CN109884144B - Preparation and application of semiconductor nano material electrode - Google Patents
Preparation and application of semiconductor nano material electrode Download PDFInfo
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- CN109884144B CN109884144B CN201910196980.XA CN201910196980A CN109884144B CN 109884144 B CN109884144 B CN 109884144B CN 201910196980 A CN201910196980 A CN 201910196980A CN 109884144 B CN109884144 B CN 109884144B
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Abstract
The invention discloses a preparation method and application of a semiconductor nano material electrode, wherein the method comprises the following steps: s11: preparation of TGA-stabilized CdS NCs: adding CdCl2Adding the solution and TGA into a container, stirring under nitrogen atmosphere for 20-40min while adjusting pH of the mixture to 7-13 with NaOH solution, and adding Na2Heating and refluxing the S solution for 3-5h at the temperature of 105-115 ℃ under the nitrogen atmosphere; s12: CdS NCs/TiO2Preparing NTs electrodes; s13: CdS NCs/TiO2Activation of NTs electrodes: CdS NCs/TiO prepared from S22Soaking the NTs electrode in an activating solution, slightly shaking for 14-18h at 35-39 ℃, and washing with ultrapure water after activation to obtain a semiconductor nano material electrode; CdS NCs/TiO prepared by the invention2NTs electrode can be used as ECL probe for detecting H2O2The concentration of the probe is wide in the linear range of 50nM to 500. mu.M, and the reproducibility and stability are good.
Description
Technical Field
The invention relates to the technical field of construction of an electrochemiluminescence system, in particular to preparation and application of a semiconductor nano material electrode.
Background
Electrogenerated Chemiluminescence (ECL) is the formation of luminophores on the surface of an electrode via electrochemical and chemical reactionsThe high-energy excited state is relaxed to generate a luminescence process. The method has become an important analysis technology due to the advantages of low background signal, high sensitivity, excellent space-time controllability and the like. In recent years, semiconductor nanomaterials (S-NMs) such as CdS, CdSe, CdTe, TiO2And the like, which has the advantages of good stability, photobleaching resistance, size/surface defect control and the like, has become a novel ECL luminophor.
However, the biggest obstacle to the construction and development of an ECL sensor based on S-NMs is its limited ECL efficiency. Because the ECL intensity of S-NMs hardly reaches that of conventional ECL reagent, such as Ru (bpy)3 2+Based on this, a number of signal amplification methods have been used to improve the sensitivity of semiconductor nanocrystal-based ECL sensors 9, including nanoparticle, enzyme, self-assembly and multiplex DNA signal amplification. Bao assembles the prepared CdSe/ZnSNCs on the surface of a glassy carbon electrode by using p-aminophenol to construct an ECL sensor for sensitive detection of dopamine. Jee designs an immunosensor based on CdS NCs by utilizing self-assembly and gold nanoparticle amplification technology, and the immunosensor is used for detecting low-density lipoprotein. In addition, early research work showed that S-NMs ECL performance is very sensitive to surface states. Passivation of semiconductor surfaces (stabilizer encapsulation) can effectively improve ECL performance for two reasons: firstly, a non-radiative surface state can be effectively removed, and the surface trap is enhanced, so that the ECL efficiency is improved; secondly, the semiconductor nano material body wrapped by the stabilizer is beneficial to the filling process of electrons and holes, so that ECL emission is enhanced. For example, Zou prepared mercaptopropionic acid and hexametaphosphoric acid subcontracted CdTe NCs using a bistable agent encapsulation method, due to its strong ECL emission, was successfully applied to the sensitive detection of dopamine in real samples without any amplification technique.
As semiconductor material, TiO2Is a novel material with stable chemical property, large specific surface area and no toxicity to organisms. With other forms of TiO2In contrast, TiO2Nanotube array (TiO)2NTs) is increasingly applied to the fields of photoelectrochemistry and electrocatalysis, but the application of NTs to ECL is relatively less. This is because nano TiO2Wider band gap(anatase: 3.2 eV; rutile: 3.0eV) makes it difficult for electrons to be excited, resulting in undesirable ECL performance. However, the compound with the narrow forbidden band semiconductor is effective for improving TiO2One method of ECL performance. A semiconductor with a narrow forbidden band width is coupled to a wide forbidden band semiconductor because it has a more negative conduction band edge to make the injection of electrons from its conduction band easier. CdS is used as a narrow forbidden band semiconductor, the forbidden band width is eV, the conduction band edge is 0.5eV, which is more negative than that of titanium dioxide, so that electrons obtained by CdS are easier to inject into TiO after the CdS and the titanium dioxide are compounded2The conduction band of (a). There have been many previous works that show that the coupling of the two has very excellent photoelectrochemical properties in the visible region. For example, CdS is deposited by carrying out continuous chemical water bath on the surface of a TiO2 nanotube, so that the photocurrent is improved by 6 times. As far as present, CdS NCs/TiO2The use of NTs composites in ECL is less. We have in the subject group used a continuous chemical bath deposition process to deposit CdS nanocrystals onto TiO2The nano composite material with high ECL performance is obtained on the surface of NTs, the luminous mechanism of the nano composite material is researched, and the nano composite material is successfully applied to the detection of prostate cancer antigen.
Cells are the basic units of the morphological structure and the life activity of organisms, and various Reactive Oxygen Species (ROS) are generated in the process of metabolism. Active oxygen plays an important role in cell signal transduction and is involved in the initiation of various factors in cell biological effects. They can also react with intracellular biological macromolecules, causing membrane lipid peroxidation, intracellular protein and enzyme denaturation, DNA damage, etc. TiO22Is an important representative of ROS in cells, has the characteristics of high stability, specific reaction selectivity, strong cell membrane permeability and the like, and the concentration of the ROS is closely related to the concentration of ROS molecules such as superoxide anions, hydroxyl free radicals and the like. The study shows that H2O2Is a key factor in regulating the apoptotic process, at low concentrations, H2O2As a second messenger, participate in cell signaling, control cell proliferation, differentiation and survival, and participate in the regulation of gene transcription; and at high concentrations, H2O2Can disrupt the intracellular balance and induce oxidative stress, resulting inCell death, tissue damage, cardiovascular diseases, tumor and neuron degeneration. Thus, for H in cells2O2High sensitivity quantitative in situ detection for understanding H2O2The role in cytopathology is of great importance in providing reliable information on diagnosis and prognosis of related diseases. The method has important practical significance in the fields of biological analysis and environment, and can accurately and quickly detect the hydrogen peroxide. Although many enzyme-based biosensors can detect hydrogen peroxide, and even an amperometric biosensor of simple design can achieve a nanomolar detection limit, enzymes cannot maintain stable catalytic performance for a long time due to their inherent instability.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides the preparation and the application of the semiconductor nano material electrode, and the CdS NCs/TiO prepared by the invention2NTs electrode can be used as ECL probe for detecting H2O2The concentration of the probe is wide in the linear range of 50nM to 500. mu.M, and the reproducibility and stability are good.
The invention provides a preparation method of a semiconductor nano material electrode, which comprises the following steps:
s11: preparation of TGA-stabilized CdS NCs: adding CdCl2Adding the solution and TGA into a container, stirring under nitrogen atmosphere for 20-40min while adjusting pH of the mixture to 7-13 with NaOH solution, and adding Na2Heating and refluxing the S solution for 3-5h at the temperature of 105-115 ℃ under the nitrogen atmosphere;
S12：CdS NCs/TiO2preparation of NTs electrode:
(1) ultrasonically cleaning the cut titanium sheet in ethanol and ultrapure water in sequence to remove impurities adsorbed on the surface;
(2) ultrasonically cleaning the titanium sheet in the step (1) in a mixed solution of hydrofluoric acid, nitric acid and water for 1-3min, and removing an oxide layer on the surface;
(3) sequentially carrying out ultrasonic treatment on the titanium sheet pickled in the step (2) in ethanol and water for 4-6min respectively, and drying the titanium sheet by nitrogen for later use;
(4) immersing the clean titanium sheet obtained in the step (3) into a hydrofluoric acid solution containing 0.4-0.6% of weight, controlling the distance between the titanium sheet and the platinum sheet as an anode and the anode to be 2-4cm under the direct current voltage of 15-25V, and oxidizing the anode for 1.5-3.5h at room temperature;
(5) ultrasonically cleaning the titanium sheet oxidized in the step (4) in ultrapure water, drying the titanium sheet by blowing with nitrogen, finally calcining the titanium sheet in a muffle furnace at the temperature of 400-600 ℃ in air atmosphere for 40-80min to prepare integrally arranged TiO2NTs electrodes;
(6) mixing the TiO in the step (5)2Washing NTs electrode with PBS buffer solution, soaking in 2% PDDA solution with zeta potential of 6.27mV, standing for 4-6min, taking out, and washing with water; placing into CdS NCs solution with zeta potential of-16.6 mV for 4-6min, taking out, and washing with water;
(7) repeating the step (6) for 2-4 times to obtain CdS NCs/TiO2NTs electrodes;
S13：CdS NCs/TiO2activation of NTs electrodes: CdS NCs/TiO prepared from S122Soaking NTs electrode in activating solution passing 0.2M Na2HPO4Adjusting the pH value of the solution to about 5.0, slightly shaking for 14-18h at 35-39 ℃, and washing with ultrapure water after activation to obtain the semiconductor nano material electrode.
Preferably, CdCl in S112The molar ratio of the CdCl to TGA is 1:6-82With Na2The molar ratio of S is 1: 1-1.2.
Preferably, the volume ratio of the hydrofluoric acid to the nitric acid to the water in the S12 is 1 (3-5) to (4-6).
Preferably, the activating solution in S13 comprises H2O2Citric acid and deionized water, and H in each liter of activating solution2O2The molar ratio of the citric acid to the citric acid is 5: 30-50.
The invention provides application of a semiconductor nano material electrode luminescent system, wherein the luminescent system comprises an activated electrode and a co-reactant H described by S132O2。
The semiconductor nano material electrode provided by the invention is H2O2Application in detection.
Hair brushThe proposed semiconductor nano-material electrode is in cell H2O2Application in detection.
Preferably, H is in said cell2O2The extraction method comprises the following steps:
s21: culturing HL-60 tumor cells in a DMEM culture medium containing 8% -12% fetal calf serum in humidified air at 35-40 ℃;
s22: centrifuging HL-60 tumor cells in exponential growth phase with sterile PBS solution, washing for 1-3 times, removing supernatant, adding PBS solution (pH7.4), and adding 10ng/ml PMA to stimulate cells (every 1.6 × 10)5Adding 1ng PMA into each tumor cell), centrifuging for 15-20s to obtain product containing H2O2The supernatant of (2).
Preferably, the humidified air in S21 includes 93% to 97% of air and 3% to 7% of carbon dioxide (volume percentage).
Preferably, the centrifugation condition in S22 is centrifugation at 6000-10000r/min for 3-7 min.
The action mechanism is as follows:
(1) the hydrogen peroxide generates hydroxyl free radicals on the surface of the electrode through reduction, the hydroxyl free radicals have the capacity of filling holes into the valence band of the semiconductor nano material, and the TiO has the capacity of filling holes into the valence band of the semiconductor nano material2Can be used as a hole fixing agent, when the electrode potential is sufficiently negative, the CdS NCs conduction band can directly obtain electrons on the surface of the electrode, and TiO of a wide forbidden band2The semiconductor is coupled with CdS with narrow forbidden band to promote CdS (e)-) Electrons in CdS NCs are transferred from conduction band to TiO2Greatly improves electron-hole recombination and TiO2 *Generation of final ECL emission enhancement;
(2)TiO2the recombination with CdS also promotes TiO2(h+) H + in (1) is derived from TiO2The valence band of (1) is transferred to the valence band of CdS NCs, so that the generation of CdS is promoted, and the emission intensity of ECL is further improved;
(3) the semiconductor nano material body wrapped by the stabilizer can not only effectively clear the non-radiative surface state, but also is beneficial to the filling process of electrons and holes, thereby improving the ECL efficiency and enhancing the ECL emission;
(4) CdS NCs and TiO2The coupling of NTs can increase the ECL emission process of each other, that is, the increase of ECL light intensity is the result of the synergistic effect of the two, and the activated electrode is enabled to be combined with TiO nanocrystalline due to the improvement of ECL performance of CdS nanocrystalline2The synergy between NTs is more pronounced, as evidenced by a further increase in ECL intensity.
Compared with the prior art, the invention has the beneficial effects that:
(1) CdS NCs/TiO prepared by the invention2NTs electrode can be used as ECL probe for detecting H2O2The linear range of the probe is wider from 50nM to 500 μ M, and the reproducibility and stability are good;
(2) CdS NCs/TiO prepared by the invention2The luminescent system composed of the NTs electrode and the hydrogen peroxide has strong luminous intensity, the luminous intensity of the common semiconductor material under the same condition is hundreds of light intensity, the light intensity of the invention can reach tens of thousands of light intensity, and the intensity is enhanced by about 70 times;
(3) the hydrogen peroxide adopted by the invention as the coreactant of the luminescent system has less pollution compared with the existing potassium persulfate coreactant.
The abbreviations used in the present invention have the following meanings:
TGA-thioglycolic acid; NCs-nanocrystals; NTs-nanotubes; PDDA-polydiallyldimethylammonium chloride; PMA-phorbol myristate acetate.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
The electrochemical and ECL experiments in the present invention were performed at room temperature on an MPI-A multifunctional electrochemical and chemiluminescent analytical system (Sierray Mimey instruments, Inc.). The scan rate during the test was 100mV s-1. In the experiment, a three-electrode system is adopted, and a working electrode is prepared TiO2NTs electrode or CdS sensitized TiO2The NTs electrode, the Pt wire electrode and the Saturated Calomel Electrode (SCE) are respectively used as a counter electrode and a reference electrode. Apoptosis of cells was measured using a flow cytometer (Becton Dickinson Medical Devices)Co ltd., usa).
For the reagent used in the present invention, polydiallyldimethylammonium chloride (PDDA; 20%, w/w in water, MW 200000-; citric acid was purchased from chemical reagent works of Jiangsu Huakang science and technology; h2O2Purchased from Shanghai chemical reagents for analytical purity; hydrofluoric acid was purchased from Nanjing chemical Co.
Example 1
The invention provides a preparation method of a semiconductor nano material electrode, which comprises the following steps:
s11: preparation of TGA-stabilized CdS NCs: 0.01M CdCl2Adding the solution and TGA into a container to obtain 50ml mixed solution, stirring under nitrogen atmosphere for 20-40min while adjusting pH to 8 with 1M NaOH solution, and adding 0.1M Na2Heating and refluxing the S solution at 105 ℃ for 3h under nitrogen atmosphere, wherein CdCl2The molar ratio of the CdCl to the TGA is 1:62With Na2The molar ratio of S is 1: 1;
S12：CdS NCs/TiO2preparation of NTs electrode:
(1) ultrasonically cleaning the cut titanium sheet in ethanol and ultrapure water in sequence to remove impurities adsorbed on the surface;
(2) ultrasonically cleaning the titanium sheet in the step (1) in a mixed solution of hydrofluoric acid, nitric acid and water for 1min, and removing an oxide layer on the surface, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water is 1:3: 4;
(3) sequentially carrying out ultrasonic treatment on the titanium sheet pickled in the step (2) in ethanol and water for 4min respectively, and drying the titanium sheet by nitrogen for later use;
(4) immersing the clean titanium sheet obtained in the step (3) into a hydrofluoric acid solution containing 0.5 wt%, controlling the distance between two electrodes to be 2cm under the direct current voltage of 15V and taking the titanium sheet as an anode and a platinum sheet as a cathode, and anodizing for 1.5h at room temperature;
(5) ultrasonically cleaning the titanium sheet oxidized in the step (4) in ultrapure water, drying the titanium sheet by blowing with nitrogen, and finally placing the titanium sheet into a muffle furnace in an air atmosphereCalcining at 400 ℃ for 40min to prepare integrally arranged TiO2NTs electrodes;
(6) mixing the TiO in the step (5)2Washing NTs electrode with PBS buffer solution, soaking in 2% PDDA solution with zeta potential of 6.27mV, standing for 4min, taking out, and washing with water; placing into CdS NCs solution with zeta potential of-16.6 mV for 4min, taking out, and washing with water;
(7) repeating the step (6) for 2 times to obtain CdS NCs/TiO2NTs electrodes;
S13：CdS NCs/TiO2activation of NTs electrodes: CdS NCs/TiO prepared from S22NTs electrode soaked in 1.5ml of hydrogen peroxide solution2O2And citric acid is used for forming an activation solution, the solution is slightly shaken for 14 to 18 hours at the temperature of between 35 and 39 ℃, and the activation solution is washed by ultrapure water to obtain the semiconductor nano material electrode, wherein H in each liter of the activation solution2O2The molar ratio to citric acid was 5: 30.
Example 2
The invention provides a preparation method of a semiconductor nano material electrode, which comprises the following steps:
s11: preparation of TGA-stabilized CdS NCs: 0.01M CdCl2Adding the solution and TGA into a container to obtain 50mL of mixed solution, stirring under nitrogen atmosphere for 40min while adjusting pH to 13 with 1M NaOH solution, and adding 0.1M Na2Heating and refluxing the S solution for 5h at 115 ℃ under the nitrogen atmosphere, wherein CdCl2The molar ratio of the CdCl to the TGA is 1:82With Na2The molar ratio of S is 1: 1.2;
S12：CdS NCs/TiO2preparation of NTs electrode:
(1) ultrasonically cleaning the cut titanium sheet in ethanol and ultrapure water in sequence to remove impurities adsorbed on the surface;
(2) ultrasonically cleaning the titanium sheet in the step (1) in a mixed solution of hydrofluoric acid, nitric acid and water for 1-3min, and removing an oxide layer on the surface, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water is 1:5: 6;
(3) sequentially carrying out ultrasonic treatment on the titanium sheet pickled in the step (2) in ethanol and water for 6min respectively, and drying the titanium sheet by nitrogen for later use;
(4) immersing the clean titanium sheet obtained in the step (3) into a hydrofluoric acid solution containing 0.6 wt%, and carrying out anodic oxidation for 3.5h at room temperature under 25V direct current voltage by taking the titanium sheet as an anode and a platinum sheet as a cathode, wherein the distance between the two electrodes is controlled to be 4 cm;
(5) ultrasonically cleaning the titanium sheet oxidized in the step (4) in ultrapure water, drying the titanium sheet by blowing with nitrogen, finally placing the titanium sheet into a muffle furnace, and calcining the titanium sheet for 80min at 600 ℃ in air atmosphere to prepare integrally arranged TiO2NTs electrodes;
(6) mixing the TiO in the step (5)2Washing NTs electrode with PBS buffer solution, soaking in 2% PDDA solution with zeta potential of 6.27mV, standing for 6min, taking out, and washing with water; placing into CdS NCs solution with zeta potential of-16.6 mV for 6min, taking out, and washing with water;
(7) repeating the step (6) for 2-4 times to obtain CdS NCs/TiO2NTs electrodes;
S13：CdS NCs/TiO2activation of NTs electrodes: CdS NCs/TiO prepared from S22NTs electrode soaked in 1.5ml of hydrogen peroxide solution2O2And citric acid into an activating solution, slightly shaking for 18H at 39 ℃, and washing with ultrapure water after activation to obtain the semiconductor nano material electrode, wherein H in each liter of the activating solution2O2The molar ratio to citric acid was 5: 50.
Example 3
The invention provides a preparation method of a semiconductor nano material electrode, which comprises the following steps:
s11: preparation of TGA-stabilized CdS NCs: 0.01M CdCl2Adding the solution and TGA into a container to obtain 50ml mixed solution, stirring under nitrogen atmosphere for 30min while adjusting pH to 10 with 1M NaOH solution, and adding 0.1M Na2Heating and refluxing the S solution at 110 ℃ for 4h under the nitrogen atmosphere, wherein CdCl2The molar ratio of the CdCl to the TGA is 1:72With Na2The molar ratio of S is 1: 1.1;
S12：CdS NCs/TiO2preparation of NTs electrode:
(1) ultrasonically cleaning the cut titanium sheet in ethanol and ultrapure water in sequence to remove impurities adsorbed on the surface;
(2) ultrasonically cleaning the titanium sheet in the step (1) in a mixed solution of hydrofluoric acid, nitric acid and water for 2min, and removing an oxide layer on the surface, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water is 1:4: 5;
(3) sequentially carrying out ultrasonic treatment on the titanium sheet pickled in the step (2) in ethanol and water for 5min respectively, and drying the titanium sheet by nitrogen for later use;
(4) immersing the clean titanium sheet obtained in the step (3) into a hydrofluoric acid solution containing 0.5 wt%, controlling the distance between two electrodes to be 3cm under 20V direct current voltage by taking the titanium sheet as an anode and a platinum sheet as a cathode, and anodizing for 2.5h at room temperature;
(5) ultrasonically cleaning the titanium sheet oxidized in the step (4) in ultrapure water, drying the titanium sheet by blowing with nitrogen, finally placing the titanium sheet into a muffle furnace, and calcining the titanium sheet for 60min at 500 ℃ in air atmosphere to prepare integrally arranged TiO2NTs electrodes;
(6) mixing the TiO in the step (5)2Washing NTs electrode with PBS buffer solution, soaking in 2% PDDA solution with zeta potential of 6.27mV, standing for 5min, taking out, and washing with water; placing into CdS NCs solution with zeta potential of-16.6 mV for 5min, taking out, and washing with water;
(7) repeating the step (6) for 3 times to obtain CdS NCs/TiO2NTs electrodes;
S13：CdS NCs/TiO2activation of NTs electrodes: CdS NCs/TiO prepared from S22NTs electrode soaked in 1.5ml of hydrogen peroxide solution2O2And citric acid into an activating solution, slightly shaking for 16H at 37 ℃, and washing with ultrapure water after activation to obtain the semiconductor nano material electrode, wherein each liter of the activating solution contains H2O2The molar ratio to citric acid was 5: 40.
Example 4
For the semiconductor nano material electrode of the invention, H in cells2O2Application in detection, the electrode obtained in example 3 is adopted for preparing the semiconductor nano material electrode, and H in cells to be detected2O2The extraction method comprises the following steps:
s21: HL-60 tumor cells were cultured in DMEM medium containing 8% fetal bovine serum in humidified air at 37 deg.C, wherein the humidified air comprises 93% air and 7% carbon dioxide (volume percent). (ii) a
S22: centrifuging HL-60 tumor cells in exponential growth phase with sterile PBS solution, washing for 2 times, discarding upper layer liquid, adding PBS solution, adding PMA stimulating cells, centrifuging for 15s to obtain product containing H2O2The centrifugation condition is that the supernatant fluid is centrifuged for 3min at the rotating speed of 6000 r/min.
Example 5
For the semiconductor nano material electrode of the invention, H in cells2O2Application in detection, the electrode obtained in example 3 is adopted for preparing the semiconductor nano material electrode, and H in cells to be detected2O2The extraction method comprises the following steps:
s21: HL-60 tumor cells were cultured in DMEM medium containing 12% fetal bovine serum in humidified air at 37 ℃, wherein the humidified air comprises 97% air and 3% carbon dioxide (volume percentage). (ii) a
S22: centrifuging HL-60 tumor cells in exponential growth phase with sterile PBS solution, washing for 2 times, discarding upper layer liquid, adding PBS solution, adding PMA to stimulate cells, centrifuging for 20s to obtain product containing H2O2The centrifugation condition of the supernatant fluid is that the supernatant fluid is centrifuged for 7min at the rotating speed of 10000 r/min.
Example 6
For the semiconductor nano material electrode of the invention, H in cells2O2Application in detection, the electrode obtained in example 3 is adopted for preparing the semiconductor nano material electrode, and H in cells to be detected2O2The extraction method comprises the following steps:
s21: HL-60 tumor cells were cultured in DMEM medium containing 10% fetal bovine serum in humidified air at 37 deg.C, wherein the humidified air comprises 95% air and 5% carbon dioxide (volume percent). (ii) a
S22: centrifuging HL-60 tumor cells in exponential growth phase with sterile PBS solution, washing for 2 times, discarding upper layer liquid, adding PBS solution, adding PMA stimulating cells, centrifuging for 17s to obtain product containing H2O2The centrifugation condition of the supernatant is 8000r/minCentrifuge at speed for 5 min.
For the PMA-stimulated cells of examples 4-6, the amount was every 1.6X1051ng of PMA was used per tumor cell.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The preparation method of the semiconductor nano material electrode is characterized by comprising the following steps:
s11: preparation of TGA-stabilized CdS NCs: adding CdCl2Adding the solution and TGA into a container, stirring under nitrogen atmosphere for 20-40min while adjusting pH of the mixture to 7-13 with NaOH solution, and adding Na2Heating and refluxing the S solution for 3-5h at the temperature of 105-115 ℃ under the nitrogen atmosphere;
S12：CdS NCs/TiO2preparation of NTs electrode:
(1) ultrasonically cleaning the cut titanium sheet in ethanol and ultrapure water in sequence to remove impurities adsorbed on the surface;
(2) ultrasonically cleaning the titanium sheet in the step (1) in a mixed solution of hydrofluoric acid, nitric acid and water for 1-3min, and removing an oxide layer on the surface;
(3) sequentially carrying out ultrasonic treatment on the titanium sheet pickled in the step (2) in ethanol and water for 4-6min respectively, and drying the titanium sheet by nitrogen for later use;
(4) immersing the clean titanium sheet obtained in the step (3) into a hydrofluoric acid solution containing 0.4-0.6% of weight, controlling the distance between the titanium sheet and the platinum sheet as an anode and the anode to be 2-4cm under the direct current voltage of 15-25V, and oxidizing the anode for 1.5-3.5h at room temperature;
(5) ultrasonically cleaning the titanium sheet oxidized in the step (4) in ultrapure water, drying the titanium sheet by blowing with nitrogen, finally calcining the titanium sheet in a muffle furnace at the temperature of 400-600 ℃ in air atmosphere for 40-80min to prepare integrally arranged TiO2NTs electrodes;
(6) mixing the TiO in the step (5)2P for NTs electrodeWashing with BS buffer solution, soaking in 2% PDDA solution with zeta potential of 6.27mV, standing for 4-6min, taking out, and washing with water; placing into CdS NCs solution with zeta potential of-16.6 mV for 4-6min, taking out, and washing with water;
(7) repeating the step (6) for 2-4 times to obtain CdS NCs/TiO2NTs electrodes;
S13：CdS NCs/TiO2activation of NTs electrodes: CdS NCs/TiO prepared from S122And soaking the NTs electrode in an activating solution, slightly shaking for 14-18h at 35-39 ℃, and washing with ultrapure water after activation to obtain the semiconductor nano material electrode.
2. The preparation of the semiconductor nanomaterial electrode of claim 1, wherein the CdCl in S11 is2The molar ratio of the CdCl to TGA is 1:6-82With Na2The molar ratio of S is 1: 1-1.2.
3. The method for preparing the semiconductor nano-material electrode as claimed in claim 1, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water in the S12 is 1 (3-5) to (4-6).
4. The method for preparing the semiconductor nano-material electrode according to claim 1, wherein the activating solution in S13 comprises H2O2Citric acid and deionized water, and H in each liter of activating solution2O2The molar ratio of the citric acid to the citric acid is 5: 30-50.
5. Use of the semiconductor nanomaterial electrode of claim 1 in a light-emitting system comprising the activated electrode of S13 and a co-reactant H2O2。
6. A semiconductor nanomaterial electrode of claim 1 in H2O2Application in detection.
7. A semiconductor nano-meter as claimed in claim 1Material electrode in cells H2O2Application in detection.
8. The semiconductor nanomaterial electrode of claim 7 in a cell H2O2Use in an assay wherein H is present in said cell2O2The extraction method comprises the following steps:
s21: culturing HL-60 tumor cells in a DMEM culture medium containing 8% -12% fetal calf serum in humidified air at 35-40 ℃;
s22: centrifuging HL-60 tumor cells in exponential growth phase with sterile PBS solution, washing for 1-3 times, discarding upper layer liquid, adding PBS solution, adding PMA stimulating cells, centrifuging for 15-20s to obtain product containing H2O2The supernatant of (2).
9. The semiconductor nanomaterial electrode of claim 8 in a cell H2O2The application in detection is characterized in that the humidified air in the S21 comprises 93-97% of air and 3-7% of carbon dioxide.
10. The semiconductor nanomaterial electrode of claim 8 in a cell H2O2The application of the method in detection is characterized in that the centrifugation condition in S22 is centrifugation for 3-7min at the rotating speed of 6000-10000 r/min.
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