CN113092549A - Preparation method of flexible photoelectric cathode sensor for sensitively detecting lead ions - Google Patents
Preparation method of flexible photoelectric cathode sensor for sensitively detecting lead ions Download PDFInfo
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- CN113092549A CN113092549A CN202110415883.2A CN202110415883A CN113092549A CN 113092549 A CN113092549 A CN 113092549A CN 202110415883 A CN202110415883 A CN 202110415883A CN 113092549 A CN113092549 A CN 113092549A
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Abstract
The invention discloses a preparation method of a flexible photoelectric cathode sensor for sensitively detecting lead ions. The porphyrin-based covalent organic framework film prepared by a liquid/liquid interface growth method is used as a photocathode material to obtain a strong initial photocurrent signal. And then, a large amount of cadmium selenide/silicon dioxide core-shell quantum dots are loaded on the porphyrin-based covalent organic framework film through a hybridization chain reaction, and the multiple quenching effect and the steric hindrance effect of the quantum dots are combined, so that the signal of the sensor is quenched to the lowest degree, and the sensitive detection of lead ions is realized. The method can improve the strength and stability of cathode photoelectric signals, reduce the interference of reducing substances on a cathode photoelectric sensor, and has wide application prospect in the aspect of detecting lead ions in tap water and lake water.
Description
Technical Field
The invention relates to the technical field of electrochemical detection, in particular to a preparation method of a flexible photoelectric cathode sensor for sensitively detecting lead ions.
Background
In recent years, lead ion pollution in water environment has received unprecedented attention from society because of its toxicity, bioaccumulation and persistence. Lead ions in various heavy metal pollutants are extremely harmful to organisms, and can interfere with various aspects of fetal development to cause brain and kidney injury and even death. In order to prevent lead ions from causing harm to organisms and environment, many analytical test techniques for rapidly and quantitatively detecting lead ions in the environment are proposed, including various methods such as electrochemistry, fluorescence, surface plasmon resonance, electrochemiluminescence and the like. However, the above-mentioned techniques rely on complicated equipment and cumbersome sample pretreatment processes, and are limited in practical applications. Therefore, there is a need for a simple, reliable, and low-cost method for measuring lead ions.
The flexible photoelectric cathode sensor receives more and more attention due to the advantages of high sensitivity, low background noise, good stability and the like. In addition, the photoelectrochemical detection method can rapidly and accurately carry out quantitative analysis on the detected object through a simple electronic reading device, and the miniaturization and the convenience of the flexible photoelectric cathode sensor are realized. At present, various n-type semiconductor materials such as ZnO and TiO are used2And CdS and the like, and develops an anode photoelectrochemical sensing platform for detecting protein, DNA and metal ions. However, the photoelectrochemical detection platforms based on the photoanode are interfered by reducing substances in real samples, so that the application of the photoelectrochemical detection platforms is limited. The photoelectric cathode material based on the p-type semiconductor can prevent the hole inherent in the photoelectric anode interface from generating oxidation reaction, and greatly widens the application range of the photoelectric cathode sensor. Therefore, the development of a new photocathode material with low cost and high efficiency for a flexible photocathode sensor is becoming increasingly slow. Fortunately, porphyrins and derivatives thereof have been widely studied as photocathode materials for flexible photocathode sensors. These tetrapyrrole macrocycles have strong light absorption at the 450 nm and 500-650 nm bands. In addition, porphyrins and their derivatives have ultra-fast electron injection, slow charge recombination kinetics and good chemical stability, and also have the advantages of fast generation of hole-electron pairs and slow charge recombination. However, disordered arrangements between porphyrin molecules and their low charge transport efficiency are the biggest challenges and challenges facing their practical application.
The covalent organic framework provides a charge transmission channel due to the conjugation of the covalent organic framework on a two-dimensional plane and the atomic periodic columnar pi array in the vertical direction, and greatly improves the charge transfer capacity. In recent years, porphyrin-based covalent organic framework materials have proven to be an excellent cathode photovoltaic material in the field of photovoltaics. Inspired by the above knowledge, a feasible way is provided for developing a high-performance flexible photocathode sensor by preparing a porphyrin-based covalent organic framework film as a photoelectric device.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of a flexible photocathode sensor for sensitively detecting lead ions, which is characterized by comprising the following steps:
(1) preparing a flexible indium tin oxide electrode: cutting the flexible indium tin oxide electrode to an area of 1 cm multiplied by 4 cm, sequentially adding acetone, absolute ethyl alcohol and ultrapure water for ultrasonic treatment for 10-20 min, and then placing under nitrogen flow for drying for 10-20 min, wherein the flexible indium tin oxide is abbreviated as PET-ITO;
(2) preparation of porphyrin-based covalent organic framework films: dissolving 3.6-3.8 mg of terephthalaldehyde in 50 mL of dichloromethane by adopting a liquid/liquid interface growth method, adding 40 mL of ultrapure water as a separation water layer to the upper layer of an aldehyde solution, then dissolving 8.4 mg of tetraaminophenylporphyrin and 9.7 mg of p-toluenesulfonic acid in a mixed solution of 35 mL of water and 15 mL of acetonitrile, slowly dripping the mixed solution onto the top of the separation water layer, and storing the whole system at room temperature for 70-74 h to form a porphyrin-based covalent organic framework film at a liquid/liquid interface, wherein the porphyrin-based covalent organic framework film is abbreviated as TAPP-COFs film;
(3) preparing the cadmium selenide/silicon dioxide core-shell quantum dots: dispersing cadmium selenide quantum dots in 300 mu L of methylbenzene, adding 1.5 mu L of ethyl orthosilicate, stirring for 20 hours to obtain silanized quantum dots, then adding 1.0 g of Igepal CO-520 and 300 mu L of silanized quantum dots into 10 mL of cyclohexane under vigorous stirring, then adding 0.3 mL of ammonia water solution, injecting 1.5 mu L of ethyl orthosilicate, controlling the reaction time to be 11-13 hours, cooling the mixed solution to room temperature after the reaction is finished, and centrifugally collecting the cadmium selenide/silicon dioxide core-shell quantum dots, wherein the cadmium selenide/silicon dioxide core-shell quantum dots are abbreviated as CdSe @ SiO2QDs；
（4）CdSe@SiO2QDs is coupled to DNA strands: mu.L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and DNA strand of 1 ODAdding into 1 mL phosphate buffered saline solution with pH 7.4, wherein the DNA chain comprises H1Chain or H2The chain, phosphate buffered saline solution is abbreviated PBS, followed by 40. mu.L of CdSe @ SiO2Adding QDs solution into the system, incubating at room temperature for 11-13H, adding 100 μ L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, oscillating for 4H, washing the excessive impurities with ultrapure water for three times under centrifugal condition, and uniformly dispersing in PBS with pH of 7.4 to obtain H1-quantum dots or H2Quantum dots of which H1-Quantum dots abbreviated as H1-QDs，H2-Quantum dots abbreviated as H2-QDs；
(5) Construction of the flexible photocathode sensor: transferring TAPP-COFs film to a clean PET-ITO substrate, drying in an oven at 40 ℃ overnight, and adding 1 OD DNAzyme S1The strand was placed in 1050-1The chain was incubated dropwise on TAPP-COFs membrane for 6 h, then 40. mu.L of 2 mM 6-mercapto-1-hexanol solution was added, washed again, and 40. mu.L of 2.5. mu. M S was added dropwise onto the sensor surface2The strands were incubated at room temperature for 6H, the unreacted DNA strands were washed off with PBS pH 7.4, and finally 35. mu.L of 1. mu.M H was added1-QDs and 35. mu.L of 1. mu.M H2And (4) incubating at room temperature for 2 h to obtain the flexible photocathode sensor for sensitively detecting lead ions.
The invention has the beneficial effects that:
(1) the TAPP-COFs film is prepared by adopting a liquid/liquid interface growth method, the preparation method is simple, the post-treatment is relatively easy, and the synthesized CdSe @ SiO is2QDs have multiple quenching and steric effects;
(2) the cathode photoelectric material used in the invention can improve the strength of cathode photoelectric signals, reduce the interference of reducing substances on the flexible cathode photoelectric sensor, improve the photoelectric property of the flexible cathode photoelectric sensor and enable the prepared flexible photoelectric cathode sensor to have higher sensitivity;
(3) the flexible photoelectric cathode sensor constructed by the invention has the advantages of wide detection linear range, low detection limit, good selectivity, good stability and reproducibility, can realize online real-time detection of lead ions in tap water and lake water samples, and has high performance when detecting the lead ions.
Drawings
FIG. 1 is a scanning electron microscope image of (A) TAPP-COFs thin film, and a scanning electron microscope cross-sectional image of (B) TAPP-COFs thin film, in which: an optical microscopy image;
FIG. 2 is a diagram of the UV-VIS absorption spectrum of TAPP-COFs thin films;
FIG. 3 is CdSe @ SiO2Transmission electron microscopy images of QDs;
FIG. 4 is a process flow diagram for the fabrication of a flexible photocathode sensor;
FIG. 5 is (A) the photocurrent values of the flexible photocathode sensor after adding lead ions of different concentrations, and (B) the calibration curve for lead ion detection at different concentrations;
FIG. 6 is a selectivity test chart of a flexible photocathode sensor;
fig. 7 is a graph of flexible photocathode sensor time-photocurrent response, inset: and testing the long-term stability of the sensor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the present invention, but the contents of the present invention are not limited to the following embodiments.
Example 1 preparation method of Flexible photocathode sensor
(1) Preparing a PET-ITO electrode: cutting a PET-ITO electrode to an area of 1 cm multiplied by 4 cm, sequentially adding acetone, absolute ethyl alcohol and ultrapure water, carrying out ultrasonic treatment for 15 min, and then placing the PET-ITO electrode under nitrogen flow for drying for 15 min;
(2) preparing a TAPP-COFs film: dissolving 3.7 mg of terephthalaldehyde in 50 mL of dichloromethane by adopting a liquid/liquid interface growth method, adding 40 mL of ultrapure water as a separation water layer to the upper layer of an aldehyde solution, then dissolving 8.4 mg of tetraaminophenylporphyrin and 9.7 mg of p-toluenesulfonic acid in a mixed solution of 35 mL of water and 15 mL of acetonitrile, slowly dripping the mixed solution on the top of the separation water layer, placing the whole system at room temperature for preservation for 72 hours, and forming a TAPP-COFs film at a liquid/liquid interface; FIG. 1 is a scanning electron microscope image of TAPP-COFs thin film, clearly showing that the appearance of TAPP-COFs thin film presents a uniform and continuous layered structure, the thickness is about 300 nm and the thickness is uniform, which indicates that the method of liquid/liquid interface growth adopted by the invention well maintains the typical structure of TAPP-COFs thin film, FIG. 2 is an ultraviolet-visible absorption spectrogram of TAPP-COFs thin film, which can show that the TAPP-COFs thin film has a wider absorption range within the range of 300-1300 nm, which indicates that the TAPP-COFs thin film prepared by the invention has stronger light-receiving capability within the range of ultraviolet and visible light;
（3）CdSe@SiO2preparation of QDs: dispersing cadmium selenide quantum dots in 300 mu L of methylbenzene, adding 1.5 mu L of ethyl orthosilicate, stirring for 20 h to obtain silanized quantum dots, then adding 1.0 g of Igepal CO-520 and 300 mu L of silanized quantum dots into 10 mL of cyclohexane under vigorous stirring, then adding 0.3 mL of ammonia water solution, injecting 1.5 mu L of ethyl orthosilicate, controlling the reaction time to be 12 h, cooling the mixed solution to room temperature after the reaction is finished, and centrifugally collecting to obtain CdSe @ SiO2QDs; FIG. 3 is CdSe @ SiO2Transmission electron microscopy of QDs clearly showing CdSe @ SiO2QDs are approximately spherical, and the diameter is 9-12 nm, which shows that the synthesis method of the invention well maintains CdSe @ SiO2Typical structures of QDs;
（4）CdSe@SiO2QDs is coupled to DNA strands: mu.L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 OD DNA strands including H were added to 1 mL of phosphate buffered saline at pH 7.41Chain or H2The chain, phosphate buffered saline solution is abbreviated PBS, followed by 40. mu.L of CdSe @ SiO2Adding QDs solution into the system, incubating at room temperature for 11-13H, adding 100 μ L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, oscillating for 4H, washing the excessive impurities with ultrapure water for three times under centrifugal condition, and uniformly dispersing in PBS with pH of 7.4 to obtain H1-quantum dots or H2Quantum dots of which H1-Quantum dots abbreviated as H1-QDs，H2-Quantum dots abbreviated as H2-QDs；
(5) Construction of the flexible photocathode sensor: transferring TAPP-COFs film to a clean PET-ITO substrate, drying in an oven at 40 ℃ overnight, and adding 1 OD DNAzyme S1The strand was placed in 1050-1The chain was incubated dropwise on TAPP-COFs membrane for 6 h, then 40. mu.L of 2 mM 6-mercapto-1-hexanol solution was added, washed again, and 40. mu.L of 2.5. mu. M S was added dropwise onto the sensor surface2The strands were incubated at room temperature for 6H, the unreacted DNA strands were washed off with PBS pH 7.4, and finally 35. mu.L of 1. mu.M H was added1-QDs and 35. mu.L of 1. mu.M H2And (4) incubating for 2 h at room temperature to obtain a flexible photocathode sensor for sensitively detecting lead ions; fig. 4 is a flow chart of a manufacturing process of the flexible photocathode sensor.
Example 2 Performance testing of Flexible photocathode Sensors
(1) By using a current-time curve method, TAPP-COFs film/CdSe @ SiO2A three-electrode system is formed by using QDS-DNA modified PET-ITO as a working electrode, a saturated calomel electrode as a reference electrode and a platinum wire as a counter electrode;
(2) determination of the working curve of the flexible photocathode sensor: dripping 35 mu L of lead ion solutions with different concentrations on a flexible photoelectric cathode sensor, washing an electrode for multiple times by PBS (phosphate buffer solution) with the pH value of 7.4 after lead ion specificity identification, drying under nitrogen flow, then carrying out photoelectrochemical signal detection, and realizing quantitative detection on target lead ions through the relation between the concentration of the target lead ions and cathode photocurrent signals; FIG. 5 is a working curve of the flexible photocathode sensor after lead ions with different concentrations are added, and it can be seen that the photocurrent intensity increases with the increase of the lead ion concentration, and the photocurrent intensity and the lead ion concentration show linear relationship in the ranges of 0.05-1 nM and 1-1000 nM, and the detection limit is 0.012 nM, which indicates that the flexible photocathode sensor prepared by the invention has a wide detection linear range and a low detection limit;
(3) selective testing of flexible photocathode sensors: selectively testing an empty sample, interfering metal ions with the concentration of 1000 nM, lead ions with the concentration of 100 nM, a mixed solution of 100 nM lead ions and all the interfering metal ions with the concentration of 1000 nM, and recording photocurrent response; FIG. 6 is a selective test chart of the flexible photocathode sensor, which is sensitive to lead ion detection and has no photoelectric signal for other interfering metal ions, and illustrates that the flexible photocathode sensor prepared by the invention can accurately detect lead ions and has good selectivity;
(4) testing the stability of the flexible photoelectric cathode sensor: recording the curves of the photocurrent and the time of 10 periods to test the stability of the sensor, storing the sensor in a refrigerator at 4 ℃ and measuring the sensor once every other week; fig. 7 is a graph of time-photocurrent response of the flexible photocathode sensor, where the photocurrent response is relatively stable during ten cycles, and the stability still reaches 90% of the initial value after continuous storage for 5 cycles, which illustrates that the flexible photocathode sensor prepared by the present invention has good reproducibility and stability.
Example 3 detection of lead ions in tap water and lake water samples by a flexible photocathode sensor
(1) The flexible photoelectric cathode sensor detects lead ions in a tap water sample: adding 1 nM, 10 nM, 50 nM and 100 nM lead ions into tap water sample by standard addition method, respectively, detecting that the tap water sample contains 0.982 nM, 10.124 nM, 48.361 nM and 99.752 nM lead ions, respectively, and the recovery rate is 96.72% -101.24%;
(2) the flexible photoelectric cathode sensor detects lead ions in the lake water sample: adding 1 nM, 10 nM, 50 nM and 100 nM lead ions into lake water sample by standard addition method, detecting that tap water sample contains 1.023 nM, 10.224 nM, 48.125 nM and 99.887 nM lead ions, recovery rate is 96.24% -102.30%;
(3) the obtained data show that the relative standard deviation of the measured result is small and is only 1.34-3.19%, the feasibility of practical application is strong, and the online and real-time monitoring on the lead ions can be realized.
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Claims (1)
1. A preparation method of a flexible photoelectric cathode sensor for sensitively detecting lead ions is characterized by comprising the following steps:
(1) preparing a flexible indium tin oxide electrode: cutting the flexible indium tin oxide electrode to an area of 1 cm multiplied by 4 cm, sequentially adding acetone, absolute ethyl alcohol and ultrapure water for ultrasonic treatment for 10-20 min, and then placing under nitrogen flow for drying for 10-20 min, wherein the flexible indium tin oxide is abbreviated as PET-ITO;
(2) preparation of porphyrin-based covalent organic framework films: dissolving 3.6-3.8 mg of terephthalaldehyde in 50 mL of dichloromethane by adopting a liquid/liquid interface growth method, adding 40 mL of ultrapure water as a separation water layer to the upper layer of an aldehyde solution, then dissolving 8.4 mg of tetraaminophenylporphyrin and 9.7 mg of p-toluenesulfonic acid in a mixed solution of 35 mL of water and 15 mL of acetonitrile, slowly dripping the mixed solution onto the top of the separation water layer, and storing the whole system at room temperature for 70-74 h to form a porphyrin-based covalent organic framework film at a liquid/liquid interface, wherein the porphyrin-based covalent organic framework film is abbreviated as TAPP-COFs film;
(3) preparing the cadmium selenide/silicon dioxide core-shell quantum dots: dispersing cadmium selenide quantum dots in 300 mu L of methylbenzene, adding 1.5 mu L of ethyl orthosilicate, stirring for 20 hours to obtain silanized quantum dots, then adding 1.0 g of Igepal CO-520 and 300 mu L of silanized quantum dots into 10 mL of cyclohexane under vigorous stirring, then adding 0.3 mL of ammonia water solution, injecting 1.5 mu L of ethyl orthosilicate, controlling the reaction time to be 11-13 hours, cooling the mixed solution to room temperature after the reaction is finished, and centrifugally collecting the cadmium selenide/silicon dioxide core-shell quantum dots, wherein the cadmium selenide/silicon dioxide core-shell quantum dots are abbreviated as CdSe @ SiO2 QDs；
（4）CdSe@SiO2QDs is coupled to DNA strands: mu.L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 OD DNA strands including H were added to 1 mL of phosphate buffered saline at pH 7.41Chain or H2The chain, phosphate buffered saline solution is abbreviated PBS, followed by 40. mu.L of CdSe @ SiO2The QDs solution is added to the above system inIncubating at room temperature for 11-13H, adding 100 μ L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, oscillating for reaction for 4H, washing excessive impurities with ultrapure water for three times under centrifugal condition, and uniformly dispersing in PBS with pH of 7.4 to obtain H1-quantum dots or H2Quantum dots of which H1-Quantum dots abbreviated as H1-QDs，H2-Quantum dots abbreviated as H2-QDs；
(5) Construction of the flexible photocathode sensor: transferring TAPP-COFs film to a clean PET-ITO substrate, drying in an oven at 40 ℃ overnight, and adding 1 OD DNAzyme S1The strand was placed in 1050-1The chain was incubated dropwise on TAPP-COFs membrane for 6 h, then 40. mu.L of 2 mM 6-mercapto-1-hexanol solution was added, washed again, and 40. mu.L of 2.5. mu. M S was added dropwise onto the sensor surface2The strands were incubated at room temperature for 6H, the unreacted DNA strands were washed off with PBS pH 7.4, and finally 35. mu.L of 1. mu.M H was added1-QDs and 35. mu.L of 1. mu.M H2And (4) incubating at room temperature for 2 h to obtain the flexible photocathode sensor for sensitively detecting lead ions.
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| CN115725100A (en) * | 2022-11-14 | 2023-03-03 | 北京科技大学 | Perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane and preparation method thereof |
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Application publication date: 20210709 |