Fibrous photoelectrochemical seawater antibiotic concentration detector and preparation method thereof

Abstract

The invention relates to a fibrous photoelectrochemical seawater antibiotic concentration detector and a preparation method thereof. The fibrous photoelectrochemical seawater antibiotic concentration detector sequentially comprises a carbon nanotube fiber serving as a substrate, an alpha-Ga2O3 film layer arranged on the carbon nanotube fiber and an inner core electrode reserved at one end of the carbon nanotube fiber. The reserved inner core electrode is used as a working electrode, a passage is formed through seawater and a counter electrode, then 254nm ultraviolet light is used for irradiation at certain light intensity, and the concentration of antibiotics in seawater is fitted according to the size of light current. The detector disclosed by the invention can work under 0V bias voltage and has the characteristic of self-powered work; the thin film of the detector is compact in surface, stable and uniform in thickness, flexible, bendable and distortable, and can be prepared in a large area. The detector has a great application prospect in the fields of seawater quality monitoring, wearable equipment, intelligent textiles and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of photoelectric detectors, and in particular relates to a fibrous photoelectrochemical seawater antibiotic concentration detector. Background Art

[0002] Water monitoring is an extremely important part of marine aquaculture. The quality of water directly affects the growth, health and yield of aquatic animals. Heavy metals such as mercury, lead, cadmium, and organic pollutants such as biphenyl and dioxin will accumulate in marine fish. Long-term consumption of seafood from polluted waters may lead to chronic poisoning, posing a potential threat to human health.

[0003] Commonly used sterilization drugs in marine aquaculture include tetracyclines (TCs), sulfonamides (SAs), quinolones (FQs) and other antibiotics. These antibiotics and their metabolites not only induce resistance genes in water bodies, but also have potential toxic effects on aquatic organisms and humans. At present, the main means of detecting the concentration of these antibiotics are spectrophotometry and atomic absorption spectroscopy. Spectrophotometers and atomic absorption spectrometers are expensive and the detection methods are complicated. Therefore, many farms ignore the detection of antibiotic content in water quality, abuse antibiotics and directly discharge wastewater into the ocean, causing seawater pollution.

[0004] So far, there are few reports on flexible antibiotic pollution detectors. The present invention uses bendable, foldable, twistable, high-temperature resistant, and conductive carbon nanotube fibers as a flexible substrate, and grows gallium oxide nanocolumn arrays on this substrate. It utilizes the natural electrolyte properties of seawater to make a convenient, wearable, flexible photoelectrochemical ultraviolet antibiotic concentration detection device.

[0005] The present invention grows a gallium oxide nanocolumn array film on a flexible fiber substrate. The process has strong controllability and is easy to operate. The obtained film has a dense surface, stable and uniform thickness, is flexible and bendable, can be prepared over a large area, has good repeatability, and has strong bonding with the substrate. The detection of antibiotic concentration is convenient and fast, and has great application prospects in the fields of wearable devices, seawater quality monitoring, and smart textiles. Summary of the invention

[0006] The purpose of the present invention is to provide a fiber-shaped photoelectrochemical seawater antibiotic concentration detector with high sensitivity, strong detection capability and self-power supply and a preparation method thereof.

[0007] The technical solution of the present invention is:

[0008] A fiber-shaped photoelectrochemical seawater antibiotic concentration detector includes a carbon nanotube fiber as a substrate, an α-Ga2O3 film layer disposed on the carbon nanotube fiber, and an inner core electrode reserved at one end of the carbon nanotube fiber. The reserved inner core electrode is used as a working electrode, and a passage is formed with the counter electrode through seawater, and then irradiated with 254nm deep ultraviolet light at a certain light intensity, and the antibiotic concentration in the seawater is fitted according to the size of the photocurrent.

[0009] The carbon nanotube fiber has a diameter of 50-80 μm and a length of 3.5 cm. The α-Ga2O3 nanocolumn array is composed of a number of α-Ga2O3 nanocolumns. The diameter of the α-Ga2O3 nanocolumns is 50-200 nm, and the length of the α-Ga2O3 nanocolumns is 1.0-1.5 μm.

[0010] The reserved inner core electrode 1 has a length of 0.5 cm and is located at one end of the carbon nanotube fiber.

[0011] The present invention also includes a second technical solution, a method for preparing a fibrous photoelectrochemical seawater antibiotic concentration detector, comprising the following steps:

[0012] First, the carbon nanotube fibers are cleaned. The cleaning process is as follows: the carbon nanotube fibers are sequentially immersed in acetone, ethanol, and deionized water for 10 minutes each, and then taken out and rinsed with deionized water, and finally blown dry with dry N2 gas for standby use;

[0013] Second, the carbon nanotube fibers are subjected to plasma treatment. The treatment process is as follows: the cleaned carbon nanotube fibers are fixed in a reaction boat with a high-temperature tape, and the reserved electrode portion of 0.5 cm is covered, and the fibers are placed in a tube furnace for plasma treatment for 5 minutes, and then taken out for use;

[0014] 3. Place a Ga(NO3)3 solution with a concentration of 15-20 g / L in a beaker, cover one end of the plasma-treated carbon nanotube fiber by 0.5 cm as a reserved electrode 1, and immerse it in the gallium nitrate solution for 15 minutes, then take out the sample, wash it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer, wherein the annealing temperature is 450°C, the annealing time is 2.0-4.0 hours, and this step is repeated once;

[0015] Fourth, a Ga(NO3)3 solution with a concentration of 5 g / L was placed in the inner tank of the reaction vessel, and then the carbon nanotube fibers obtained in step 3 were immersed in the gallium nitrate solution for 12 hours;

[0016] 5. Place the reactor liner obtained in step 4 in a reactor and then transfer it to an oven, react at 150°C for 12 hours, then take out the sample, clean it, dry it, and anneal it to obtain a CNTF / α-Ga2O3 nanocolumn array, wherein the annealing temperature is 450°C and the annealing time is 4 hours.

[0017] Among them, in step 2, the plasma gas is O2, the power is 150W, and the processing time is 5 minutes.

[0018] Among them, the concentration of Ga(NO3)3 solution in step 4 is 5g / L, the immersion time is 12h, and the immersion environment is room temperature and normal pressure environment.

[0019] Among them, in steps two and three, the inner core electrode is reserved as the working electrode.

[0020] Beneficial effects of the present invention

[0021] (1) The fiber-shaped photoelectrochemical seawater antibiotic concentration detector of the present invention has a strong bond between the nanocolumn array and the CNTF substrate. CNTF is easy to process as a flexible working electrode, and has excellent electrical conductivity, thermal conductivity, and high temperature resistance, which greatly reduces the cost of the seawater antibiotic concentration UV detector. The detector of the present invention is a fiber-type detector, which can be bent and twisted, and can be used in portable wearable UV seawater quality monitoring equipment. The detector of the present invention can detect the concentration of antibiotics such as tetracyclines (TCs), sulfonamides (SAs), and quinolones (FQs) in seawater, and has stable performance and sensitive response. The α-Ga2O3 nanocolumn array used is uniform and orderly, and the size of the nanocolumns is controllable.

[0022] (2) In the fiber-shaped photoelectrochemical seawater antibiotic concentration detector of the present invention, the carbon nanotube fibers are immersed in a gallium nitrate solution for 12 hours, and the grown α-Ga2O3 nanocolumn array has a more uniform morphology, better flexibility and firmness, and better photoelectric performance.

[0023] (3) The preparation method of the present invention generates a gallium oxide nanocolumn array on a flexible CNTF substrate, so that the gallium oxide nanocolumn array is firmly bonded to the flexible substrate. The gallium oxide nanocolumn array is uniform, orderly, and has controllable size; the detector is flexible and bendable, easy to prepare on a large scale, and has good repeatability, and has great application prospects in the fields of wearable devices and seawater quality monitoring.

[0024] (4) The preparation method of the present invention adopts a hydrothermal method to prepare a gallium oxide nanorod array. The method for preparing the nanorod array has the advantages of low cost, controllable process, large-area preparation and good repeatability.

[0025] (5) The preparation method of the present invention can obtain an ordered array and size of gallium oxide nanorods by reasonably controlling the reaction conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of the structure of a fiber-shaped photoelectrochemical seawater antibiotic concentration detector;

[0027] Figure 2is the XRD pattern of α-Ga2O3 nanorod array;

[0028] Figure 3 is a SEM photo of α-Ga2O3 nanorod array;

[0029] Figure 4 It is the It diagram of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector under 0V bias voltage for different concentrations of tetracycline hydrochloride artificial seawater solution under different light intensities to 254nm ultraviolet light;

[0030] Figure 5 It is the It diagram of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector under 0V bias voltage for different concentrations of sulfamethoxazole artificial seawater solution under different light intensities to 254nm ultraviolet light;

[0031] Figure 6 It is the It diagram of the fibrous photoelectrochemical seawater antibiotic concentration detector under 0V bias and different concentrations of nicotinic acid norfloxacin artificial seawater solution under different light intensities in response to 254nm ultraviolet light. DETAILED DESCRIPTION

[0032] The following is a clear and complete description of the content of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, other embodiments obtained by ordinary technicians in this field without creative work are all within the scope of protection of the present invention.

[0033] Example 1

[0034] The preparation method of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector comprises the following steps:

[0035] (1) Cleaning the carbon nanotube fiber 2, the cleaning process is as follows: soak the carbon nanotube fiber 2 in acetone, ethanol, and deionized water for 10 minutes each, take it out and rinse it with deionized water, and finally blow it dry with dry N2 gas for standby use;

[0036] (2) Plasma treatment of the carbon nanotube fiber 2 is performed as follows: the cleaned carbon nanotube fiber 2 is fixed in the reaction boat with a high temperature tape, and the reserved electrode portion of 0.5 cm is covered, and the fiber is placed in a tube furnace for plasma treatment for 5 min, and then taken out for use;

[0037] (3) Place a Ga(NO3)3 solution with a concentration of 15-20 g / L in a beaker, cover one end of the plasma-treated carbon nanotube fiber by 0.5 cm as a reserved electrode 1, and immerse it in the gallium nitrate solution for 15 min, then take out the sample, wash it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer, wherein the annealing temperature is 450°C, the annealing time is 2.0-4.0 h, and this step is repeated once;

[0038] (4) placing a 5 g / L Ga(NO3)3 solution in the reactor liner, and then immersing the carbon nanotube fiber 2 obtained in step 3 in the gallium nitrate solution for 12 h;

[0039] (5) The reactor liner obtained in step 4 is placed in a reactor and then transferred to an oven for reaction at 150° C. for 12 h. The sample is then taken out, cleaned, dried, and annealed to obtain a CNTF / α-Ga2O3 nanorod array, wherein the annealing temperature is 450° C. and the annealing time is 4 h.

[0040] Specifically, in step (2), the plasma gas is O2, the power is 150W, and the processing time is 5 minutes.

[0041] Among them, the concentration of Ga(NO3)3 solution in step (4) is 5g / L, the immersion time is 12h, and the immersion environment is room temperature and normal pressure environment.

[0042] Among them, in steps (2) and (3), the inner core electrode 1 is reserved as the working electrode.

[0043] After the above experimental process, a self-powered fiber-shaped photoelectrochemical seawater antibiotic concentration detector can be prepared, such as Figure 1 As shown, it includes a carbon nanotube fiber 2 as a substrate, an α-Ga2O3 thin film layer 3 disposed on the carbon nanotube fiber, and an inner core electrode 1 reserved at one end of the carbon nanotube fiber. The reserved inner core electrode 1 is used as a working electrode, and a passage is formed with the counter electrode through seawater. Then, 254nm ultraviolet light is irradiated at a certain light intensity, and the antibiotic concentration in the seawater is fitted according to the size of the photocurrent.

[0044] The sample obtained in step (5) was subjected to XRD analysis, as shown in FIG. Figure 2 As shown in the figure, all the diffraction peaks in the spectrum are characteristic peaks of α-Ga2O3, and no characteristic peaks of other impurities are found, indicating that the material grown on the surface of CNTF is α-Ga2O3. The sample obtained in step (5) was observed under a scanning electron microscope, and it was found that the nanocolumns grew uniformly, as shown in FIG. Figure 3 As shown, the α-Ga2O3 nanocolumns grow evenly and have neat morphology.

[0045] The photoelectric performance of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector obtained in step (5) was tested. The results showed that the device can operate under a bias voltage of 0V and has the characteristic of being self-powered. Figure 4 The results show that the concentration of tetracycline hydrochloride artificial seawater solution changes from 0g / ml to 3.33×10 -3 g / ml, 254nm light intensity from 200μW / cm 2 Up to 2000μW / cm 2 It curve measured by turning the light on and off continuously under ultraviolet light; Figure 5 The results show that the concentration of sulfamethoxazole artificial seawater solution changes from 0g / ml to 3.33×10 -3 g / ml, 254nm light intensity from 200μW / cm 2 Up to 2000μW / cm 2 It curve measured by turning the light on and off continuously under ultraviolet light; Figure 6 The results show that the concentration of nicotinate norfloxacin artificial seawater solution changes from 0g / ml to 3.33×10 -3 g / ml, 254nm light intensity from 200μW / cm 2 Up to 2000μW / cm 2 The It curve was measured by turning the light on and off under ultraviolet light. The test was repeated for 1 hour. The device showed good repeatability. -3 g / ml, and at 2000μW / cm 2 When irradiated with 254nm ultraviolet light, the photocurrent reaches 1056nA, 18.6μA / cm 2 The above experiment shows that the flexible ultraviolet seawater antibiotic concentration detector obtained by the present invention can stably detect the concentration of tetracyclines (TCs), sulfonamides (SAs), quinolones (FQs) and other antibiotics in seawater, and is expected to be widely used in the fields of seawater quality monitoring, portable wearable devices and smart textiles.

[0046] Example 2

[0047] The preparation method of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector comprises the following steps:

[0048] (1) Cleaning the carbon nanotube fiber 2, the cleaning process is as follows: soak the carbon nanotube fiber 2 in acetone, ethanol, and deionized water for 10 minutes each, take it out and rinse it with deionized water, and finally blow it dry with dry N2 gas for standby use;

[0049] (2) Plasma treatment of the carbon nanotube fiber 2 is performed as follows: the cleaned carbon nanotube fiber 2 is fixed in the reaction boat with a high temperature tape, and the reserved electrode portion of 0.3 cm is covered, and the fiber is placed in a tube furnace for plasma treatment for 10 min, and then taken out for use;

[0050] (3) Place a Ga(NO3)3 solution with a concentration of 15-20 g / L in a beaker, cover one end of the plasma-treated carbon nanotube fiber by 0.3 cm as a reserved electrode 1, and immerse it in the gallium nitrate solution for 15 min, then take out the sample, wash it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer, wherein the annealing temperature is 450°C, the annealing time is 2.0-4.0 h, and this step is repeated once;

[0051] (4) placing a 5 g / L Ga(NO3)3 solution in the reactor liner, and then immersing the carbon nanotube fiber 2 obtained in step 3 in the gallium nitrate solution for 12 h;

[0052] (5) The reactor liner obtained in step 4 is placed in a reactor and then transferred to an oven for reaction at 150° C. for 12 h. The sample is then taken out, cleaned, dried, and annealed to obtain a CNTF / α-Ga2O3 nanorod array, wherein the annealing temperature is 450° C. and the annealing time is 4 h.

[0053] Specifically, in step (2), the plasma gas is O2, the power is 150 W, and the processing time is 10 min.

[0054] Among them, the concentration of Ga(NO3)3 solution in step (4) is 5g / L, the immersion time is 12h, and the immersion environment is room temperature and normal pressure environment.

[0055] Among them, in steps (2) and (3), the inner core electrode 1 is reserved as the working electrode.

[0056] A self-powered flexible gallium oxide nanorod array photoelectrochemical fiber ultraviolet seawater antibiotic concentration detector was obtained. Figure 1 shown.

[0057] Example 3

[0058] The preparation method of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector comprises the following steps:

[0059] (1) Cleaning the carbon nanotube fiber 2, the cleaning process is as follows: soak the carbon nanotube fiber 2 in acetone, ethanol, and deionized water for 10 minutes each, take it out and rinse it with deionized water, and finally blow it dry with dry N2 gas for standby use;

[0060] (2) Plasma treatment of the carbon nanotube fiber 2 is performed as follows: the cleaned carbon nanotube fiber 2 is fixed in the reaction boat with a high temperature tape, and the reserved electrode portion of 0.5 cm is covered, and the fiber is placed in a tube furnace for plasma treatment for 5 min, and then taken out for use;

[0061] (3) Place a Ga(NO3)3 solution with a concentration of 15-20 g / L in a beaker, cover one end of the plasma-treated carbon nanotube fiber by 0.5 cm as a reserved electrode 1, and immerse it in the gallium nitrate solution for 10 min, then take out the sample, wash it, dry it, and anneal it to obtain an α-Ga2O3 seed layer, wherein the annealing temperature is 450°C, the annealing time is 2.0 h, and this step is repeated twice;

[0062] (4) placing a 7 g / L Ga(NO3)3 solution in the reactor, and then immersing the carbon nanotube fiber 2 obtained in step 3 in the gallium nitrate solution for 12 h;

[0063] (5) The reactor liner obtained in step 4 is placed in a reactor and then transferred to an oven for reaction at 150° C. for 12 h. The sample is then taken out, cleaned, dried, and annealed to obtain a CNTF / α-Ga2O3 nanorod array, wherein the annealing temperature is 450° C. and the annealing time is 4 h.

[0064] Specifically, in step (2), the plasma gas is O2, the power is 150 W, and the processing time is 5 minutes.

[0065] Among them, the concentration of Ga(NO3)3 solution in step (4) is 5g / L, the immersion time is 12h, and the immersion environment is room temperature and normal pressure environment.

[0066] Among them, in steps (2) and (3), the inner core electrode 1 is reserved as the working electrode.

[0067] A self-powered flexible gallium oxide nanorod array photoelectrochemical fiber ultraviolet seawater antibiotic concentration detector was obtained. Figure 1 shown.

[0068] Example 4

[0069] The preparation method of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector comprises the following steps:

[0070] (1) Cleaning the carbon nanotube fiber 2, the cleaning process is as follows: soak the carbon nanotube fiber 2 in acetone, ethanol, and deionized water for 10 minutes each, take it out and rinse it with deionized water, and finally blow it dry with dry N2 gas for standby use;

[0071] (2) Plasma treatment of the carbon nanotube fiber 2 is performed as follows: the cleaned carbon nanotube fiber 2 is fixed in the reaction boat with a high temperature tape, and the reserved electrode portion of 0.5 cm is covered, and the fiber is placed in a tube furnace for plasma treatment for 5 min, and then taken out for use;

[0072] (3) Place a Ga(NO3)3 solution with a concentration of 15-20 g / L in a beaker, cover one end of the plasma-treated carbon nanotube fiber by 0.5 cm as a reserved electrode 1, and immerse it in the gallium nitrate solution for 15 min, then take out the sample, wash it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer, wherein the annealing temperature is 450°C, the annealing time is 2.0-4.0 h, and this step is repeated once;

[0073] (4) placing a 7 g / L Ga(NO3)3 solution in the reactor, and then immersing the carbon nanotube fiber 2 obtained in step 3 in the gallium nitrate solution for 9 h;

[0074] (5) The reactor liner obtained in step 4 is placed in a reactor and then transferred to an oven for reaction at 150° C. for 12 h. The sample is then taken out, cleaned, dried, and annealed to obtain a CNTF / α-Ga2O3 nanorod array, wherein the annealing temperature is 450° C. and the annealing time is 4 h.

[0075] Specifically, in step (2), the plasma gas is O2, the power is 150W, and the processing time is 5 minutes.

[0076] Among them, the concentration of Ga(NO3)3 solution in step (4) is 7g / L, the immersion time is 9h, and the immersion environment is room temperature and normal pressure environment.

[0077] Among them, in steps (2) and (3), the inner core electrode 1 is reserved as the working electrode.

[0078] A self-powered flexible gallium oxide nanorod array photoelectrochemical fiber ultraviolet seawater antibiotic concentration detector was obtained. Figure 1 shown.

[0079] Example 5

[0080] The preparation method of the fiber-shaped photoelectrochemical seawater antibiotic concentration detector comprises the following steps:

[0081] (1) Cleaning the carbon nanotube fiber 2, the cleaning process is as follows: soak the carbon nanotube fiber 2 in acetone, ethanol, and deionized water for 10 minutes each, take it out and rinse it with deionized water, and finally blow it dry with dry N2 gas for standby use;

[0082] (2) Plasma treatment of carbon nanotube fiber 2, the treatment process is as follows: fix the cleaned carbon nanotube fiber in the reaction boat with high temperature tape, cover the 0.5 cm reserved electrode part, put it into the tube furnace for plasma treatment for 5 minutes, and take it out for use;

[0083] (3) Place a Ga(NO3)3 solution with a concentration of 15-20 g / L in a beaker, cover one end of the plasma-treated carbon nanotube fiber by 0.5 cm as a reserved electrode 1, and immerse it in the gallium nitrate solution for 15 min, then take out the sample, wash it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer, wherein the annealing temperature is 450°C, the annealing time is 2.0-4.0 h, and this step is repeated once;

[0084] (4) placing a 5 g / L Ga(NO3)3 solution in the reactor liner, and then immersing the carbon nanotube fiber 2 obtained in step 3 in the gallium nitrate solution for 12 h;

[0085] (5) Place the reactor liner obtained in step 4 in a reactor and then transfer it to an oven, react at 150° C. for 12 h, then take out the sample, clean it, dry it, and anneal it to obtain a CNTF / α-Ga2O3 nanorod array, wherein the annealing temperature is 400° C. and the annealing time is 6 h.

[0086] Specifically, in step (2), the plasma gas is O2, the power is 150 W, and the processing time is 5 minutes.

[0087] Among them, the concentration of Ga(NO3)3 solution in step (4) is 5g / L, the immersion time is 12h, and the immersion environment is room temperature and normal pressure environment.

[0088] Among them, in steps (2) and (3), the inner core electrode 1 is reserved as the working electrode.

[0089] A self-powered flexible gallium oxide nanorod array photoelectrochemical fiber ultraviolet seawater antibiotic concentration detector was obtained. Figure 1 shown.

[0090] Obviously, the above embodiments are merely examples for clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, any modification, substitution, or improvement made on the basis of the above description and within the method and principle of the present invention should be included in the protection scope of the present invention. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A fiber-shaped photoelectrochemical seawater antibiotic concentration detector, characterized in that: It comprises, in sequence, a carbon nanotube fiber (2) serving as a substrate, an α-Ga2O3 film layer (3) arranged on the carbon nanotube fiber, and an inner core electrode (1) reserved at one end of the carbon nanotube fiber.

2. The fibrous photoelectrochemical seawater antibiotic concentration detector according to claim 1, characterized in that: The carbon nanotube fiber has a diameter of 50-80 μm and a length of 3.5 cm; the α-Ga2O3 thin film layer (3) has a thickness of 1.0-1.5 μm; the nanocolumn array is neatly and evenly covered on the surface of the carbon nanotube fiber, with a length of 3 cm; the remaining 0.5 cm uncovered area is a reserved inner core electrode (1); and the ultraviolet detector can be bent, twisted and folded.

3. The fibrous photoelectrochemical seawater antibiotic concentration detector according to claim 2, characterized in that: The fiber-shaped photoelectrochemical seawater antibiotic concentration detector can separate photogenerated carriers in a seawater environment, so that the detector can work under a 0V bias voltage to detect the concentration of seawater antibiotics with a detection accuracy of up to 0.3×10 -4 g / ml.

4. The method for preparing the fibrous photoelectrochemical seawater antibiotic concentration detector according to any one of claims 1 to 3, characterized in that: The steps include: Step 1, cleaning the carbon nanotube fiber (2), the cleaning process is as follows: soak the carbon nanotube fiber in acetone, ethanol, and deionized water in turn for 10 minutes each, take it out and rinse it with deionized water, and finally blow it dry with dry N2 gas for standby use; Step 2: Plasma treatment is performed on the carbon nanotube fiber (2). The treatment process is as follows: the cleaned carbon nanotube fiber (2) is fixed in the reaction boat with a high-temperature tape, and the 0.5 cm reserved electrode (1) portion is covered, and the fiber is placed in a tube furnace for plasma treatment for 5 minutes, and then taken out for use; Step 3, taking a Ga(NO3)3 solution with a concentration of 15-20 g / L and placing it in a beaker, covering one end of the plasma-treated carbon nanotube fiber (2) by 0.5 cm as a reserved electrode, and immersing it in the gallium nitrate solution for 15 minutes, then taking out the sample, washing, drying, and annealing to obtain an α-Ga2O3 seed crystal layer, wherein the annealing temperature is 450°C, the annealing time is 2.0-4.0 hours, and this step is repeated once; Step 4: Place a 5 g / L Ga(NO3)3 solution in the inner container of a reaction vessel, and then immerse the carbon nanotube fiber (2) obtained in step 3 in the gallium nitrate solution for 12 hours; Step 5, place the reactor liner obtained in step 4 in a reactor and then transfer it to an oven, react at 150°C for 12 hours, then take out the sample, clean, dry, and anneal to obtain a CNTF / α-Ga2O3 nanocolumn array, wherein the annealing temperature is 450°C and the annealing time is 4 hours.

5. The method for preparing the fibrous photoelectrochemical seawater antibiotic concentration detector according to claim 4, characterized in that: In the step 2, the plasma gas is O2, the power is 150W, and the processing time is 5 minutes.

6. The method for preparing the fibrous photoelectrochemical seawater antibiotic concentration detector according to claim 4, characterized in that: In step 4, the concentration of Ga(NO3)3 solution is 5 g / L, the immersion time is 12 h, and the immersion environment is room temperature and normal pressure environment.

7. The method for preparing the fibrous photoelectrochemical seawater antibiotic concentration detector according to claim 4, characterized in that: In the steps 2 and 3, the inner core electrode (1) is reserved as a working electrode.

Images