CN113866237A - Flexible photoelectrochemical aptamer sensor and preparation method and application thereof - Google Patents
Flexible photoelectrochemical aptamer sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a flexible photoelectrochemistry aptamer sensor and a preparation method and application thereof. The preparation method comprises the following steps: preparing a functional three-dimensional carbon fiber composite material; the specific aptamer probe self-assembles the load. The flexible photoelectrochemistry aptamer sensor has the advantages of long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy, wide application range and the like, can be widely used for detecting target molecules (such as antibiotic molecules) in a solution, has high use value and good application prospect, develops a new way for obtaining a portable flexible sensor, has the advantages of simple process, convenience and quickness in operation, safety, low cost, no pollution, high manufacturing efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the technical field of biosensors, and relates to a flexible photoelectrochemical aptamer sensor and a preparation method and application thereof, in particular to a functionalized three-dimensional carbon fiber composite material-based flexible photoelectrochemical aptamer sensor and a preparation method and application thereof.
Background
In recent years, a photoelectrochemical detection technology attracts more and more attention, and the technology is a novel analysis method developed based on photoelectric conversion, wherein light is applied to a photosensitive material to cause electron excitation and charge transfer, an electron hole pair is formed at an interface after photons are absorbed and undergoes an oxidation-reduction reaction with a specific target detection object to influence the charge transfer, and the obtained electric signal is further analyzed to obtain quantitative analysis on the target detection object. The photoelectrochemical aptamer sensing technology belongs to one of photoelectrochemical detection technologies, adopts a nucleic acid aptamer as a photoelectric detection technology of an identification element, has the advantages of higher stability, easy synthesis, easy modification, lower cost, higher selectivity and the like, and is widely concerned in the field of micromolecular detection.
Currently, most photoelectrochemical aptamer sensors rely on the immobilization of an optoelectronically active material on a rigid, non-recyclable substrate surface, such as Indium Tin Oxide (ITO) or fluorine-doped SnO2Conductive glass (FTO), which greatly hinders the development of photoelectric aptamer sensors in the portable and wearable direction, and limits their practical application potential. For the above reasons, if a flexible photoelectric chemical aptamer sensor based on a flexible material is obtained, the sensor has certain wearable and portable capabilities, which is beneficial to improving the practical application capability of the sensor. However, so far, no relevant report on "flexible photoelectric chemical aptamer sensor based on flexible material" is seen. In addition, another key to the development of ultrasensitive photoresponsive sensors is the design of a photoelectrically active material with higher photoelectric conversion efficiency, however, most of the currently available photoelectrically active materials, such as titanium dioxide (TiO)2) Molybdenum disulfide (MoS)2) Gallium nitride (GaN) and the like have higher photon-generated carrier recombination rate and lower photoelectric conversion efficiency, and directly influence the sensitivity of the photoelectric sensor. Therefore, the development of a photoelectric active material with strong visible light absorption capacity, low photon-generated carrier recombination rate and high photoelectric conversion efficiency is very important for obtaining a flexible photoelectrochemical aptamer sensor with long service life, strong anti-interference capacity, wide detection range, low detection limit, high sensitivity, high accuracy and wide application range.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a flexible photoelectrochemical aptamer sensor which has the advantages of high stability, long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy and wide application range, also provides a preparation method of the flexible photoelectrochemical aptamer sensor which has the advantages of simple process, convenient operation, safety, low cost, no pollution and high preparation efficiency, and also provides an application of the flexible photoelectrochemical aptamer sensor in the detection of antibiotics.
In order to solve the technical problems, the invention adopts the following technical scheme:
a flexible photoelectrochemical aptamer sensor comprises a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes a three-dimensional carbon fiber composite material as a carrier, the surface of the three-dimensional carbon fiber composite material is loaded with a composite film, the composite film is composed of a modified graphite-phase carbon nitride nanosheet composite material, the modified graphite-phase carbon nitride nanosheet composite material comprises a thermally defective graphite-phase carbon nitride nanosheet and alpha-iron oxide nanoparticles, and the alpha-iron oxide nanoparticles are modified on the thermally defective graphite-phase carbon nitride nanosheet; the surface of the composite membrane is self-assembled with a specific aptamer probe for recognizing and capturing target molecules.
In the flexible photoelectrochemical aptamer sensor, the mass ratio of the alpha-iron oxide nanoparticles to the thermally defective graphite-phase carbon nitride nanosheets in the modified graphite-phase carbon nitride nanosheet composite material is further improved to be 1: 8.33-25; the particle size of the alpha-ferric oxide nano-particles is 8 nm-10 nm; the three-dimensional carbon fiber composite material is carbon fiber cloth; the length of the carbon fiber cloth is 1cm, the width of the carbon fiber cloth is 2cm, and the thickness of the carbon fiber cloth is 1 mm.
As a general technical concept, the present invention also provides a method for preparing the above-mentioned flexible photoelectrochemical aptamer sensor, comprising the steps of:
s1, coating the modified graphite phase carbon nitride nanosheet composite suspension on the surface of the three-dimensional carbon fiber composite, and forming a composite membrane on the surface of the three-dimensional carbon fiber composite to obtain a functionalized three-dimensional carbon fiber composite;
and S2, dropwise adding the specific aptamer probe solution to the composite membrane on the surface of the functionalized three-dimensional carbon fiber composite material obtained in the step S1, and incubating to enable the specific aptamer probe to be self-assembled on the surface of the composite membrane, so that the flexible photoelectrochemical aptamer sensor is obtained.
In step S1, the modified graphite-phase carbon nitride nanosheet composite suspension is coated on the surface of the three-dimensional carbon fiber composite material according to the dosage of 100 μ L for each coating, and the coating is dried and repeated for 3 to 5 times; the modified graphite phase carbon nitride nanosheet composite suspension is prepared by the following method: ultrasonically dispersing the modified graphite-phase carbon nitride nanosheet composite material in a perfluorosulfonic acid/ethanol mixed solution to obtain a modified graphite-phase carbon nitride nanosheet composite material suspension; the mass-to-volume ratio of the modified graphite-phase carbon nitride nanosheet composite to the perfluorosulfonic acid/ethanol mixed solution in the modified graphite-phase carbon nitride nanosheet composite suspension is 4 mg-10 mg: 1 mL; the volume ratio of the perfluorosulfonic acid to the ethanol in the perfluorosulfonic acid/ethanol mixed solution is 1: 1-2.
In a further improvement of the above preparation method, the preparation method of the modified graphite phase carbon nitride nanosheet composite material comprises the following steps:
(1) mixing the thermally-defective graphite-phase carbon nitride nanosheets with an aqueous solution containing ferric salt and polyvinylpyrrolidone, ultrasonically dispersing, and stirring to obtain a thermally-defective graphite-phase carbon nitride nanosheet suspension;
(2) and (2) carrying out hydrothermal reaction, centrifugation and drying on the thermally-defective graphite-phase carbon nitride nanosheet suspension obtained in the step (1) to obtain the modified graphite-phase carbon nitride nanosheet composite material.
In the step (1), the mass-to-volume ratio of the thermally defective graphite-phase carbon nitride nanosheet to the aqueous solution containing the ferric salt and the polyvinylpyrrolidone is 2.5-3.0 mg: 2.0 mL; the thermal defect graphite phase carbon nitride nanosheet is prepared by the following preparation method: heating melamine to 640-700 ℃ according to the heating rate of 2-5 ℃/min, carrying out heat treatment for 2-4 h, and cooling to obtain the graphite phase carbon nitride nanosheet with thermal defects; the mass ratio of the trivalent ferric salt to the polyvinylpyrrolidone in the aqueous solution containing the trivalent ferric salt and the polyvinylpyrrolidone is 1-3: 2; the trivalent ferric salt is ferric nitrate nonahydrate; the ultrasonic dispersion time is 30-60 min; the rotating speed of the stirring is 500-600 rpm; the stirring time is 20 min;
in the step (2), the hydrothermal reaction is carried out at the temperature of 160-180 ℃; the time of the hydrothermal reaction is 12-16 h; the rotation speed of the centrifugation is 2500 rpm-3500 rpm; the drying is carried out under vacuum conditions; the temperature of the drying was 75 ℃.
In a further improvement of the above preparation method, in step S2, the specific aptamer probe solution is prepared by the following method: mixing N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and a solution containing a specific aptamer for activation to obtain a specific aptamer probe solution; the activation is carried out at a temperature of 37 ℃; the activation time is 20-28 h; the incubation is carried out at a temperature of 25-35 ℃; the incubation time is 30-60 min.
As a general technical concept, the invention also provides an application of the flexible photoelectrochemical aptamer sensor or the flexible photoelectrochemical aptamer sensor prepared by the preparation method in detection of antibiotics.
The application is further improved, and comprises the following steps: dripping an antibiotic solution on the surface of a composite membrane of the flexible photoelectric chemical aptamer sensor for reaction, and performing specific identification and capture on the antibiotic by using a specific aptamer probe on the surface of the composite membrane; testing a standard antibiotic solution by adopting a chronoamperometry under intermittent illumination to construct a detection linear regression equation of antibiotic concentration and photocurrent change; and detecting the light current value of the antibiotic solution to be detected, and calculating the concentration of the antibiotic in the antibiotic solution to be detected by detecting a linear regression equation according to the light current value of the antibiotic solution to be detected.
In the above application, it is further improved that when the antibiotic in the antibiotic solution is ampicillin, the nucleotide sequence of the specific aptamer probe in the flexible photoelectric chemical aptamer sensor is 5 '-COOH-TTA GTT GGG GTT CAG TTG G-3'; the linear regression equation for detecting the concentration and the photocurrent change of the ampicillin is as follows:
(I-I0)/I0＝0.5844×LogC+2.205 (1)
in the formula (1), I0Represents the background peak current, I represents the detected peak current, in μ a; c is the concentration of ampicillin in the solution to be tested, and the unit is nM; correlation coefficient R of formula (1)20.9953, the linear detection range is 0.5pM to 50nM, the lower detection limit is 0.0125 pM;
the reaction time is 0.5 h-1 h; during the test, the bias voltage was set to 0V, and the lamp was switched every 20 s.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a flexible photoelectrochemical aptamer sensor which comprises a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes a three-dimensional carbon fiber composite material as a carrier, a composite film is loaded on the surface of the three-dimensional carbon fiber composite material, the composite film is composed of a modified graphite-phase carbon nitride nanosheet composite material, the modified graphite-phase carbon nitride nanosheet composite material comprises a thermally-defective graphite-phase carbon nitride nanosheet and alpha-iron oxide nanoparticles, the alpha-iron oxide nanoparticles are modified on the thermally-defective graphite-phase carbon nitride nanosheet, and a specific aptamer probe for identifying and capturing target object molecules is self-assembled on the surface of the composite film. In the invention, the three-dimensional carbon fiber composite material is taken as a carrier, which is a flexible material, so that the composite membrane is loaded on the three-dimensional carbon fiber composite material, and the surface of the composite membrane is self-assembled with a specific aptamer probe for identifying and capturing target molecules, so that the flexible photoelectric chemical aptamer sensor can be formed, and has very good performance in both bending and flat states. On one hand, the adopted three-dimensional carbon fiber composite material has excellent flexibility, a stronger three-dimensional skeleton structure, higher strength and better conductivity, the former is beneficial to constructing a unique three-dimensional hierarchical structure, and the latter improves the separation efficiency of charge carriers, which is vital to a flexible photoelectrochemical aptamer sensor based on a nano structure, so that the three-dimensional carbon fiber composite material is taken as a carrier, the reaction site area can be increased, the rapid reaction kinetics can be realized, the transportation of target molecules under convection can be improved, the signal amplification effect can be realized, and favorable conditions can be created for improving the photoelectric performance of the flexible photoelectrochemical sensor. On the other hand, the composite film adopted in the invention is composed of a modified graphite phase carbon nitride nanosheet composite material, the modified graphite phase carbon nitride nanosheet composite material is formed by compounding thermally defective graphite phase carbon nitride nanosheets and alpha-iron oxide nanoparticles, wherein the thermally defective graphite phase carbon nitride nanosheets have high visible light absorption capacity, proper energy band width and good photochemical stability, and meanwhile, the alpha-iron oxide nanoparticles are modified on the thermally defective graphite phase carbon nitride nanosheets to form an all-solid-state Z-shaped heterojunction, so that the photoelectric activity of the thermally defective graphite phase carbon nitride nanosheets can be improved, and electron hole pairs with high oxidation reduction performance can be reserved. Specifically, the alpha-iron oxide nanoparticles and the thermally-defective graphite-phase carbon nitride nanosheets form a heterojunction, so that the recombination rate of photon-generated carriers is reduced; in addition, the all-solid-state Z-type heterojunction can change an electron transfer path in the traditional II-type heterojunction, so that photo-generated electrons and holes are respectively gathered on a high-potential energy band, the oxidation reduction capability of electron holes is improved, the strategy converts the defects of a sub-gap structure existing in the graphite-phase carbon nitride nanosheet with thermal defects into advantages, the material keeps higher visible light absorption capability and photoelectric conversion efficiency, and therefore, the modified graphite-phase carbon nitride nanosheet composite material with strong visible light absorption capability, low photo-generated carrier recombination rate and high photoelectric conversion efficiency is obtained, and is a novel functional material for constructing a high-performance sensor, so that the modified graphite-phase carbon nitride nanosheet composite material is used as a main body optical activity material, and the composite film formed by the modified graphite-phase carbon nitride nanosheet composite material is fixed on the three-dimensional carbon fiber composite material, the sensitivity of the flexible photoelectric chemical aptamer sensor can be greatly improved, and the signal to noise ratio can be reduced, so that the flexible photoelectric chemical aptamer sensor has a wide detection range and a low detection limit. Therefore, the flexible photoelectrochemistry aptamer sensor has the advantages of long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy, wide application range and the like, can be widely used for detecting target molecules in a solution, and if the target molecules exist in the solution to be detected, the specific aptamer probe can specifically identify and capture the target molecules, at the moment, a photo-generated cavity and hydroxyl free radicals gathered on the sensor electrode can generate an oxidation-reduction reaction with the target molecules to promote the transfer of photoelectric charges on the electrode, and a photocurrent signal is increased along with the increase of the concentration of the target molecules, so that the purpose of detecting the target is achieved.
(2) In the flexible photoelectrochemistry aptamer sensor, the mass ratio of the alpha-iron oxide nanoparticles to the thermally defective graphite-phase carbon nitride nanosheets in the modified graphite-phase carbon nitride nanosheet composite material is optimized to be 1: 8.33-25, so that the photoelectric activity of the composite material is favorably improved, the modified graphite-phase carbon nitride nanosheet composite material with excellent photoelectric conversion performance is obtained, and the sensitivity and the accuracy of the flexible photoelectrochemistry aptamer sensor are favorably improved.
(3) The invention also provides a preparation method of the flexible photoelectrochemical aptamer sensor, which comprises the steps of coating the modified graphite-phase carbon nitride nanosheet composite suspension on the surface of the three-dimensional carbon fiber composite to form a composite film on the surface of the three-dimensional carbon fiber composite to form a functionalized three-dimensional carbon fiber composite, then dropwise adding the specific aptamer probe solution onto the composite film on the surface of the functionalized three-dimensional carbon fiber composite obtained in the step S1 for incubation, and enabling the specific aptamer probe to be self-assembled on the surface of the composite film, so that the flexible photoelectrochemical aptamer sensor which is long in service life, strong in anti-interference capability, wide in detection range, low in detection limit, high in sensitivity, high in accuracy and wide in application range is prepared. The preparation method only needs conventional operations such as a traditional tube furnace, hydrothermal operation, coating annealing and the like, does not introduce any toxic elements, has the advantages of simple process, convenience and safety in operation, low cost, no pollution, high manufacturing efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(4) The invention also provides application of the flexible photoelectrochemistry aptamer sensor in detection of antibiotics, wherein an antibiotic solution is dripped on the surface of the composite membrane of the flexible photoelectrochemistry aptamer sensor for reaction, specificity identification and capture are carried out on the antibiotics by using the specific aptamer probe on the surface of the composite membrane, and the concentration of the antibiotics in the solution to be detected is calculated according to the light current value of the solution to be detected and by detecting a linear regression equation, so that the concentration of the antibiotics in the solution to be detected can be quickly and accurately obtained. Taking an ampicillin solution as an example, when the flexible photoelectrochemistry aptamer sensor is used for detecting ampicillin, ampicillin in media such as water, food and the like can be detected, a better detection range and a better detection limit can be obtained, and the sensor has the advantages of simple operation, low cost, wide application range, high application value and the like, and has very important significance for realizing effective treatment of antibiotic wastewater.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a graph of ultraviolet diffuse reflection spectra of modified graphite-phase carbon nitride nanosheet composites of different mass ratios prepared in example 1 of the present invention.
Fig. 2 is a comparative graph of photocurrent of modified graphite-phase carbon nitride nanosheet composites of different mass ratios prepared in example 1 of the present invention.
FIG. 3 shows a functionalized three-dimensional carbon fiber composite material (α -Fe) prepared in example 1 of the present invention2O3/d-C3N4/CFT) in a scanning electron microscope.
FIG. 4 shows a functionalized three-dimensional carbon fiber composite material (α -Fe) according to example 1 of the present invention2O3/d-C3N4/CFT) and flexibilityPhotoelectrochemical aptamer sensor (aptamer/alpha-Fe)2O3/d-C3N4/CFT).
Fig. 5 is a diagram showing the photocurrent response of the sensor for detecting ampicillin solutions of different concentrations in example 1.
FIG. 6 is a graph of linear regression of the detection of the change in photocurrent versus ampicillin concentration in example 1 of the present invention.
Fig. 7 is a photo current response diagram corresponding to the flexible photoelectrochemical aptamer sensor in example 3 of the present invention when the sensor detects different antibiotic solutions.
Fig. 8 is a photo current response diagram corresponding to the functionalized three-dimensional carbon fiber composite material obtained under different processing conditions in embodiment 4 of the present invention.
FIG. 9 shows a flexible photoelectric chemical aptamer sensing electrode (aptamer/alpha-Fe) in example 5 of the present invention2O3/d-C3N4/CFT) photocurrent signal response plot over 15 days.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples, unless otherwise specified, the raw materials and equipment used were commercially available, the process used was a conventional one, the equipment used was conventional, and the data obtained were average values of three or more repeated experiments.
The light source is taken from a high-brightness xenon lamp parallel light source system instrument, and a 300W xenon lamp (Beijing Pofely) is taken as a visible light source. Electrochemical experiments used the CHI660B electrochemical workstation (shanghai chenhua instruments ltd).
Example 1
A flexible photoelectrochemical aptamer sensor comprises a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes a three-dimensional carbon fiber composite material as a carrier, the surface of the three-dimensional carbon fiber composite material is loaded with a composite film, the composite film is composed of a modified graphite-phase carbon nitride nanosheet composite material, the modified graphite-phase carbon nitride nanosheet composite material comprises a thermal defect graphite-phase carbon nitride nanosheet and alpha-iron oxide nanoparticles, the alpha-iron oxide nanoparticles are modified on the thermal defect graphite-phase carbon nitride nanosheet, and a specific aptamer probe (which can be selected according to actual needs) for identifying and capturing target molecules is self-assembled on the surface of the composite film.
In this example, the mass ratio of the α -iron oxide nanoparticles to the thermally deficient graphite-phase carbon nitride nanosheets in the α -iron oxide nanoparticle-modified thermally deficient graphite-phase carbon nitride nanosheet composite material is 1: 12.5; the average particle size of the alpha-iron oxide nanoparticles is 8 nm; the three-dimensional carbon fiber composite material is carbon fiber cloth, the length is 1cm, the width is 2cm, and the thickness is 1 mm.
In this example, the α -iron oxide nanoparticles were modified on the surface of the thermally deficient graphite-phase carbon nitride nanosheets by a hydrothermal reaction method.
In this embodiment, the thermally defective graphite-phase carbon nitride nanosheet composite modified by the α -iron oxide nanoparticles is loaded on the surface of a carbon fiber cloth (also referred to as a three-dimensional carbon fiber cloth) by a method of repeated coating-baking annealing.
A method for preparing the photoelectrochemical aptamer sensor of the above embodiment includes the following steps:
(1) spreading 8.0g of melamine in a quartz boat, placing the quartz boat in a tube furnace, heating the quartz boat to 640 ℃ at the speed of 3 ℃/min under the air condition, carrying out heat treatment for 3h, naturally cooling and grinding the quartz boat to obtain the graphite-phase carbon nitride nanosheet with thermal defects, wherein the thermal defect graphite-phase carbon nitride nanosheet is marked as d-C3N4。
(2) Weighing 100mg of the thermally defective graphite-phase carbon nitride nanosheet obtained in the step (1), dissolving the thermally defective graphite-phase carbon nitride nanosheet in 80mL of a mixed solution containing 80mg of ferric nitrate nonahydrate and 80mg of polyvinylpyrrolidone, ultrasonically dispersing for 40min, and stirring for 20min at a rotating speed of 500-600 rpm (which can be adjusted according to actual conditions and can be carried out at a rotating speed of 500-600 rpm), so as to obtain a thermally defective graphite-phase carbon nitride nanosheet suspension. Pouring the thermal defect graphite phase carbon nitride nanosheet suspension into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a matched steel sleeve, putting the polytetrafluoroethylene lining into an oven, heating the polytetrafluoroethylene lining to 160 ℃ from room temperature, keeping the polytetrafluoroethylene lining for 12 hours, and coolingCooling to room temperature, centrifuging the obtained mixed solution at the speed of 3000rpm, drying the product obtained by centrifuging at the temperature of 75 ℃ to obtain the thermal defect graphite phase carbon nitride nanosheet composite material modified by the alpha-iron oxide nanoparticles, namely the modified graphite phase carbon nitride nanosheet composite material, marked as alpha-Fe2O3/d-C3N4。
(3) 4mg of the alpha-iron oxide nanoparticle-modified thermally-deficient graphite-phase carbon nitride nanosheet composite material (alpha-Fe) prepared in the step (2)2O3/d-C3N4) Adding the mixture into 1mL of perfluorosulfonic acid/ethanol mixed solution (the volume ratio of perfluorosulfonic acid to ethanol in the mixed solution is 1: 1), uniformly mixing, and performing ultrasonic treatment for 40min to obtain the thermal defect graphite-phase carbon nitride nanosheet composite suspension modified by the alpha-iron oxide nanoparticles.
(4) Uniformly coating 100 mu L of the alpha-iron oxide nanoparticle modified thermally-defective graphite-phase carbon nitride nanosheet composite suspension obtained in the step (3) on the surface of a three-dimensional carbon fiber composite (three-dimensional carbon fiber cloth CFT) which is processed cleanly, placing the three-dimensional carbon fiber composite in a muffle furnace for baking and annealing, repeating the steps for three times, and forming a composite film consisting of the alpha-iron oxide nanoparticle modified thermally-defective graphite-phase carbon nitride nanosheet composite on the surface of the three-dimensional carbon fiber composite to obtain alpha-Fe2O3/d-C3N4The loaded three-dimensional carbon fiber cloth is the functionalized three-dimensional carbon fiber composite material which is marked as alpha-Fe2O3/d-C3N4/CFT。
(5) Sucking a solution containing 2mol/L of N-hydroxysuccinimide (NHS) and 5mol/L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), mixing the solution with 20 mu L of a solution containing a specific aptamer with the concentration of 2 mu mol/L, and reacting at 37 ℃ to activate the aptamer to obtain an activated specific aptamer probe solution, wherein the specific activation time can be adjusted according to actual conditions and can be within 20-28 h; dropwise adding the activated specific aptamer probe solution into the functionalized three-dimensional carbon fiber composite material (alpha-Fe) in the step (4)2O3/d-C3N4/CFT) composite membrane surface, placing in 30 deg.C environmentIncubating for 40min to fix the specific aptamer probe on the surface of the carbon fiber cloth to obtain the flexible photoelectrochemical aptamer sensor which is recorded as aptamer/alpha-Fe2O3/d-C3N4/CFT。
In this embodiment, thermal defect graphite phase carbon nitride nanosheet composite materials (modified graphite phase carbon nitride nanosheet composite materials) modified by α -iron oxide nanoparticles with different mass ratios are also prepared, wherein when the content of ferric nitrate nonahydrate in the mixed solution adopted in the step (2) is 120mg, 100mg, 60mg and 40mg respectively, and the content of corresponding polyvinylpyrrolidone is 120mg, 100mg, 60mg and 40mg respectively, other conditions are the same, and thus the α -iron oxide nanoparticles (α -Fe) in the prepared thermal defect graphite phase carbon nitride nanosheet composite materials modified by α -iron oxide nanoparticles are prepared2O3) With thermally deficient graphite phase carbon nitride nanosheets (d-C)3N4) The mass ratio of the components is 1: 8.33, 1: 10, 1: 16.67 and 1: 25 in sequence.
The visible light absorption capability of the modified graphite-phase carbon nitride nanosheet composite materials with different mass ratios is inspected, and the ultraviolet diffuse reflection test is performed on the modified graphite-phase carbon nitride nanosheet composite materials with different mass ratios, which are prepared in the embodiment 1 of the present invention, and the result is shown in fig. 1. Fig. 1 is a graph of ultraviolet diffuse reflection spectra of modified graphite-phase carbon nitride nanosheet composites of different mass ratios prepared in example 1 of the present invention. As can be seen from FIG. 1, in the wavelength range of 200-800nm, when the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite-phase carbon nitride nanosheets is 1: 8.33, 1: 10, 1: 12.5, 1: 16.67, 1: 25 in this order, the obtained alpha-iron oxide nanoparticle modified thermally-deficient graphite-phase carbon nitride nanosheet composite (modified graphite-phase carbon nitride nanosheet composite) shows a very strong light absorption signal, has a very good light absorption capacity, in particular, when the mass ratio of the alpha-iron oxide nano-particles to the thermal defect graphite phase carbon nitride nano-sheets is 1: 12.5, the obtained alpha-iron oxide nanoparticle modified thermally-deficient graphite-phase carbon nitride nanosheet composite material (modified graphite-phase carbon nitride nanosheet composite material) has the strongest light absorption signal, which indicates that the composite material has the best visible light absorption capability.
Photocurrent tests were performed on the modified graphite-phase carbon nitride nanosheet composite materials of different mass ratios prepared in example 1 of the present invention, and the results are shown in fig. 2. Fig. 2 is a comparative graph of photocurrent of modified graphite-phase carbon nitride nanosheet composites of different mass ratios prepared in example 1 of the present invention. As can be seen from fig. 2, when the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite-phase carbon nitride nanosheets is 1: 8.33, 1: 10, 1: 12.5, 1: 16.67, and 1: 25 in this order, the obtained thermally defective graphite-phase carbon nitride nanosheet composite material (modified graphite-phase carbon nitride nanosheet composite material) modified by the α -iron oxide nanoparticles exhibits a very strong photocurrent signal and has a very good light absorption capability, and particularly, when the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite-phase carbon nitride nanosheets is 1: 12.5, the photocurrent signal of the obtained thermally defective graphite-phase carbon nitride nanosheet composite material (modified graphite-phase carbon nitride nanosheet composite material) modified by the α -iron oxide nanoparticles is the highest, indicating that the thermally defective graphite-phase carbon nitride nanosheet composite material has the best photoelectric conversion efficiency, as can be seen, when the α -iron oxide nanoparticles are too many, agglomeration is easy to occur, and the light absorption effect of the thermal defect graphite phase carbon nitride nanosheet is not improved; when the amount of the alpha-iron oxide nanoparticles is too small, the small amount of the alpha-iron oxide nanoparticles is not enough to form a heterojunction with the thermally defective graphite-phase carbon nitride nanosheet, so that the advantages of the alpha-iron oxide nanoparticles are exerted, and therefore, a photocurrent signal is relatively weak, and the photoelectric activity is not improved.
For the functionalized three-dimensional carbon fiber composite material (alpha-Fe) prepared in the embodiment 1 of the invention2O3/d-C3N4/CFT) for scanning electron microscopy imaging analysis. The results are shown in FIG. 3. FIG. 3 shows a functionalized three-dimensional carbon fiber composite material (α -Fe) prepared in example 1 of the present invention2O3/d-C3N4/CFT) in a scanning electron microscope. As can be seen from FIG. 3a, the thermally-deficient graphite-phase carbon nitride nanosheet composite material modified by the alpha-iron oxide nanoparticles is well loaded on the fiber surface of the three-dimensional carbon fiber cloth to form a composite film, as can be seen from FIG. 3b, the thermally-deficient graphite-phase carbon nitride nanosheets have a typical lamellar structure, the surface of the thermally-deficient graphite-phase carbon nitride nanosheets is modified by the alpha-iron oxide nanoparticles with the average particle size of 8nm, and the particles of the thermally-deficient graphite-phase carbon nitride nanosheets are uniform in sizeAnd the distribution is uniform, which shows that the modified graphite phase carbon nitride nanosheet composite material compounded by the alpha-iron oxide nanoparticles and the thermally defective graphite phase carbon nitride nanosheets is successfully loaded on the three-dimensional carbon fiber composite material, namely the functionalized three-dimensional carbon fiber composite material (alpha-Fe)2O3/d-C3N4/CFT) was successfully prepared.
An application of the flexible photoelectrochemical aptamer sensor of the embodiment in detection of antibiotics specifically is as follows: the application of the flexible photoelectrochemistry aptamer sensor in detecting ampicillin, wherein a specific aptamer probe in the flexible photoelectrochemistry aptamer sensor has the functions of specifically recognizing and capturing ampicillin, and the method comprises the following steps of
(a) Ampicillin solutions (ampicillin concentrations of 0.0005nM, 0.001nM, 0.005nM, 0.01nM, 0.05nM, 0.1nM, 0.5nM, 1nM, 5nM, 10nM, and 50nM) were added dropwise to the surface of the composite membrane of the flexible photoelectrochemical aptamer sensor prepared in example 1, and the surface was incubated at 37 ℃ for 30 minutes to allow the aptamer probe on the surface of the flexible photoelectrochemical aptamer sensor to specifically recognize and capture ampicillin. In this example, the nucleotide sequence of the specific aptamer probe in the flexible photoelectrochemical aptamer sensor was 5 '-COOH-TTA GTT GGG GTT CAG TTG G-3', and the other parameters were the same as those of the flexible photoelectrochemical aptamer sensor of example 1.
(b) And testing under intermittent illumination by adopting a timing current method, establishing a relation between the concentration of ampicillin and the change of photocurrent, and constructing a linear regression equation for detection.
(c) Detecting the ampicillin solution to be detected according to the operations in the steps (a) and (b), obtaining the photocurrent value of the ampicillin solution to be detected, and meanwhile, calculating the concentration of ampicillin in the ampicillin solution to be detected according to the photocurrent value of the ampicillin solution to be detected and the detection linear regression equation obtained in the step (b).
For the functionalized three-dimensional carbon fiber composite material (alpha-Fe) prepared in the embodiment 1 of the invention2O3/d-C3N4/CFT) and flexible photoelectricityAptamer sensor (aptamer/alpha-Fe)2O3/d-C3N4/CFT in a mixture containing KCl and potassium ferricyanide ([ Fe (CN))6]3-/4-) (iii) an aqueous solution of (KCl concentration of the aqueous solution was 0.1M, [ Fe (CN))6]3-/4-Concentration of (b)' in mM) "was subjected to an impedance test, and the results are shown in fig. 4. FIG. 4 shows a functionalized three-dimensional carbon fiber composite material (α -Fe) according to example 1 of the present invention2O3/d-C3N4CFT) and flexible photoelectrochemical aptamer sensors (aptamer/alpha-Fe)2O3/d-C3N4/CFT). As can be seen from FIG. 4, following the modification of the ampicillin-specific aptamer probe to α -Fe2O3/d-C3N4On CFT, aptamer/alpha-Fe2O3/d-C3N4The resistance of the/CFT is increased, which indicates that the specific probe is successfully modified to alpha-Fe2O3/d-C3N4a/CFT surface.
Fig. 5 is a diagram showing the photocurrent response of the sensor for detecting ampicillin solutions of different concentrations in example 1. As can be seen from FIG. 5, the photocurrent increased with increasing concentration of ampicillin.
FIG. 6 is a graph of linear regression of the detection of the change in photocurrent versus ampicillin concentration in example 1 of the present invention. As can be seen from FIG. 6, the linear regression equation for the detection of the change in concentration of ampicillin and photocurrent is:
(I-I0)/I0＝0.5844×LogC+2.205 (1)
in the formula (1), I0Represents the background peak current, I represents the detected peak current, in μ a; c is the concentration of ampicillin in the solution to be tested, and the unit is nM; correlation coefficient R of formula (1)2The linear range of detection was 0.5pM to 50nM, with a lower limit of detection of 0.0125pM, 0.9953.
It can be seen that the functionalized three-dimensional carbon fiber composite material (alpha-Fe)2O3/d-C3N4CFT) and specific probe (nucleotide sequence is 5 '-COOH-TTA GTT GGG GTT CAG TTG G-3') are compounded to form flexible photoelectrochemical adapterThe body sensor can be used for detecting ampicillin, and can calculate the concentration of ampicillin to be detected according to a detection linear regression equation.
Example 2
To further verify the three-dimensional carbon fiber composite material (alpha-Fe) functionalized in example 12O3/d-C3N4The detection effect of the flexible photoelectrochemistry aptamer sensor compounded by the CFT) and the specific probe (the nucleotide sequence is 5 '-COOH-TTA GTT GGG GTT CAG TTG G-3') in practical application further comprises the following treatment: the recovery rate test was performed using a flexible photoelectrochemical aptamer sensor for detection of a target in an actual sample (measurement method refer to example 1).
The concentration of the target substance in the sample (containing ampicillin) was referred to in table 1, and the flexible photoelectrochemical aptamer sensor was finally used for detection of the target substance in the actual sample (the measurement method was referred to in example 1), and a recovery rate test was conducted. The results of the measurement are shown in Table 1.
TABLE 1 results of recovery verification of test solutions
As can be seen from Table 1, the recovery rate of the flexible photoelectrochemical aptamer sensor is basically 95.70-105.87% within the measurable concentration range, the measurement result is ideal, and compared with the traditional detection technology, the detection method adopting the flexible photoelectrochemical aptamer sensor is simple and rapid to operate.
As can be seen from Table 1, the functionalized three-dimensional carbon fiber composite material (α -Fe)2O3/d-C3N4CFT) and a specific probe (the nucleotide sequence is 5 '-COOH-TTA GTT GGG GTT CAG TTG G-3') can be used for detecting ampicillin in lake water and milk samples, can obtain better detection precision, and can be suitable for different detection systems.
Example 3
And (5) observing the anti-interference capability of the flexible photoelectrochemistry aptamer sensor. The flexible photoelectrochemical aptamer sensor of example 1 was used for the detection of ampicillin, ampicillin and penicillin solutions having a concentration of 0.5nM (a mixed solution of ampicillin and penicillin having a concentration of 0.5nM and penicillin having a concentration of 500nM), a mixed solution of ampicillin and amoxicillin having a concentration of 0.5nM and amoxicillin having a concentration of 500nM, a mixed solution of ampicillin and tetracycline having a concentration of 0.5nM and tetracycline having a concentration of 500nM, a mixed solution of ampicillin and tobramycin having a concentration of 0.5nM and tobramycin having a concentration of 500nM, a mixed solution of ampicillin and kanamycin having a concentration of 0.5nM and kanamycin having a concentration of 500nM, and a mixed solution of penicillin and penicillin having a concentration of 500nM, respectively, The amoxicillin solution at a concentration of 500nM, tetracycline solution at a concentration of 500nM, tobramycin solution at a concentration of 500nM, and kanamycin solution at a concentration of 500nM were tested (test method reference example 1) with the numbers a, b, c, d, e, f, g, h, i, j, and k, respectively, and the results are shown in FIG. 7.
Fig. 7 is a photo current response diagram corresponding to the flexible photoelectrochemical aptamer sensor in example 3 of the present invention when the sensor detects different antibiotic solutions. As can be seen from fig. 7, the flexible photoelectric chemical aptamer sensor in example 3 of the present invention has a better photocurrent response to ampicillin and no photocurrent response to other antibiotics, which indicates that the flexible photoelectric chemical aptamer sensor of the present invention has a better anti-interference capability.
Example 4
For the reproducibility of the flexible photoelectrochemical aptamer sensor, 5 parts of the functionalized three-dimensional carbon fiber composite material (α -Fe) prepared in example 1 were each separately prepared2O3/d-C3N4/CFT), 5 parts of functionalized three-dimensional carbon fiber composite material (0.5nM penbritin/alpha-Fe) formed by dripping and incubating 0.5nM ampicillin solution2O3/d-C3N4/CFT) and 5 parts of a solution of ampicillin 10nM after drop coating and incubationFunctionalized three-dimensional carbon fiber composite material (10nM penbritin/alpha-Fe)2O3/d-C3N4/CFT) photocurrent was tested. Three tests were performed per electrode and the results are shown in figure 8.
Fig. 8 is a photo current response diagram corresponding to the functionalized three-dimensional carbon fiber composite material obtained under different processing conditions in embodiment 4 of the present invention. As can be seen from fig. 8, the magnitude of the photocurrent signals obtained from the different functionalized three-dimensional carbon fiber composite materials obtained under different processing conditions in embodiment 4 of the present invention is substantially the same, which indicates that the flexible photoelectric chemical aptamer sensor of the present invention has better reproducibility.
Example 5
And (5) observing the service life of the flexible photoelectrochemical aptamer sensor. The flexible photoelectric chemical aptamer sensing electrode (aptamer/alpha-Fe) prepared in example 12O3/d-C3N4/CFT) was stored in a refrigerator for 15 days, and the coated and incubated solution of ampicillin 0.5nM was taken out at the same time every day and the photocurrent was measured, and the average value was taken three times for each measurement, and the results are shown in fig. 9.
FIG. 9 shows a flexible photoelectric chemical aptamer sensing electrode (aptamer/alpha-Fe) in example 5 of the present invention2O3/d-C3N4/CFT) photocurrent signal response plot over 15 days. As can be seen from FIG. 9, the magnitude of the photocurrent signal measured by the same electrode every day is substantially the same within 15 days, and remains about 95% of the initial value, which indicates that the flexible photoelectric chemical aptamer sensor of the invention has a long service life, and can be normally used within at least 15 days.
The detection results show that the functionalized three-dimensional carbon fiber composite material (alpha-Fe)2O3/d-C3N4CFT) and a specific probe, and the flexible photoelectrochemistry aptamer sensor has the advantages of wide detection range, low detection limit, strong anti-interference capability, long service life and the like, can be widely used for detecting target molecules (such as antibiotic molecules) in a solution, and if the target molecules exist in the solution to be detected, the specific aptamer probe can specifically identify and capture the target moleculesAt the moment, the photo-induced holes and hydroxyl radicals gathered on the sensor electrode can generate oxidation-reduction reaction with target molecules to promote the transfer of photo-generated charges on the electrode, and the photocurrent signal is increased along with the increase of the concentration of the target, so that the purpose of detecting the target is achieved.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A flexible photoelectrochemical aptamer sensor is characterized by comprising a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes a three-dimensional carbon fiber composite material as a carrier, a composite film is loaded on the surface of the three-dimensional carbon fiber composite material, the composite film is composed of a modified graphite-phase carbon nitride nanosheet composite material, the modified graphite-phase carbon nitride nanosheet composite material comprises a thermally defective graphite-phase carbon nitride nanosheet and alpha-iron oxide nanoparticles, and the alpha-iron oxide nanoparticles are modified on the thermally defective graphite-phase carbon nitride nanosheet; the surface of the composite membrane is self-assembled with a specific aptamer probe for recognizing and capturing target molecules.
2. The flexible photoelectrochemical aptamer sensor of claim 1, wherein the mass ratio of the alpha-iron oxide nanoparticles to the thermally deficient graphite phase carbon nitride nanosheets in the modified graphite phase carbon nitride nanosheet composite is 1: 8.33-25; the particle size of the alpha-ferric oxide nano-particles is 8 nm-10 nm; the three-dimensional carbon fiber composite material is carbon fiber cloth; the length of the carbon fiber cloth is 1cm, the width of the carbon fiber cloth is 2cm, and the thickness of the carbon fiber cloth is 1 mm.
3. A method for preparing a flexible photoelectrochemical aptamer sensor according to claim 1 or 2, comprising the steps of:
s1, coating the modified graphite phase carbon nitride nanosheet composite suspension on the surface of the three-dimensional carbon fiber composite, and forming a composite membrane on the surface of the three-dimensional carbon fiber composite to obtain a functionalized three-dimensional carbon fiber composite;
and S2, dropwise adding the specific aptamer probe solution to the composite membrane on the surface of the functionalized three-dimensional carbon fiber composite material obtained in the step S1, and incubating to enable the specific aptamer probe to be self-assembled on the surface of the composite membrane, so that the flexible photoelectrochemical aptamer sensor is obtained.
4. The preparation method according to claim 3, wherein in step S1, the modified graphite phase carbon nitride nanosheet composite suspension is coated on the surface of the three-dimensional carbon fiber composite in an amount of 100 μ L per coating, dried, and repeated for 3 to 5 times; the modified graphite phase carbon nitride nanosheet composite suspension is prepared by the following method: ultrasonically dispersing the modified graphite-phase carbon nitride nanosheet composite material in a perfluorosulfonic acid/ethanol mixed solution to obtain a modified graphite-phase carbon nitride nanosheet composite material suspension; the mass-to-volume ratio of the modified graphite-phase carbon nitride nanosheet composite to the perfluorosulfonic acid/ethanol mixed solution in the modified graphite-phase carbon nitride nanosheet composite suspension is 4 mg-10 mg: 1 mL; the volume ratio of the perfluorosulfonic acid to the ethanol in the perfluorosulfonic acid/ethanol mixed solution is 1: 1-2.
5. The method of manufacturing of claim 4, wherein the method of manufacturing the modified graphite phase carbon nitride nanosheet composite comprises the steps of:
(1) mixing the thermally-defective graphite-phase carbon nitride nanosheets with an aqueous solution containing ferric salt and polyvinylpyrrolidone, ultrasonically dispersing, and stirring to obtain a thermally-defective graphite-phase carbon nitride nanosheet suspension;
(2) and (2) carrying out hydrothermal reaction, centrifugation and drying on the thermally-defective graphite-phase carbon nitride nanosheet suspension obtained in the step (1) to obtain the modified graphite-phase carbon nitride nanosheet composite material.
6. The preparation method according to claim 5, wherein in the step (1), the mass-to-volume ratio of the thermally-defective graphite-phase carbon nitride nanosheets to the aqueous solution containing the ferric salt and the polyvinylpyrrolidone is 2.5 mg-3.0 mg: 2.0 mL; the thermal defect graphite phase carbon nitride nanosheet is prepared by the following preparation method: heating melamine to 640-700 ℃ according to the heating rate of 2-5 ℃/min, carrying out heat treatment for 2-4 h, and cooling to obtain the graphite phase carbon nitride nanosheet with thermal defects; the mass ratio of the trivalent ferric salt to the polyvinylpyrrolidone in the aqueous solution containing the trivalent ferric salt and the polyvinylpyrrolidone is 1-3: 2; the trivalent ferric salt is ferric nitrate nonahydrate; the ultrasonic dispersion time is 30-60 min; the rotating speed of the stirring is 500-600 rpm; the stirring time is 20 min;
in the step (2), the hydrothermal reaction is carried out at the temperature of 160-180 ℃; the time of the hydrothermal reaction is 12-16 h; the rotation speed of the centrifugation is 2500 rpm-3500 rpm; the drying is carried out under vacuum conditions; the temperature of the drying was 75 ℃.
7. The method according to any one of claims 3 to 6, wherein in step S2, the specific aptamer probe solution is prepared by: mixing N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and a solution containing a specific aptamer for activation to obtain a specific aptamer probe solution; the activation is carried out at a temperature of 37 ℃; the activation time is 20-28 h; the incubation is carried out at a temperature of 25-35 ℃; the incubation time is 30-60 min.
8. Use of the flexible photoelectrochemical aptamer sensor according to claim 1 or 2 or the flexible photoelectrochemical aptamer sensor prepared by the preparation method according to any one of claims 3 to 7 in the detection of antibiotics.
9. Use according to claim 8, characterized in that it comprises the following steps: dripping an antibiotic solution on the surface of a composite membrane of the flexible photoelectric chemical aptamer sensor for reaction, and performing specific identification and capture on the antibiotic by using a specific aptamer probe on the surface of the composite membrane; testing a standard antibiotic solution by adopting a chronoamperometry under intermittent illumination to construct a detection linear regression equation of antibiotic concentration and photocurrent change; and detecting the light current value of the antibiotic solution to be detected, and calculating the concentration of the antibiotic in the antibiotic solution to be detected by detecting a linear regression equation according to the light current value of the antibiotic solution to be detected.
10. The use according to claim 9, wherein when the antibiotic in the antibiotic solution is ampicillin, the nucleotide sequence of the specific aptamer probe in the flexible photoelectric electrochemical aptamer sensor is 5 '-COOH-TTA GTT GGG GTT CAG TTG G-3'; the linear regression equation for detecting the concentration and the photocurrent change of the ampicillin is as follows:
(I-I0)/I0＝0.5844×LogC+2.205 (1)
in the formula (1), I0Represents the background peak current, I represents the detected peak current, in μ a; c is the concentration of ampicillin in the solution to be tested, and the unit is nM; correlation coefficient R of formula (1)20.9953, the linear detection range is 0.5pM to 50nM, the lower detection limit is 0.0125 pM;
the reaction time is 0.5 h-1 h; during the test, the bias voltage was set to 0V, and the lamp was switched every 20 s.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017012210A1 (en) * | 2015-07-21 | 2017-01-26 | 北京化工大学 | Metal oxide-carbon nitride composite material and preparation method and use thereof |
| CN108593719A (en) * | 2018-06-26 | 2018-09-28 | 浙江大学 | A kind of immunosensor based on flexible electrode |
| CN112250118A (en) * | 2020-10-16 | 2021-01-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of composite material modified graphene, product and application thereof |
| CN112371146A (en) * | 2020-10-14 | 2021-02-19 | 江苏大学 | Preparation method and application of Z-type carbon nitride-iron oxide catalyst containing nitrogen defect structure |
| CN112768257A (en) * | 2020-12-15 | 2021-05-07 | 大连理工大学 | Nickel-cobalt oxide flexible electrode and preparation method and application thereof |
| CN112824884A (en) * | 2019-11-21 | 2021-05-21 | 湖南大学 | Photoelectrochemical aptamer sensor and preparation method and application thereof |
| CN113145154A (en) * | 2021-03-06 | 2021-07-23 | 徐州工程学院 | Preparation method of composite catalyst for photocatalytic reduction of chromium (VI) -containing wastewater |
| CN113265873A (en) * | 2021-05-14 | 2021-08-17 | 南开大学 | Flexible sensing fabric carrying metal oxide, conductive polymer and two-dimensional nano material, preparation method and application thereof |
-
2021
- 2021-09-16 CN CN202111086805.9A patent/CN113866237B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017012210A1 (en) * | 2015-07-21 | 2017-01-26 | 北京化工大学 | Metal oxide-carbon nitride composite material and preparation method and use thereof |
| CN108593719A (en) * | 2018-06-26 | 2018-09-28 | 浙江大学 | A kind of immunosensor based on flexible electrode |
| CN112824884A (en) * | 2019-11-21 | 2021-05-21 | 湖南大学 | Photoelectrochemical aptamer sensor and preparation method and application thereof |
| CN112371146A (en) * | 2020-10-14 | 2021-02-19 | 江苏大学 | Preparation method and application of Z-type carbon nitride-iron oxide catalyst containing nitrogen defect structure |
| CN112250118A (en) * | 2020-10-16 | 2021-01-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of composite material modified graphene, product and application thereof |
| CN112768257A (en) * | 2020-12-15 | 2021-05-07 | 大连理工大学 | Nickel-cobalt oxide flexible electrode and preparation method and application thereof |
| CN113145154A (en) * | 2021-03-06 | 2021-07-23 | 徐州工程学院 | Preparation method of composite catalyst for photocatalytic reduction of chromium (VI) -containing wastewater |
| CN113265873A (en) * | 2021-05-14 | 2021-08-17 | 南开大学 | Flexible sensing fabric carrying metal oxide, conductive polymer and two-dimensional nano material, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHUO WANG等: "Mechanistic insight into photocatalytic CO2 reduction by a Z-scheme g-C3N4 TiO2 heterostructure", NEW JOURNAL OF CHEMISTRY, vol. 45, pages 11474 - 11480 * |
| 韩俊;吕旭初;贺山山;刘茂祥;王霜;张树鹏;: "电化学储能及传感器用氮化碳基复合材料设计策略", 大学化学, no. 02, pages 1 - 11 * |
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