A fibrous photoelectrochemical seawater antibiotic concentration detector and a preparation method thereof

Abstract

The present application relates to a kind of fibrous photoelectrochemical seawater antibiotic concentration detector and its preparation method, in turn including carbon nanotube fiber as substrate, alpha-Ga2O3 film layer being arranged on carbon nanotube fiber, and the inner core electrode reserved in one end of carbon nanotube fiber.The reserved inner core electrode is used as working electrode, forms passway with counter electrode by seawater, then 254nm ultraviolet light is irradiated with certain light intensity, and antibiotic concentration in seawater is fitted according to photocurrent size.The detector of the present application can work at 0V bias, with the characteristics of self-powered work;The film surface of the detector is dense, and the thickness is stable and uniform, flexible and bendable, twisted, and can be prepared in large area.The detector has great application prospect in the fields of seawater quality monitoring, wearable devices and intelligent textiles.

Description

Technical Field

[0001] This invention belongs to the field of photoelectric detector technology, specifically relating to a fiber-shaped photoelectrochemical seawater antibiotic concentration detector. Background Technology

[0002] Water quality monitoring is a crucial aspect of mariculture, as it directly impacts the growth, health, and yield of aquatic animals. Heavy metals such as mercury, lead, and cadmium, as well as organic pollutants like biphenyls and dioxins, can 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 sterilizing agents in marine aquaculture include tetracyclines (TCs), sulfonamides (SAs), and quinolones (FQs). These antibiotics and their metabolites can induce resistance genes in water bodies and also have potential toxic effects on aquatic organisms and humans. Currently, the main methods for detecting the concentration of these antibiotics are spectrophotometry and atomic absorption spectrometry. However, spectrophotometers and atomic absorption spectrometers are expensive and the detection methods are complex. Therefore, many aquaculture farms neglect to detect antibiotic levels in water, overuse antibiotics, and directly discharge wastewater into the ocean, causing marine pollution.

[0004] To date, there have been few reports on flexible antibiotic contamination detectors. This invention uses flexible, foldable, tortuous, high-temperature resistant, and highly conductive carbon nanotube fibers as a flexible substrate, and grows gallium oxide nanopillar arrays on this substrate. By utilizing the natural electrolyte properties of seawater, a convenient, wearable, flexible photoelectrochemical ultraviolet antibiotic concentration detection device is fabricated.

[0005] This invention involves growing gallium oxide nanopillar array thin films on flexible fiber substrates. The process is highly controllable and easy to operate. The resulting films have a dense surface, stable and uniform thickness, are flexible and bendable, can be prepared on a large scale, have good repeatability, and have strong adhesion to the substrate. They are also convenient and quick for detecting antibiotic concentrations and have great application prospects in wearable devices, seawater quality monitoring, and smart textiles. Summary of the Invention

[0006] The purpose of this invention is to provide a fiber-shaped photoelectrochemical seawater antibiotic concentration detector with high sensitivity, strong detection capability, and self-powered operation, as well as its preparation method.

[0007] The technical solution of this invention is as follows:

[0008] A fiber-shaped photoelectrochemical seawater antibiotic concentration detector comprises, in sequence, a carbon nanotube fiber as a substrate, an α-Ga₂O₃ thin 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 serves as the working electrode, forming a path with the counter electrode through seawater. The detector is then irradiated with 254nm deep ultraviolet light at a certain intensity, and the antibiotic concentration in the seawater is fitted based on the photocurrent magnitude.

[0009] The carbon nanotube fibers have a diameter of 50-80 μm and a length of 3.5 cm. The α-Ga2O3 nanopillar array is composed of several α-Ga2O3 nanopillars with a diameter of 50-200 nm and a length of 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 fiber-shaped photoelectrochemical seawater antibiotic concentration detector, comprising the following steps:

[0012] First, clean the carbon nanotube fibers. The cleaning process is as follows: Soak the carbon nanotube fibers in acetone, ethanol, and deionized water for 10 minutes each, then rinse them with deionized water and finally dry them with dry N2 gas.

[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 the reaction boat with high-temperature tape, and the reserved electrode part is covered by 0.5cm. The carbon nanotube fibers are then placed in a tube furnace for plasma treatment for 5 minutes and then taken out for use.

[0014] Third, take a Ga(NO3)3 solution with a concentration of 15-20 g / L and place it in a beaker. Cover one end of the plasma-treated carbon nanotube fiber with a thickness of 0.5 cm to serve as the reserved electrode 1, and immerse it in gallium nitrate solution for 15 min. Then take out the sample, clean it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer. The annealing temperature is 450℃ and the annealing time is 2.0-4.0 h. This step is repeated once.

[0015] Fourth, place a 5 g / L Ga(NO3)3 solution into the inner liner of the reactor, and then immerse the carbon nanotube fibers obtained in step three in gallium nitrate solution for 12 h.

[0016] Fifth, place the inner liner of the reaction vessel obtained in step four into the reaction vessel 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 the CNTF / α-Ga2O3 nanopillar array. The annealing temperature is 450°C and the annealing time is 4 hours.

[0017] In step two, the plasma gas is O2, the power is 150W, and the processing time is 5min.

[0018] In step four, the concentration of Ga(NO3)3 solution is 5 g / L, the soaking time is 12 h, and the soaking environment is room temperature and normal pressure.

[0019] 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 present invention relates to a fiber-based photoelectrochemical seawater antibiotic concentration detector. The nanopillar array and CNTF substrate are firmly bonded. CNTF, as a flexible working electrode, is easy to process and exhibits excellent electrical and thermal conductivity and high-temperature resistance, significantly reducing the cost of the seawater antibiotic concentration UV detector. The detector of the present invention is a fiber-type detector, which is flexible and tortuous, and can be applied to portable wearable UV seawater quality monitoring devices. The detector of the present invention can detect the concentration of antibiotics such as tetracyclines (TCs), sulfonamides (SAs), and quinolones (FQs) in seawater, exhibiting stable performance and high sensitivity. The α-Ga2O3 nanopillar array used is uniform and ordered, and the nanopillar size is controllable.

[0022] (2) The fiber-shaped photoelectrochemical seawater antibiotic concentration detector of the present invention is made by immersing carbon nanotube fibers in gallium nitrate solution for 12 hours. The resulting α-Ga2O3 nanopillar 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 nanopillar array on a flexible CNTF substrate, thereby making the gallium oxide nanopillar array firmly bonded to the flexible substrate. The gallium oxide nanopillar array is uniform, ordered, and has controllable size; the detector is flexible and bendable, easy to prepare on a large area, and has good repeatability, and has great application prospects in wearable devices, seawater quality monitoring and other fields.

[0024] (4) The preparation method of the present invention uses a hydrothermal method to prepare gallium oxide nanopillar arrays. The method of preparing nanopillar arrays 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 gallium oxide nanopillar array and its size by reasonably controlling the reaction conditions. Attached Figure Description

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

[0027] Figure 2The image shows the XRD pattern of an α-Ga2O3 nanopillar array.

[0028] Figure 3 This is a SEM image of an α-Ga2O3 nanopillar array;

[0029] Figure 4 The image shows the It graph of different concentrations of tetracycline hydrochloride artificial seawater solutions under different light intensities and 254nm ultraviolet light under a 0V bias voltage and a fiber photoelectrochemical seawater antibiotic concentration detector.

[0030] Figure 5 The image shows the It graphs of different concentrations of sulfamethoxazole artificial seawater solutions under different light intensities and 254nm ultraviolet light under different light intensities in a fiber photoelectrochemical seawater antibiotic concentration detector at 0V bias.

[0031] Figure 6 This is an It graph showing the response of fiber-optic photoelectrochemical seawater antibiotic concentration detector to 254nm ultraviolet light under different light intensities in artificial seawater solutions of different concentrations of nicotinic acid and norfloxacin at a bias voltage of 0V. Detailed Implementation

[0032] The present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0033] Example 1

[0034] A method for preparing a fiber-reinforced photoelectrochemical seawater antibiotic concentration detector includes the following steps:

[0035] (1) Clean 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 later use.

[0036] (2) The carbon nanotube fiber 2 was subjected to plasma treatment. The treatment process is as follows: the cleaned carbon nanotube fiber 2 was fixed in the reaction boat with high temperature tape and the 0.5cm reserved electrode part was covered. The carbon nanotube fiber 2 was placed in the tube furnace for plasma treatment for 5 minutes and then taken out for use.

[0037] (3) Take a Ga(NO3)3 solution with a concentration of 15-20 g / L and place it in a beaker. Cover one end of the plasma-treated carbon nanotube fiber with 0.5 cm as a reserved electrode 1 and immerse it in gallium nitrate solution for 15 min. Then take out the sample, clean it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer. The annealing temperature is 450℃ and the annealing time is 2.0-4.0 h. This step is repeated once.

[0038] (4) Take a Ga(NO3)3 solution with a concentration of 5 g / L and place it in the inner liner of the reactor. Then immerse the carbon nanotube fiber 2 obtained in step 3 in gallium nitrate solution for 12 h.

[0039] (5) Place the inner liner of the reaction vessel obtained in step four into the reaction vessel and then transfer it to the oven. React at 150°C for 12 hours. Then take out the sample, clean it, dry it, and anneal it to obtain CNTF / α-Ga2O3 nanopillar array. The annealing temperature is 450°C and the annealing time is 4 hours.

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

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

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

[0043] A self-powered fiber-shaped photoelectrochemical seawater antibiotic concentration detector can be prepared through the above experimental process, such as... Figure 1 As shown, the structure sequentially includes a carbon nanotube fiber 2 serving 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 serves as the working electrode, forming a path with the counter electrode through seawater, and is then irradiated with 254nm ultraviolet light at a certain intensity. The concentration of antibiotics in the seawater is fitted based on the magnitude of the photocurrent.

[0044] The sample obtained in step (5) was subjected to XRD analysis, such as... Figure 2 As shown, all diffraction peaks in the spectrum are characteristic peaks of α-Ga2O3, and no characteristic peaks of other impurities were found, indicating that α-Ga2O3 material is grown on the CNTF surface. The sample obtained in step (5) was observed under a scanning electron microscope, and the nanopillars were found to grow uniformly, as shown... Figure 3 As shown, the α-Ga2O3 nanopillars grow uniformly and have a 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 0V bias voltage and has the characteristic of self-powered operation. Figure 4 The concentrations of tetracycline hydrochloride in artificial seawater solutions under a 0V bias voltage range from 0 g / ml to 3.33 × 10⁻⁶ g / ml. -3 g / ml, 254nm light intensity from 200μW / cm 2 Up to 2000 μW / cm 2 The It curve was measured under ultraviolet light by continuously turning the lamp on and off; Figure 5 The concentrations of sulfamethoxazole-based artificial seawater solutions at 0V bias range from 0 g / ml to 3.33 × 10⁻⁶ g / ml. -3 g / ml, 254nm light intensity from 200μW / cm 2 Up to 2000 μW / cm 2 The It curve was measured under ultraviolet light by continuously turning the lamp on and off; Figure 6 The concentrations of norfloxacin nicotinic acid in artificial marine solutions at 0V bias range from 0 g / ml to 3.33 × 10⁻⁶ g / ml. -3 g / ml, 254nm light intensity from 200μW / cm 2 Up to 2000 μW / cm 2 The It curve, measured under ultraviolet light with the lamp continuously switched on and off, was repeated for 1 hour, and the device exhibited good repeatability. The detector was tested in an artificial seawater solution containing tetracycline hydrochloride at a concentration of 1.33 × 10⁻⁶. -3 g / ml, and at 2000 μW / cm 2 When irradiated with 254nm ultraviolet light, the photocurrent reaches 1056nA, or 18.6μA / cm. 2 It exhibits excellent photoelectric properties. The aforementioned experiments demonstrate that the flexible ultraviolet seawater antibiotic concentration detector obtained in this invention can stably detect the concentrations of antibiotics such as tetracyclines (TCs), sulfonamides (SAs), and quinolones (FQs) in seawater, and is expected to be widely used in 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 includes the following steps:

[0048] (1) Clean 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 later use.

[0049] (2) The carbon nanotube fiber 2 was subjected to plasma treatment. The treatment process is as follows: the cleaned carbon nanotube fiber 2 was fixed in the reaction boat with high temperature tape and the reserved electrode part was covered with 0.3cm. The carbon nanotube fiber 2 was placed in the tube furnace for plasma treatment for 10 minutes and then taken out for use.

[0050] (3) Take a Ga(NO3)3 solution with a concentration of 15-20 g / L and place it in a beaker. Cover one end of the plasma-treated carbon nanotube fiber with 0.3 cm as a reserved electrode 1 and immerse it in gallium nitrate solution for 15 min. Then take out the sample, clean it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer. The annealing temperature is 450℃ and the annealing time is 2.0-4.0 h. This step is repeated once.

[0051] (4) Take a Ga(NO3)3 solution with a concentration of 5 g / L and place it in the inner liner of the reactor. Then immerse the carbon nanotube fiber 2 obtained in step 3 in gallium nitrate solution for 12 h.

[0052] (5) Place the inner liner of the reaction vessel obtained in step four into the reaction vessel and then transfer it to the oven. React at 150°C for 12 hours. Then take out the sample, clean it, dry it, and anneal it to obtain CNTF / α-Ga2O3 nanopillar array. The annealing temperature is 450°C and the annealing time is 4 hours.

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

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

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

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

[0057] Example 3

[0058] A method for preparing a fiber-reinforced photoelectrochemical seawater antibiotic concentration detector includes the following steps:

[0059] (1) Clean 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 later use.

[0060] (2) The carbon nanotube fiber 2 was subjected to plasma treatment. The treatment process is as follows: the cleaned carbon nanotube fiber 2 was fixed in the reaction boat with high temperature tape and the 0.5cm reserved electrode part was covered. The carbon nanotube fiber 2 was placed in the tube furnace for plasma treatment for 5 minutes and then taken out for use.

[0061] (3) Take a Ga(NO3)3 solution with a concentration of 15-20 g / L and place it in a beaker. Cover one end of the plasma-treated carbon nanotube fiber with 0.5 cm as a reserved electrode 1 and immerse it in gallium nitrate solution for 10 min. Then take out the sample, clean it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer. The annealing temperature is 450℃ and the annealing time is 2.0 h. This step is repeated twice.

[0062] (4) Place a Ga(NO3)3 solution with a concentration of 7 g / L into the inner liner of the reactor, and then immerse the carbon nanotube fiber 2 obtained in step 3 in gallium nitrate solution for 12 h.

[0063] (5) Place the inner liner of the reaction vessel obtained in step four into the reaction vessel and then transfer it to the oven. React at 150°C for 12 hours. Then take out the sample, clean it, dry it, and anneal it to obtain CNTF / α-Ga2O3 nanopillar array. The annealing temperature is 450°C and the annealing time is 4 hours.

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

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

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

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

[0068] Example 4

[0069] A method for preparing a fiber-reinforced photoelectrochemical seawater antibiotic concentration detector includes the following steps:

[0070] (1) Clean 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 later use.

[0071] (2) The carbon nanotube fiber 2 was subjected to plasma treatment. The treatment process is as follows: the cleaned carbon nanotube fiber 2 was fixed in the reaction boat with high temperature tape and the 0.5cm reserved electrode part was covered. The carbon nanotube fiber 2 was placed in the tube furnace for plasma treatment for 5 minutes and then taken out for use.

[0072] (3) Take a Ga(NO3)3 solution with a concentration of 15-20 g / L and place it in a beaker. Cover one end of the plasma-treated carbon nanotube fiber with 0.5 cm as a reserved electrode 1 and immerse it in gallium nitrate solution for 15 min. Then take out the sample, clean it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer. The annealing temperature is 450℃ and the annealing time is 2.0-4.0 h. This step is repeated once.

[0073] (4) Place a Ga(NO3)3 solution with a concentration of 7 g / L into the inner liner of the reactor, and then immerse the carbon nanotube fiber 2 obtained in step 3 in gallium nitrate solution for 9 h;

[0074] (5) Place the inner liner of the reaction vessel obtained in step four into the reaction vessel and then transfer it to the oven. React at 150°C for 12 hours. Then take out the sample, clean it, dry it, and anneal it to obtain CNTF / α-Ga2O3 nanopillar array. The annealing temperature is 450°C and the annealing time is 4 hours.

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

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

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

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

[0079] Example 5

[0080] A method for preparing a fiber-reinforced photoelectrochemical seawater antibiotic concentration detector includes the following steps:

[0081] (1) Clean 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 later use.

[0082] (2) The carbon nanotube fiber 2 was subjected to plasma treatment. The treatment process is as follows: the cleaned carbon nanotube fiber was fixed in the reaction boat with high temperature tape and the 0.5cm reserved electrode part was covered. The carbon nanotube fiber was placed in the tube furnace for plasma treatment for 5 minutes and then taken out for use.

[0083] (3) Take a Ga(NO3)3 solution with a concentration of 15-20 g / L and place it in a beaker. Cover one end of the plasma-treated carbon nanotube fiber with 0.5 cm as a reserved electrode 1 and immerse it in gallium nitrate solution for 15 min. Then take out the sample, clean it, dry it, and anneal it to obtain an α-Ga2O3 seed crystal layer. The annealing temperature is 450℃ and the annealing time is 2.0-4.0 h. This step is repeated once.

[0084] (4) Take a Ga(NO3)3 solution with a concentration of 5 g / L and place it in the inner liner of the reactor. Then immerse the carbon nanotube fiber 2 obtained in step 3 in gallium nitrate solution for 12 h.

[0085] (5) Place the inner liner of the reaction vessel obtained in step four into the reaction vessel and then transfer it to the oven. React at 150°C for 12 hours. Then take out the sample, clean it, dry it, and anneal it to obtain CNTF / α-Ga2O3 nanopillar array. The annealing temperature is 400°C and the annealing time is 6 hours.

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

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

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

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

[0090] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. For those skilled in the art, any modifications, equivalent substitutions, or improvements made based on the above description and within the methods and principles of this invention should be included within the scope of protection of this invention. It is neither necessary nor possible to exhaustively describe all embodiments here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A fibrous photoelectrochemical type seawater antibiotic concentration detector, characterized by, The carbon nanotube fiber (2) as a substrate, an α-Ga2O3 thin film layer (3) arranged on the carbon nanotube fiber, and an inner core electrode (1) reserved at one end of the carbon nanotube fiber are sequentially included.

2. The fibrous photoelectrochemical seawater antibiotic concentration detector according to claim 1, wherein 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, and the nanocolumn array is regularly and uniformly arranged on the surface of the carbon nanotube fiber, with a length of 3 cm, and the remaining 0.5 cm is the 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-like photoelectrochemical seawater antibiotic concentration detector can separate photo-generated carriers in a seawater environment, so that the detector can work at 0 V bias, realize detection of seawater antibiotic concentration, and the detection precision can reach 0.3*10 -4 g / ml.

4. The method for preparing a fibrous photoelectrochemical seawater antibiotic concentration detector according to any one of claims 1 to 3, characterized in that, The method comprises the following steps: In step one, the carbon nanotube fiber (2) is cleaned by immersing it in acetone, ethanol and deionized water for 10 min each, rinsing with deionized water, and then blowing dry with dry N2 gas; In step two, the carbon nanotube fiber (2) is treated by plasma, and the treatment process is as follows: the cleaned carbon nanotube fiber (2) is fixed in a reaction boat by using a high-temperature adhesive tape, and the 0.5 cm reserved electrode (1) is covered, and then the reaction boat is put into a tube furnace for plasma treatment for 5 min, and then taken out for use; In step three, a Ga(NO3)3 solution with a concentration of 15-20 g / L is placed in a beaker, one end of the carbon nanotube fiber (2) treated by plasma is covered with a 0.5 cm reserved electrode, and then immersed in the gallium nitrate solution for 15 min, and then the sample is taken out, cleaned, dried and annealed to obtain an α-Ga2O3 seed layer, wherein the annealing temperature is 450°C, and the annealing time is 2.0-4.0 h, and this step is repeated once; In step four, a Ga(NO3)3 solution with a concentration of 5 g / L is placed in the inner container of a reaction kettle, and then the carbon nanotube fiber (2) obtained in step three is immersed in the gallium nitrate solution for 12 h; In step five, the inner container of the reaction kettle obtained in step four is placed in the reaction kettle and then transferred to an oven for reaction at 150°C for 12 h, and then the sample is taken out, cleaned, dried and annealed to obtain a CNTF / α-Ga2O3 nanocolumn array, wherein the annealing temperature is 450°C, and the annealing time is 4 h.

5. The method for preparing the fiber-shaped photoelectrochemical seawater antibiotic concentration detector according to claim 4, characterized in that, In step two, the plasma gas is O2, the power is 150 W, and the treatment time is 5 min.

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

7. The method for preparing the fiber-shaped photoelectrochemical seawater antibiotic concentration detector according to claim 4, characterized in that, In steps two and three, the reserved inner core electrode (1) is used as a working electrode.

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