CN115078499A - Preparation method of photoelectrochemical sensor for detecting microcystin LR - Google Patents
Preparation method of photoelectrochemical sensor for detecting microcystin LR Download PDFInfo
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- 108010073357 cyanoginosin LR Proteins 0.000 title claims abstract description 32
- ZYZCGGRZINLQBL-GWRQVWKTSA-N microcystin-LR Chemical compound C([C@H](OC)[C@@H](C)\C=C(/C)\C=C\[C@H]1[C@@H](C(=O)N[C@H](CCC(=O)N(C)C(=C)C(=O)N[C@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@H]([C@H](C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N1)C(O)=O)C(O)=O)C)C1=CC=CC=C1 ZYZCGGRZINLQBL-GWRQVWKTSA-N 0.000 title claims abstract description 32
- DIDLWIPCWUSYPF-UHFFFAOYSA-N microcystin-LR Natural products COC(Cc1ccccc1)C(C)C=C(/C)C=CC2NC(=O)C(NC(CCCNC(=N)N)C(=O)O)NC(=O)C(C)C(NC(=O)C(NC(CC(C)C)C(=O)O)NC(=O)C(C)NC(=O)C(=C)N(C)C(=O)CCC(NC(=O)C2C)C(=O)O)C(=O)O DIDLWIPCWUSYPF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010931 gold Substances 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 108091023037 Aptamer Proteins 0.000 claims abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000002135 nanosheet Substances 0.000 claims description 19
- 239000002356 single layer Substances 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012488 sample solution Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 4
- 238000003892 spreading Methods 0.000 claims description 4
- 239000012086 standard solution Substances 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000010884 ion-beam technique Methods 0.000 abstract 1
- 230000004298 light response Effects 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 239000004408 titanium dioxide Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 3
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- 239000002096 quantum dot Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 230000003448 neutrophilic effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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Abstract
The invention relates to a preparation method of a photoelectrochemical sensor for detecting microcystin LR, and the photoelectrochemical sensor is applied to the detection of the microcystin LR in lake water. The invention adopts Ti 3 C 2 T x Supported TiO 2 Nanoarrays as photosensitive substrate material, TiO 2 Stable performance and low cost, and Ti 3 C 2 T x Has the property similar to metal, excellent conductivity and stronger surface plasma resonance, and can effectively improve TiO 2 The electron-hole recombination and the visible light response of the material are improved. The material compounding scheme adopted by the invention reserves TiO 2 The microstructure of the nano array can be used as a good sensing carrier to ensure the stability of signal output, and gold nano is introduced by ion beam sputteringIons provide more active sites for the immobilization of aptamers, and microcystin LR is used as a natural electron donor to realize the sensing conversion from self concentration to a visual photocurrent signal.
Description
Technical Field
The invention relates to a preparation method of a photoelectrochemical sensor for detecting microcystin LR, in particular to a method for preparing a photoelectrochemical sensor for detecting microcystin LR by TiO 2 /Ti 3 C 2 T x The method is used as a substrate material for preparing a non-marking photoelectrochemical sensor for detecting microcystin LR, and belongs to the technical field of novel functional materials and biosensing detection.
Background
Titanium dioxide (TiO) 2 ) The advantages of non-toxicity, low cost and stability of the material are widely concerned in photocatalysis and photoelectrochemical sensing, but the defect is obvious, the wide energy band forces the material to have obvious response only to short-wavelength ultraviolet light with higher energy, the absorption result to visible light is not satisfactory, and the electron-hole recombination rate is high, so that the application of the material in different fields is limited. For TiO 2 The modification of the quantum dot/dye-sensitized solar cell is widely applied to means such as quantum dot/dye sensitization, precious metal loading, ion doping, heterojunction construction and the like at present.
MXene based on two-dimensional transition metal carbide/nitride is a novel two-dimensional functional material, has an electronic structure which can be continuously adjusted from metallicity to semiconductors and abundant surface chemical properties, shows wide application prospects in various fields of energy storage, catalysis, environment, biology, electronics, electromagnetic shielding, superconduction, sensing, separation technology, superconduction and the like, and provides wide space for the regulation and control of physicochemical properties and service functions by virtue of multiple chemical compositions and crystal structures. Ti 3 C 2 T x Compared with noble metal nanoparticles, the MXene material has metalloid intrinsic carrier concentration which is 4-5 orders of magnitude lower than that of metal and a larger two-dimensional light absorption cross section, has a remarkable surface plasmon resonance effect in a visible light region, and has great potential in visible light energy accumulation to improve visible light absorption of a wide-energy-band semiconductor.
In the invention, TiO is added 2 With Ti 3 C 2 T x Compounding with Ti 3 C 2 T x Ultra-high conductivity of (2) to realize TiO 2 Fast transfer of neutrophilic electrons and benefiting from Ti 3 C 2 T x The surface plasma resonance effect of the titanium dioxide and the titanium dioxide realizes the collection of visible light energy in the two, thereby improving the TiO 2 In the visible light utilization rate of (1), and in the presence of TiO 2 /Ti 3 C 2 T x The photoelectric generator shows satisfactory results when applied to the detection of microcystin LR in lake water.
Disclosure of Invention
One of the objects of the invention is to use TiO 2 /Ti 3 C 2 T x As a substrate material to produce a photoelectric response. Ti 3 C 2 T x As a metal-like quick bleaching agent, can effectively improve TiO through surface plasma resonance 2 Provides the photocurrent basis for subsequent testing.
Another objective of the invention is to control TiO 2 /Ti 3 C 2 T x The microscopic morphology of the nano array, the final product preserves TiO 2 The micro-morphology of the nano-rods promotes electrons to be transferred along the nano-rods with sufficient density orientation, and the stability of the sensor among batches is ensured.
The third purpose of the invention is that the proposed photoelectrochemical sensor is of a signal rise type, namely, the photocurrent increases with the rise of the concentration of a target substance, because the microcystin LR is an electron donor, and the power supply scheme replaces the scheme of the traditional unmarked photoelectric sensor which realizes signal change by means of steric hindrance of the surface of an electrode, so that the photoelectrochemical sensor has higher sensitivity.
The technical scheme of the invention is as follows:
1. a preparation method of a photoelectrochemical sensor for detecting microcystin LR comprises the following steps:
（1）TiO 2 preparing a nano array: flatly paving the FTO glass with the conductive surface facing upwards at the bottom of a hydrothermal reaction kettle, pouring a mixed solution containing 8-45 mL of deionized water, 8-45 mL of concentrated hydrochloric acid and 0.2-1.2 mL of tetrabutyl titanate, and putting the mixed solution at 120-160 mL o Keeping the temperature for 8-12 h under C to obtain TiO 2 Washing the nano array with deionized water for many times and drying;
(2) single layer of Ti 3 C 2 T x Preparing a nano sheet: taking 0.1-0.5 g of accordion-shaped Ti 3 C 2 T x Dispersing in 15-25 mL of dimethyl sulfoxide, fully stirring at room temperature for 18-36 h to crack the accordion structure to obtain single-layer Ti 3 C 2 T x Performing nanosheet, centrifuging the mixture at 4000-6000 rpm for 20-40 min, and washing the precipitate for multiple times by using deionized water to remove all dimethyl sulfoxide to finally obtain a single layerTi 3 C 2 T x A nanosheet;
（3）TiO 2 /Ti 3 C 2 T x preparing a nano array: a single layer of Ti 3 C 2 T x Re-dispersing the nanosheets in a three-neck flask filled with 20-100 mL of deionized water, bubbling with argon to exhaust air, then carrying out ultrasonic treatment in an ice-water bath for 4-18 h, standing the obtained product for 8-12 h, and taking the upper-layer colloid; 50-200 mu L of upper layer colloid is dripped on TiO in a plastic culture dish for exhausting air by using argon 2 Naturally volatilizing the nano-array for 12-24 h at room temperature under the argon atmosphere for 200-300 h o Calcining C for 2-3 h to obtain TiO 2 /Ti 3 C 2 T x Nano-array, storing the final product at low temperature in argon environment;
(4) preparing a photoelectrochemical sensor: using ion beam sputtering apparatus on TiO 2 /Ti 3 C 2 T x Sputtering a layer of gold nanoparticles on the surface of the nano array, adjusting the current of a sputtering instrument to be 10-30 mu A, and adjusting the sputtering time to be 30-80 s to obtain TiO 2 /Ti 3 C 2 T x Au; dropwise adding 6 muL and 20-100 mumol/L aptamer solution with sulfydryl modified at the 3' end to TiO 2 /Ti 3 C 2 T x Drying the Au surface naturally at room temperature; dropwise adding 3 muL of 6-mercaptohexane-1-alcohol solution with the mass fraction of 1% on the surface of the modified electrode; and continuously dropwise adding 6 muL of standard microcystin LR with different concentrations to complete the construction of the sensor.
2. A photoelectrochemical sensor for detecting microcystin LR comprises the following detection steps:
(1) testing by using an electrochemical workstation and a three-electrode system, wherein an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and the prepared sensor is used as a working electrode and is tested in 10 mL of carbonic acid buffer solution with the pH value of 9.8-14;
(2) detecting microcystin LR by time-current method for 120 s at light source wavelength of 450 nm;
(3) after the electrodes are placed, turning on the lamp every 12s for continuously irradiating for 12s, recording the photocurrent, and drawing a working curve;
(4) and (3) replacing the standard microcystin LR standard solution with the lake water sample solution to be detected for detection.
Detailed description of the preferred embodiments
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention, and not to limit the scope of the claims.
Example 1
（1）TiO 2 Preparing a nano array: spreading FTO glass with conductive surface facing upwards at the bottom of hydrothermal reaction kettle, pouring mixed solution containing 8 mL of deionized water, 8 mL of concentrated hydrochloric acid and 0.2 mL of tetrabutyl titanate, and stirring at 120 DEG o Keeping the temperature for 8 hours under C to obtain TiO 2 Washing the nano array with deionized water for many times and drying;
(2) single layer of Ti 3 C 2 T x Preparing a nano sheet: take 0.1 g of accordion-shaped Ti 3 C 2 T x Dispersing in 15 mL of dimethyl sulfoxide, fully stirring for 18 h at room temperature to crack the accordion structure to obtain a single-layer Ti 3 C 2 T x Nano-plate, centrifuging the mixture at 4000 rpm for 20 min, washing the precipitate with deionized water for multiple times to remove all dimethyl sulfoxide, and finally obtaining single-layer Ti 3 C 2 T x Nanosheets;
（3）TiO 2 /Ti 3 C 2 T x preparing a nano array: a single layer of Ti 3 C 2 T x Dispersing the nanosheets again in a three-neck flask filled with 20 mL of deionized water, bubbling argon to exhaust air, performing ultrasonic treatment in an ice-water bath for 4 hours, standing the obtained product for 8 hours, and taking upper-layer colloid; 50 μ L of the supernatant gel was applied dropwise to TiO in a plastic petri dish purged of air with argon 2 Naturally volatilizing the nano-array for 12 h at room temperature under the argon atmosphere for 200 h o Calcining the mixture for 2 hours to obtain TiO 2 /Ti 3 C 2 T x Nano-array, and storing the final product at low temperature in an argon environment;
(4) preparing a photoelectrochemical sensor: use the ionBeam sputtering on TiO 2 /Ti 3 C 2 T x Sputtering a layer of gold nanoparticles on the surface of the nano array, adjusting the current of a sputtering instrument to 10 mu A, and sputtering for 30 s to obtain TiO 2 /Ti 3 C 2 T x Au; dropwise adding 6 muL and 20 mumol/L aptamer solution with sulfydryl modified at 3' end to TiO 2 /Ti 3 C 2 T x Drying the Au surface naturally at room temperature; dropwise adding 3 muL of 6-mercaptohexane-1-alcohol solution with the mass fraction of 1% on the surface of the modified electrode; continuously dripping 6 muL and 10 ng/mL of standard microcystin LR to obtain the photoelectrochemical sensor.
Example 2
（1）TiO 2 Preparing a nano array: spreading FTO glass with conductive surface facing upwards at the bottom of hydrothermal reaction kettle, pouring mixed solution containing 20 mL of deionized water, 20 mL of concentrated hydrochloric acid and 0.5 mL of tetrabutyl titanate, and heating at 150 deg.C o Keeping the temperature for 10 hours under C to obtain TiO 2 Washing the nano array with deionized water for many times and drying;
(2) single layer of Ti 3 C 2 T x Preparing a nano sheet: 0.3 g of accordion-shaped Ti is taken 3 C 2 T x Dispersing in 20 mL of dimethyl sulfoxide, and fully stirring at room temperature for 25 h to crack the accordion structure to obtain a single-layer Ti 3 C 2 T x Nanosheet, centrifuging the mixture at 5000 rpm for 30 min, washing the precipitate with deionized water for multiple times to remove all dimethyl sulfoxide, and finally obtaining single-layer Ti 3 C 2 T x Nanosheets;
（3）TiO 2 /Ti 3 C 2 T x preparing a nano array: a single layer of Ti 3 C 2 T x Re-dispersing the nano sheets in a three-neck flask filled with 80 mL of deionized water, bubbling argon to exhaust air, performing ultrasonic treatment in an ice-water bath for 15 hours, standing the obtained product for 10 hours, and taking upper-layer colloid; 100 μ L of the supernatant gel was applied drop-wise to TiO in a plastic petri dish purged of air with argon 2 Naturally volatilizing the nano-array for 18 h at room temperature under the argon atmosphere for 250 h o Calcining for 3 h to obtain TiO 2 /Ti 3 C 2 T x Nano-array, storing the final product at low temperature in argon environment;
(4) preparation of photoelectrochemical sensor by ion beam sputtering on TiO 2 /Ti 3 C 2 T x Sputtering a layer of gold nanoparticles on the surface of the nano array, adjusting the current of a sputtering instrument to be 20 mu A, and sputtering for 60 s to obtain TiO 2 /Ti 3 C 2 T x Au; dropwise adding 6 mu L and 80 mu mol/L aptamer solution with sulfydryl modified at 3' end to TiO 2 /Ti 3 C 2 T x Drying the Au surface naturally at room temperature; dropwise adding 3 muL of 6-mercaptohexane-1-alcohol solution with the mass fraction of 1% on the surface of the modified electrode; continuously dripping 6 muL and 100 ng/mL of standard microcystin LR to obtain the photoelectrochemical sensor.
Example 3
（1）TiO 2 Preparing a nano array: spreading FTO glass with conductive surface facing upwards at the bottom of hydrothermal reaction kettle, pouring mixed solution containing 45 mL of deionized water, 45 mL of concentrated hydrochloric acid and 1.2 mL of tetrabutyl titanate, and stirring at 160 DEG for o Keeping the temperature for 12 hours under C to obtain TiO 2 Washing the nano array with deionized water for many times and drying;
(2) single layer of Ti 3 C 2 T x Preparing a nano sheet: 0.5 g of accordion-shaped Ti is taken 3 C 2 T x Dispersing in 25 mL of dimethyl sulfoxide, and fully stirring at room temperature for 36 h to crack the accordion structure to obtain a single-layer Ti 3 C 2 T x Nanosheet, centrifuging the mixture at 6000 rpm for 40 min, washing the precipitate with deionized water for multiple times to remove all dimethyl sulfoxide, and finally obtaining single-layer Ti 3 C 2 T x Nanosheets;
（3）TiO 2 /Ti 3 C 2 T x preparing a nano array: a single layer of Ti 3 C 2 T x Re-dispersing the nano sheets in a three-neck flask filled with 100 mL of deionized water, bubbling argon to exhaust air, performing ultrasonic treatment in an ice-water bath for 18 hours, standing the obtained product for 12 hours, and taking upper-layer colloid; 200 μ L of the supernatant gel was applied drop-wise to TiO in a plastic petri dish purged of air with argon 2 On the nano arrayNaturally volatilizing for 24 h at room temperature under argon atmosphere for 300 h o Calcining for 3 h to obtain TiO 2 /Ti 3 C 2 T x Nano-array, and storing the final product at low temperature in an argon environment;
(4) preparing a photoelectrochemical sensor: using ion beam sputtering apparatus on TiO 2 /Ti 3 C 2 T x Sputtering a layer of gold nanoparticles on the surface of the nano array, adjusting the current of a sputtering instrument to be 30 mu A, and sputtering for 80 s to obtain TiO 2 /Ti 3 C 2 T x Au; dropwise adding 6 mu L and 100 mu mol/L aptamer solution with sulfydryl modified at 3' end to TiO 2 /Ti 3 C 2 T x Drying the Au surface naturally at room temperature; dropwise adding 3 muL of 6-mercaptohexane-1-alcohol solution with the mass fraction of 1% on the surface of the modified electrode; and continuously dropwise adding the standard microcystin LR with the concentration of 6 muL and 500 ng/mL to obtain the photoelectric chemical sensor.
Example 4
The prepared photoelectrochemical sensor is used for detecting microcystin LR, an electrochemical workstation is used for testing by a three-electrode system, an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, the prepared sensor is used as a working electrode, and the testing is carried out in 10 mL of aqueous solution with the pH value of 10; detecting microcystin LR by time-current method for 120 s at light source wavelength of 450 nm; after the electrodes are placed, turning on the lamp every 12s for continuously irradiating for 12s, recording the photocurrent, and drawing a working curve; and (3) replacing the microcystin LR standard solution with the lake water sample solution to be detected for detection.
Example 5
The prepared photoelectrochemical sensor is used for detecting microcystin LR, an electrochemical workstation is used for testing by a three-electrode system, an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, the prepared sensor is used as a working electrode, and the testing is carried out in 10 mL of aqueous solution with the pH value of 12; detecting microcystin LR by time-current method for 120 s at light source wavelength of 450 nm; after the electrodes are placed, turning on the lamp every 12s for continuously irradiating for 12s, recording the photocurrent, and drawing a working curve; and (3) replacing the microcystin LR standard solution with the lake water sample solution to be detected for detection.
The photoelectric chemical sensor for detecting microcystin LR prepared by the invention is successfully used for detecting microcystin LR samples in water, and the recovery rate is 92.3-105.4%.
Claims (2)
1. A preparation method of a photoelectrochemical sensor for detecting microcystin LR is characterized by comprising the following steps: (1) TiO 2 2 Preparing a nano array: spreading the FTO glass with the conductive surface facing upwards at the bottom of a hydrothermal reaction kettle, pouring a mixed solution containing 8-45 mL of deionized water, 8-45 mL of concentrated hydrochloric acid and 0.2-1.2 mL of tetrabutyl titanate into the kettle, and adding the mixed solution into the kettle at a temperature of 120-160 mL o Keeping the temperature for 8-12 h under C, washing with deionized water for multiple times and drying to obtain TiO 2 A nano-array;
single layer of Ti 3 C 2 T x Preparing a nano sheet: taking 0.1-0.5 g of accordion-shaped Ti 3 C 2 T x Dispersing in 15-25 mL of dimethyl sulfoxide, fully stirring at room temperature for 18-36 h to crack the accordion structure to obtain single-layer Ti 3 C 2 T x Nanosheet, centrifuging the mixture at 4000-6000 rpm for 20-40 min, and washing the precipitate for multiple times by using deionized water to remove all dimethyl sulfoxide to obtain single-layer Ti 3 C 2 T x Nanosheets;
TiO 2 /Ti 3 C 2 T x preparing a nano array: the single layer of Ti in the step (2) 3 C 2 T x Re-dispersing the nanosheets in a three-neck flask filled with 20-100 mL of deionized water, bubbling with argon to exhaust air, then carrying out ultrasonic treatment in an ice-water bath for 4-18 h, standing the obtained product for 8-12 h, and taking the upper-layer colloid; 50-200 mu L of upper layer colloid is dripped on TiO in a plastic culture dish for exhausting air by using argon 2 Naturally volatilizing the nano-array for 12-24 h at room temperature under the argon atmosphere for 200-300 h o Calcining C for 2-3 h to obtain TiO 2 /Ti 3 C 2 T x Nano-array, and storing the final product at low temperature in an argon environment;
(4) manufacture of photoelectrochemical sensorsPreparing: using ion beam sputtering apparatus on TiO 2 /Ti 3 C 2 T x Sputtering a layer of gold nanoparticles on the surface of the nano array, adjusting the current of a sputtering instrument to be 10-30 mu A, and adjusting the sputtering time to be 30-80 s to obtain TiO 2 /Ti 3 C 2 T x Au; dropwise adding 6 muL and 20-100 mumol/L aptamer solution with sulfydryl modified at the 3' end to TiO 2 /Ti 3 C 2 T x Drying the Au surface naturally at room temperature; dropwise adding 3 muL of 6-mercaptohexane-1-alcohol solution with the mass fraction of 1% on the surface of the modified electrode; and continuously dropwise adding 6 mu L of standard microcystin LR with different concentrations to complete the construction of the sensor.
2. The sensor prepared by the preparation method of the photoelectrochemical sensor for detecting microcystin LR according to claim 1, wherein the steps for detecting microcystin LR are as follows:
(1) testing by using an electrochemical workstation and a three-electrode system, wherein an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, the prepared sensor is used as a working electrode, and the testing is carried out in 10 mL of carbonic acid buffer solution with the pH value of 9.8-14; (2) detecting microcystin LR by time-current method for 120 s at light source wavelength of 450 nm;
(3) after the electrodes are placed, turning on the lamp every 12s for continuously irradiating for 12s, recording the photocurrent, and drawing a working curve;
(4) and (3) replacing the standard microcystin LR standard solution with the lake water sample solution to be detected for detection.
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