actual water samples

[0078] Three water samples with different concentrations of TDG were selected: 1 ng / mL (sample 1), 10 ng / mL (sample 2), and 100 ng / mL (sample 3). 60 μL of each sample was dripped onto the RF / Au@Cu-BTC / SPE. Differential pulse voltammetry (DPV) was used on an electrochemical workstation to measure the TDG solutions at different concentrations. The corresponding response currents were recorded. The TDG concentration in each water sample was calculated using the working curve Y = 199.27 log C + 1861.21 obtained in Step 3. The test results are shown in Table 3.

[0079] Table 3 Detection of TDG in actual samples by RF / Au@Cu-BTC / SPE sensor (n=3)

[0080]

Claims

1. An electrochemical sensing glove based on Cu-BTC and Au@Cu-BTC materials, comprising a protective glove (1), a screen-printed (SPE) electrode (2) and an adapter (6), wherein the SPE electrode is composed of a counter electrode (3), a working electrode (4) and a reference electrode (5), and is characterized in that: The working electrode (4) is modified with two metal organic framework materials, Cu-BTC material (41) and Au@Cu-BTC material (42); the adapter (6) leads out three wires (7) at equal intervals, which are respectively connected to the three electrodes of the SPE, and a protective layer (8) is attached to the lead wires (7).

2. A method for preparing an electrochemical sensing glove based on Cu-BTC and Au@Cu-BTC materials, using the electrochemical sensing glove based on Cu-BTC and Au@Cu-BTC materials according to claim 1, characterized in that The method comprises the following steps: Step 1: Preparation of Cu-BTC and Au@Cu-BTC electrode modification materials (1) Preparation of Cu-BTC Copper nitrate trihydrate (Cu(NO3)2·3H2O) was weighed and dissolved in ethanol. Acetic acid (CH3COOH) and trimethylamine (C3H9N, TMA) were then added sequentially and stirred. Trimellitic acid (H3BTC) was then added to the solution, stirred evenly, and transferred to a polytetrafluoroethylene-lined autoclave. After continuous heating and insulation for a period of time, the mixture was naturally cooled to room temperature, centrifuged, and washed several times with ethanol. (2) Preparation of gold nanoparticles (AuNPs) To obtain an aqueous solution of AuNPs, a mixed aqueous solution of tetrachloroauric acid (HAuCl4) and sodium citrate was treated with an alternating current-driven low-temperature plasma. The plasma jet was placed above the solution. The plasma jet used a needle-ring electrode structure as the high-voltage electrode, and a copper strip wrapped around the surface of a quartz tube as the ground electrode. After a period of plasma treatment, the color of the solution gradually changed from light yellow to pink, and Au nanoparticles were obtained. (3) Preparation of Au@Cu-BTC Cu-BTC and polyvinylpyrrolidone (PVP) were dissolved in ethanol solution, and then the prepared AuNPs were added during stirring. The mixture was vigorously stirred at room temperature, and the sample was centrifuged and washed to prepare Au@Cu-BTC. Step 2: Preparation of SPE based on Cu-BTC and Au@Cu-BTC (1) Immersing the SPE in sulfuric acid solution, performing cyclic voltammetry scanning, washing with ultrapure water, and drying to obtain an activated screen-printed electrode; (2) Adding Cu-BTC and Au@Cu-BTC suspensions to the surface of the above electrodes and drying them at room temperature to obtain Cu-BTC / SPE and Au@Cu-BTC / SPE electrodes; Step 3: Preparation of SPE electrochemical sensing gloves The Cu-BTC / SPE and Au@Cu-BTC / SPE electrodes obtained in step 2 were combined with protective gloves. Cu-BTC / SPE was loaded on the index finger to form IF / Cu-BTC / SPE for EMPA detection; / Cu-BTC / SPE was loaded on the middle finger to form MF / Cu-BTC / SPE for IMPA detection; Au@Cu-BTC / SPE was loaded on the ring finger to form RF / Au@Cu-BTC / SPE for TDG detection; Step 4: SPE electrochemical sensing gloves performance test (1) Phosphate buffered saline (PBS) and different concentrations of EMPA, IMPA, and TDG solutions were added dropwise onto the surface of the screen-printed electrode prepared in step 2; (2) activating and stabilizing the electrode using cyclic voltammetry; (3) Perform differential pulse voltammetry (DPV) measurements on the screen-printed electrode with PBS buffer added, and record its response current, which is recorded as I0; (4) The DPV current change of the screen-printed electrode with different concentrations of EMPA was measured and the current response was recorded. Finally, a standard curve was drawn with the current change as the ordinate and the EMPA concentration as the abscissa, with a scanning voltage of -0.6 to 0.6 V, and the detection limit (LOD) was calculated; (5) Measure the DPV current change of the screen-printed electrode with different concentrations of IMPA added, and record the current response. Finally, draw a standard curve with the current change as the ordinate and the IMPA concentration as the abscissa, and calculate the detection limit (LOD); (6) The DPV current change of the screen-printed electrode with different concentrations of TDG was measured and the current response was recorded. Finally, a standard curve was drawn with the current change as the ordinate and the TDG concentration as the abscissa, and the detection limit (LOD) was calculated.

3. The method for preparing an electrochemical sensing glove based on Cu-BTC and Au@Cu-BTC materials according to claim 2, characterized in that: In step 1, the volume of the ethanol solution ranged from 100 to 120 mL, the mass of copper nitrate trihydrate ranged from 1.0 g to 4.35 g, the volume of acetic acid ranged from 6 to 10 mL, the volume of trimethylamine ranged from 5.0 to 10 mL, and the mass of trimesic acid (H3BTC) ranged from 2.10 to 4.50 g; the stirring time was 0.5 h, the heating temperature was 100 °C, and the holding time ranged from 12 to 24 h; the mixing ratio of HAuCl4 and sodium citrate was 1:5 to 1:10, the plasma jet was placed 1 to 3 cm above the solution, the high-voltage electrode hollow stainless steel tube had an inner diameter of 1.5 mm, a wall thickness of 0.1 mm, and a length of 150 mm; the copper strip had a width of 10 mm and a thickness of 180 µm, and the plasma treatment time was 30 to 90 s; the mixing ratio of Cu-BTC and polyvinyl pyrrolidone was 1:10, dissolved in 50 to 100 mL of ethanol solution, and 0.1 to 1 g of H3BTC was added. AuNPs; the mixture was vigorously stirred for 1-2 h and centrifuged at 8000-10000 rpm for 5-10 min.

4. The method for preparing an electrochemical sensing glove based on Cu-BTC and Au@Cu-BTC materials according to claim 2, characterized in that: In step 2, the mass fraction of the sulfuric acid solution is 1%~5%, and the cyclic voltammetry scan voltage is -1 V~1 V; the volume range of the Cu-BTC and Au@Cu-BTC suspensions is 1~100 μL, and the concentration is 5 mg / mL.

5. The method for preparing an electrochemical sensing glove based on Cu-BTC and Au@Cu-BTC materials according to claim 2, characterized in that: In step 3, the pH value of the phosphate buffer solution was 6, the concentrations of EMPA, IMPA, and TDG solutions were 1 ng / mL to 100 μg / mL, the scanning voltage range of cyclic voltammetry was -1 V to 1 V, the scanning speed was 20 mV / s to 50 mV / s, and the number of scanning cycles was 5 to 10 cycles. The scanning voltage of differential pulse voltammetry was -0.6 to 0.6 V, and the scanning rate was 0.005 V s -1 , the pulse amplitude is 0.05 V, the sampling width is 0.05 s, the pulse period is 0.5 s, and the sensitivity is 1.0×10 -3 AV -1 .

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