CN112903767B - WO (WO) 3 Molecular imprinting photoelectrochemical sensor and preparation method and application thereof - Google Patents
WO (WO) 3 Molecular imprinting photoelectrochemical sensor and preparation method and application thereof Download PDFInfo
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- CN112903767B CN112903767B CN202110098446.2A CN202110098446A CN112903767B CN 112903767 B CN112903767 B CN 112903767B CN 202110098446 A CN202110098446 A CN 202110098446A CN 112903767 B CN112903767 B CN 112903767B
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- 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
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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
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Abstract
The invention discloses a PCB52 (2, 2', 5' -tetrachlorobiphenyl) molecular imprinting photoelectrochemical sensor, a preparation method and application thereof, wherein the sensor comprises a substrate with WO on the surface 3 Tungsten platelet matrix of layers and UV-visible driven WO deposited on the surface of said matrix by hydrothermal synthesis technique 3 A layer of material, said WO 3 The material layer has PCB52 molecularly imprinted sites. The sensor has the advantages of high sensitivity, good selectivity, wide detection range, detection limit up to 0.001pM to PCB52 molecules, simple preparation method and low cost.
Description
Technical Field
The invention relates to the technical field of sensing, in particular to a WO 3 A molecular imprinting photoelectrochemical sensor and a preparation method and application thereof.
Background
Polychlorinated biphenyls are carcinogens which accumulate in adipose tissue easily, cause diseases of brain, skin and viscera, affect the nervous, reproductive and immune systems, and have the ability to resist degradation, long-distance transportation and deposition, so the invention of an effective method for detecting polychlorinated biphenyls in water has great significance to human beings. Currently, there are many methods for detecting polychlorinated biphenyls (e.g., PCB52 (i.e., 2', 5' -tetrachlorobiphenyl)), such as gas chromatography, gas chromatography/mass spectrometry, etc., which are reliable in sensitivity but costly and require specialized technicians to detect.
The molecular imprinting photoelectrochemical sensor combines the photoelectrochemical sensor with the molecular imprinting technology, so that the molecular imprinting photoelectrochemical sensor has the advantages of low cost, high sensitivity, simplicity in operation, wide detection range and high detection speed of the traditional photoelectrochemical sensor, and the added molecular imprinting technology improves the selectivity of the photoelectrochemical sensor to an object to be detected. In recent years, researchers have synthesized a number of semiconductor materials to achieve the aim of obtaining photocurrent signals by exciting electrons with uv-vis light, thus uv-vis light driven lightElectrochemical detection means have been rapidly developed. For example, such materials are Cu 2 O、TiO 2 、g-C 3 N 4 、Fe 2 O 3 、ZnS 2 Etc.
Disclosure of Invention
An aspect of the present invention is directed to a PCB52 (2, 2', 5' -tetrachlorobiphenyl) molecularly imprinted photoelectrochemical sensor comprising a substrate having WO on its surface 3 Tungsten plate substrate of layer and ultraviolet-visible light driving WO deposited on surface of substrate by hydro-thermal synthesis technology 3 A layer of material, said WO 3 The material layer has PCB52 molecularly imprinted sites. The sensor has the characteristics of high sensitivity, good selectivity and wide detection range to PCB52 molecules, and the minimum detection limit reaches 0.001 pM.
In another aspect, the present invention provides a method for preparing the PCB52 molecularly imprinted photoelectrochemical sensor, which comprises the following steps:
(1) Calcining the tungsten sheet at 300-600 ℃ for 20-50 minutes to form WO on the surface of the tungsten sheet 3 A layer, a surface having WO 3 A tungsten plate matrix of the layer;
(2) Na is mixed with 2 WO 4 Mixing the aqueous solution with polyethylene glycol, adding ethanol solution containing PCB52 molecules, and regulating the pH of the mixed solution to 2.0 by using inorganic acid;
(3) Forming WO on the surface prepared in the step (1) 3 The tungsten chip substrate of the layer is put into the mixed solution in the step (2) to react for 4 to 8 hours at the temperature of 150 to 210 ℃ so that the surface of the substrate forms the PCB52/WO 3 A composite material layer;
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 Calcining the matrix of the composite material layer at 450-700 ℃ for 2-4 hours to form WO (WO) with PCB52 molecular imprinting sites on the surface of the matrix 3 And (5) the material layer is used for obtaining the PCB52 molecular imprinting photoelectrochemical sensor.
Preferably, in the step (1), the tungsten sheet is ultrasonically cleaned 2 to 5 times by acetone, ethanol and water in sequence before being calcined, and then dried for 20 to 40 minutes at a temperature of between 40 and 70 ℃.
Preferably, in the step (1), the calcination temperature of the tungsten sheet is 400-500 ℃ and the time is 20-40 minutes.
Preferably, the polyethylene glycol is selected from polyethylene glycol 200.
Preferably, in step (2) of the above preparation method, na 2 WO 4 The mass concentration of the substances in the aqueous solution is 0.01 to 0.03mol/L -1 。
Preferably, in step (2) of the above preparation method, na is by weight 2 WO 4 : PCB52 is 300000 ～ 900000:1, na 2 WO 4 : polyethylene glycol is 1:10 to 100.
Preferably, in step (2) of the above preparation method, the inorganic acid is selected from dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid, and dilute nitric acid. More preferably, the mineral acid is selected from dilute hydrochloric acid.
Preferably, in step (3) of the above preparation method, WO is formed on the surface 3 The reaction temperature of the tungsten sheet of the layer and the mixed solution is 170-190 ℃ and the time is 5-7 hours. More preferably, the reaction temperature is 180℃and the time is 6 hours.
Preferably, in step (4), the surface is formed with a PCB52/WO 3 The matrix of the composite material layer is repeatedly washed for 2 to 6 times by distilled water before calcination, and then is put into a constant temperature drying oven with the temperature of 40 to 80 ℃ for about 20 to 50 minutes.
Preferably, in the step (4) of the preparation method, the calcination of the tungsten sheet is performed at 550-600 ℃ for 2-4 hours.
In a further aspect, the present invention provides the use of the above-described PCB52 molecularly imprinted photoelectrochemical sensor for detecting PCB52 molecules in a medium.
Preferably, the medium is selected from an aqueous medium or soil.
In yet another aspect, the present invention provides a method for detecting PCB52 molecules in a medium using the above-described PCB52 molecularly imprinted photoelectrochemical sensor, the method comprising the steps of:
(1) Drawing a standard curve: by Na 2 SO 4 The aqueous solution is prepared into a standard solution of PCB52 with a series of concentrations, the PCB52 molecular imprinting photoelectrochemical sensor is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a counter electrodeThe reference electrode, regard ultraviolet-visible light source as the excitation light source, utilize i-t technology, add bias voltage of 0.6V on CHI660e electrochemical workstation, detect the standard solution of PCB52 sequentially according to the order from low to high of concentration, get different photocurrent density, establish the linear relation with concentration of PCB52 with the said photocurrent density finally, draw the standard curve;
(2) Adding a sample of the medium to be tested containing PCB52 to Na 2 SO 4 Obtaining a solution containing the PCB52 in the aqueous solution, testing the photocurrent density of the solution under the test condition of the step (1), and obtaining Na by using the standard curve 2 SO 4 The concentration of PCB52 in the solution is then determined as the concentration of PCB52 in the medium.
Preferably, in step (1) of the above method, when the medium sample contains precipitate, the precipitate is filtered with a sand core funnel for 2-5 times, and then added to Na 2 SO 4 In an aqueous solution.
Preferably, in step (1) and step (2) of the above method, na for configuring the PCB52 solution 2 SO 4 The concentration of the aqueous solution is 0.05 to 0.15 mol.L-1, more preferably 0.1 mol.L -1 。
Preferably, in step (1) of the above method, the uv-vis light source is selected from xenon lamp sources.
The PCB52 molecular imprinting photoelectrochemical sensor is a semiconductor material synthesized by a hydrothermal method, has stable structure, forms specific molecular recognition sites with good stability, has high detection sensitivity, good selectivity and wide detection range on the PCB52, can rapidly and conveniently detect PCB52 pollutants in a medium (such as sewage and soil), and has the lowest detection limit of 0.001pM (S/N=3) (0.29 pg.L) -1 )。
Therefore, compared with the conventional method, the PCB52 molecular imprinting photoelectrochemical sensor of the invention has the following advantages:
(1) The photoelectrochemistry detection range is wide and can be set at 0.005pM (1.45 pg.L) -1 )～4.0μM(1.16mg·L -1 ) The detection is carried out in the concentration range (namely, the detection has wider response range and lower detection limit), the sensitivity is high, the selectivity is good, the anti-interference capability is strong,the method is applicable to the rapid on-line detection of the water body, and provides a new method for the rapid on-line detection of the PCB 52.
(2) The synthesis method of the PCB52 molecular imprinting photoelectrochemical sensor is simple and rapid and has low cost.
Drawings
FIGS. 1A and 1B show the surface-formed PCB52/WO obtained in step (3) and step (4), respectively, of example 1 3 The matrix and surface of the composite layer are formed with WO with PCB52 molecular imprinting 3 Scanning electron microscope image of tungsten sheet matrix of material layer.
FIG. 2 shows the results of step (4) and step (3), respectively, of example 1, with a surface formed with a WO having a molecular imprinting of PCB52 3 The substrate and surface of the material layer are formed with a PCB52/WO 3 X-ray diffraction pattern (top to bottom order) of the matrix of the composite layer, and of the commercially available metallic tungsten sheet.
FIG. 3A shows the concentration of the PCB52 solutions (the concentrations of the PCB52 from a to m are 0,5.12 ×10 respectively) of the PCB52 molecular imprinting photoelectrochemical sensor prepared in example 1 -15 mol·L -1 ,5.12×10 -14 mol·L -1 ,5.12×10 - 13 mol·L -1 ,5.12×10 -12 mol·L -1 ,5.12×10 -11 mol·L -1 ,2.56×10 -10 mol·L -1 ,1.28×10 - 9 mol·L -1 ,6.40×10 -9 mol·L -1 ,3.20×10 -8 mol·L -1 ,1.60×10 -7 mol·L -1 ,8.00×10 -7 mol·L -1 ,4.00×10 -6 mol·L -1 ) Is a photo current response graph of (a). The graph shows that the photocurrent density gradually increases with increasing concentration of PCB 52.
FIG. 3B is a ΔI/I of example 1 0 And PCB52 concentration from 5.12×10 -15 mol·L -1 To 4.00×10 -6 mol·L -1 Is a logarithmic linear relationship (where Δi=i-I 0 Wherein I is the photocurrent density corresponding to the a to m concentration of PCB52 solution, I 0 Is 0.1 mol.L -1 Na 2 SO 4 Photocurrent density of the solution. The figure illustrates that at 5.12X10 -15 To 1.28×10 -9 mol·L -1 And 1.28X10 -9 To 4.00×10 -6 mol·L -1 The change in photocurrent density is linearly proportional to the logarithm of the concentration of the PCB 52. Wherein at 5.12X10 -15 Up to 1.28X10 -9 mol·L -1 The linear regression equation in the range is delta I/I 0 =0.8530+0.0286 lgc, correlation coefficient (R 2 ) 0.9778. At 1.28X10 -9 To 4.0X10 -6 mol·L -1 Within (2), the linear regression equation is DeltaI/I 0 =3.3126+0.3077 lgc, correlation coefficient (R 2 ) 0.9941. Further, the detection Limit (LOD) was about 0.001pM (S/n=3).
FIG. 4 shows the concentration of the PCB52 molecular imprinting photoelectrochemical sensor prepared in example 1 at a concentration of 4.00×10 -6 mol·L -1 Stability test results in PCB52 solution.
Fig. 5 is a graph of relative photocurrent densities of the PCB52 molecularly imprinted photoelectrochemical sensor prepared in example 1 in a PCB52 solution with different interferents [ PCB3, bisphenol a (BPA), diphenolic acid (d-PA), 4-chlorophenol (p-CP) ] added.
Detailed Description
In the description of the present invention, tungsten flakes are commercially available, for example, in a size of 0.2 x 100mm 3 When in use, the tungsten alloy can be sheared into small tungsten slices with the length of 3cm and the width of 1 cm.
In the description of the present invention, in the method for manufacturing the PCB52 molecularly imprinted photoelectrochemical sensor, the calcination of the tungsten sheet in the step (1) forms WO on the surface thereof 3 The layer may be carried out in a muffle furnace, and the calcination of the tungsten sheet in step (4) may also be carried out in a muffle furnace.
In the preparation method of the PCB52 molecular imprinting photoelectrochemical sensor, polyethylene glycol is added to dissolve the PCB52, ethanol is added to dissolve the PCB52 and the polarity of water is regulated so as to change WO 3 Is a crystallization process of (a).
Stability and repeatability determination method of PCB52 molecular imprinting photoelectrochemical sensor
Stability and repeatability are prerequisites for sensor materials to be applied in practical production. At the position ofIn the present invention, the inventors examined the stability and reproducibility of the PCB52 molecularly imprinted photoelectrochemical sensor by continuously recording photocurrent in the PCB52 solution. Specifically, in the utilization of Na 2 SO 4 In a PCB52 solution with a certain concentration, which is prepared by an aqueous solution, a PCB52 molecular imprinting photoelectrochemical sensor is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, an ultraviolet-visible light source is used as an excitation light source, an i-t technology is utilized on a CHI660e electrochemical workstation, a 0.6V bias voltage is applied, the light source is turned on for multiple times, and the photocurrent rising condition is observed. If the light source is turned on/off multiple times, the illumination period remains relatively stable for a period of time (e.g., 5000 s), indicating that the molecularly imprinted photoelectrochemical sensor has high stability and good repeatability.
Selective determination method of PCB52 molecular imprinting photoelectrochemical sensor
In the utilization of Na 2 SO 4 The aqueous solution is configured with a plurality of PCB52 solutions of the same concentration, wherein one of the PCB52 solutions is free of interferents and the other PCB52 solutions are respectively provided with different interferents. The PCB52 molecularly imprinted photoelectrochemical sensor is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, an ultraviolet-visible light source is used as an excitation light source, an i-t technology is utilized on a CHI660e electrochemical workstation, bias voltage of 0.6V is applied to obtain the photocurrent densities of the PCB52 solutions, and the influence of the interferents on the PCB52 detected by the PCB52 molecularly imprinted photoelectrochemical sensor can be obtained by comparing the photocurrent densities of the PCB52 solution added with the interferents with the photocurrent densities of the PCB52 solution without the interferents.
The PCB52 molecular imprinting photoelectrochemical sensor is based on the combination of a molecular imprinting technology and a photoelectrochemical sensing technology to detect the PCB 52. The PCB52 molecular imprinting photoelectrochemical sensor has WO on the surface 3 The tungsten sheet of the layer is used as a matrix, and a layer of WO with PCB52 molecular imprinting sites is deposited on the surface of the tungsten sheet by a hydrothermal synthesis technology 3 A material layer. Under the irradiation of ultraviolet-visible light, the PCB52 is detected by the I-t technology, and the concentration of the PCB52 can be accurately calculated by recording the photocurrent response valueDegree. Has higher photocurrent response and better selectivity to the PCB52 in the medium. The results of the study showed that the log of the concentration of PCB52 exhibited a better linear relationship with the change in photocurrent density in the range of 0.005 to 1.28nM and 1.28nM to 4.0 μm, with a minimum detection Limit (LOD) of about 0.001pM (S/n=3).
In addition, the selectivity test of the PCB52 molecular imprinting photoelectrochemical sensor shows that the sensor has good selectivity to PCB52 molecules. Stability and repeatability test experiments of the PCB52 molecular imprinting photoelectrochemical sensor show that the sensor provided by the invention has good stability and repeatability.
The invention will be further illustrated with reference to specific examples. The specific embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and operation processes are given. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedure, in which no specific conditions are noted in the examples below, is generally carried out according to conventional conditions. Unless otherwise indicated, proportions and percentages are by weight.
In the following examples, tungsten flakes were purchased from midkeno technologies, inc., and the X-ray diffractometer model used in X-ray diffraction analysis was D8 advance, brucker, germany.
Example 1
1.1 a preparation method of a PCB52 molecular imprinting photoelectrochemical sensor, which comprises the following steps:
(1) Cutting the purchased tungsten sheet into small tungsten sheets with the length of 3cm and the width of 1cm, respectively ultrasonically cleaning the tungsten sheets with acetone, ethanol and water for 3 times, and drying the tungsten sheets at 60 ℃ for 30mins; and (3) placing the dried tungsten sheet in a muffle furnace, and calcining for 30min at 450 ℃ to form a tungsten trioxide layer on the surface of the tungsten sheet.
(2) Preparing 0.02 mol.L -1 Na of (2) 2 WO 4 Taking 45mL of the solution into a small beaker with 100mL, adding 5mL of polyethylene glycol 200, and then adding 5mL of ethanol containing a certain amount of PCB52 molecules; the pH of the mixed solution was adjusted to 2.0 with 6M hydrochloric acid, wherein Na 2 WO 4 Mass of PCB52, polyethylene glycol 200The ratio is 360000:1:7700000.
(3) Placing the mixed solution obtained in the step (2) into a reaction kettle with a polytetrafluoroethylene lining of 100mL, and forming WO on the surface obtained in the step (1) 3 The tungsten plate substrate is vertically placed in the reaction mixed solution, the reaction kettle is placed in a baking oven, the reaction temperature is adjusted to be 180 ℃ for 6 hours, and the surface of the substrate is formed into the PCB52/WO 3 A composite material layer; after the reaction is finished, the surface is formed with PCB52/WO 3 The matrix of the composite layer was removed, repeatedly rinsed several times with distilled water, and then placed in a constant temperature oven at 60 ℃ for about 30mins.
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 And placing the matrix of the composite material layer in a muffle furnace, and calcining at 550 ℃ for 3 hours to obtain the matrix of the composite material with the surface provided with the PCB52 molecular imprinting, namely the PCB52 molecular imprinting photoelectrochemical sensor.
1.2 formation of PCB52/WO on the surface obtained in step (3) and step (4) of this example 3 The matrix and surface of the composite layer are formed with WO with PCB52 molecular imprinting 3 The matrix of the material layer was observed by scanning electron microscopy, and the results are shown in fig. 1A and 1B, respectively. Step (3) surface Forming WO 3 The tungsten plate of the PCB52 is of a nano columnar structure, the length of the nano column is 3-3.5 mu m, and the width and the thickness are respectively about 350nm and 200nm. WO (WO) with PCB52 molecular imprinting formed on surface of step (4) obtained after annealing treatment 3 The tungsten plate of the material layer is of an irregular plate-shaped structure, and comparing FIG. 1A and FIG. 1B can clearly see that the surface of the group forms the WO 52 molecular imprinting of the PCB 3 A material layer.
1.3 WO with molecular imprinting of PCB52 is formed on the surface obtained in step (4) of this example 3 Matrix of material layer (i.e. PCB52 molecular imprinting WO 3 Photoelectrochemical sensor), the surface obtained in step (3) is formed with a PCB52 and WO 3 The matrix of the composite material, as well as the commercially available metallic tungsten flakes, were subjected to X-ray diffraction analysis, as shown in fig. 2 (in order from top to bottom in fig. 2). From the lowest curve in the graph, it can be seen that the commercially available metallic tungsten sheet has a strong diffraction peak at 58.32 ° and a weak diffraction peak at 73.26 °, bothPeaks were attributed to (200) and (211) peaks of cubic phase metal tungsten (PDF # 04-0806), respectively. The (110) peak does not appear due to the shape of the tungsten plate. From the middle curve in the figure it can be seen that the surface is formed with a PCB52/WO 3 WO with diffraction peaks ascribed to hexagonal phases for the matrix of the composite material 3 ·0.33H 2 O (PDF # 35-1001) where the strong peak of 28.20 ° is the diffraction peak of the (200) plane, indicating preferential growth of the resulting material along the (200) plane. From the uppermost curve in the figure, it can be seen that diffraction peaks with 2 theta values of 24.42 DEG, 58.32 DEG and 73.26 DEG of the PCB52 molecular imprinting photoelectrochemical sensor can be attributed to WO in quadrature phase 3 (PDF # 20-1324) and illustrates that the material preferentially grows along the (200) plane.
1.4 the PCB52 molecularly imprinted photoelectrochemical sensor prepared in example 1 was used to detect the content of PCB52 in river water, comprising the steps of:
(1) Drawing a standard curve: by Na 2 SO 4 Aqueous solution (0.1 mol.L) -1 pH 6.8) is provided with a series of concentrations of standard solutions of PCB 52: 5.12X10 -15 mol·L -1 ,5.12×10 -14 mol·L -1 ,5.12×10 -13 mol·L -1 ,5.12×10 -12 mol·L -1 ,5.12×10 -11 mol·L -1 ,2.56×10 -10 mol·L -1 ,1.28×10 -9 mol·L -1 ,6.40×10 -9 mol·L -1 ,3.20×10 -8 mol·L -1 ,1.60×10 -7 mol·L -1 ,8.00×10 -7 mol·L -1 ,4.00×10 -6 mol·L -1 Taking the PCB52 molecularly imprinted photoelectrochemical sensor as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, taking an ultraviolet-visible light source as an excitation light source, applying a bias voltage of 0.6V on a CHI660e electrochemical workstation by using an i-t technology, sequentially detecting standard solutions of the PCB52 according to the sequence from low concentration to high concentration to obtain different photocurrent densities (see FIG. 3A), creating a linear relation between the photocurrent densities and the concentration of the PCB52, and drawing a standard curve (see FIG. 3B);
(2) Determining the content of PCB52 in river: filtering river water with sand core funnel for 3 times to remove water sampleAdding 50mL of filtered river water into 50mL of Na 2 SO 4 Solution (0.1 mol.L) -1 pH 6.8) to obtain a solution containing PCB52, testing the photocurrent density of the solution under the test conditions of step (1), and obtaining Na by using the standard curve 2 SO 4 The concentration of PCB52 in the solution was 0.0012nmol L -1 Then, the concentration of PCB52 in the river water was determined to be 0.0024 nmol.L - 1 mol·L -1 。
1.5 determination of stability and repeatability of the PCB52 molecularly imprinted photoelectrochemical sensor prepared in example 1 according to the aforementioned stability and repeatability determination method of the PCB52 molecularly imprinted photoelectrochemical sensor, specifically:
in the utilization of Na 2 SO 4 Aqueous solution (0.1 mol.L) -1 pH 6.8) configured to a concentration of 4.00×10 -6 mol·L -1 In the PCB52 solution, a PCB52 molecular imprinting photoelectrochemical sensor is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, an ultraviolet-visible light source is used as an excitation light source, an i-t technology is used on a CHI660e electrochemical workstation, a bias voltage of 0.6V is applied, and the light source is turned on for multiple times to observe the photocurrent condition. The results are shown in FIG. 4. From this figure, it can be seen that the photocurrent density of the sensor in the PCB52 solution immediately increased under light illumination, and remained relatively stable for 5000 seconds over multiple on/off power cycles, indicating that the sensor prepared in this example had high stability and good repeatability.
1.6 the selectivity of the PCB52 molecularly imprinted photoelectrochemical sensor prepared in example 1 to PCB52 molecules was determined according to the aforementioned selectivity determination method of the PCB52 molecularly imprinted photoelectrochemical sensor, specifically:
by Na 2 SO 4 Aqueous solution (0.1 mol.L) -1 pH 6.8) was set at 4.00X 10 at 5 concentrations -6 mol·L -1 To four of the PCB52 solutions, 3-chlorobiphenyl (PCB 3), bisphenol A (BPA), bisphenol acid (d-PA) and 4-chlorophenol (p-CP) interferents were added, respectively, at concentrations 100 times the concentration of PCB 52. Among the above 5 solutionsThe photocurrent densities of the 5 solutions were measured by using a PCB52 molecularly imprinted photoelectrochemical sensor as a working electrode, a platinum sheet as a counter electrode, ag/AgCl as a reference electrode, an ultraviolet-visible light source as an excitation light source, and an i-t technique on a CHI660e electrochemical workstation, with a bias voltage of 0.6V applied. And according toThe relative photocurrent density of the solution of PCB52 with the addition of the interferents was calculated, where I' is the relative photocurrent density of the solution after the addition of the interferents (concentration of interferents 4.00 x 10 - 4 mol·L -1 ) I is the photocurrent density in the PCB52 solution without adding an interfering substance, I 0 Is 0.1 mol.L -1 Na 2 SO 4 Photocurrent density of the solution. The R (%) value of the PCB52 solution without the interfering substance was set to 100%, and the result is shown in fig. 5. From the relative photocurrent density plot of this plot, it can be seen that in the solution of PCB52 with the interferents added, PCB52 molecularly imprinted WO 3 The value of R (%) of the photoelectrochemical sensor is significantly lower than the molecular imprinting WO of PCB52 in the solution of PCB52 3 R (%) value of photoelectrochemical sensor. This is attributable to the specificity of the molecularly imprinted recognition sites, only the specific molecular PCB52 perfectly binds to the recognition sites and causes a large change in photocurrent, whereas the dry-wound material, although similar to PCB52, has a small change in photocurrent due to low matching with the molecularly imprinted specific sites of the photosensor. Thus, due to the specificity of the molecularly imprinted recognition site, PCB52 molecularly imprinted WO 3 Photoelectrochemical sensor sensors have good selectivity for PCB52 molecules.
Example 2
A method for preparing a PCB52 molecular imprinting photoelectrochemical sensor, which comprises the following steps:
(1) Cutting the purchased tungsten sheet into small tungsten sheets with the length of 3cm and the width of 1cm, respectively ultrasonically cleaning the tungsten sheets with acetone, ethanol and water for 3 times, and drying the tungsten sheets at 60 ℃ for 30mins; placing the dried tungsten sheet in a muffle furnace, and calcining for 30mins at 550 ℃ to form a tungsten trioxide layer on the surface of the tungsten sheet;
(2) Preparation of 0.02mol·L -1 Na of (2) 2 WO 4 Taking 45mL of the solution into a small beaker with 100mL, adding 5mL of polyethylene glycol 200, and then adding 1mL of ethanol containing a certain amount of PCB52 molecules; the pH of the mixed solution was adjusted to 2.0 with hydrochloric acid having a concentration of 6M, wherein the mass ratio of sodium tungstate, PCB52, polyethylene glycol 200 was 360000:1:7700000.
(3) Placing the mixed solution obtained in the step (2) into a reaction kettle with a polytetrafluoroethylene lining of 100mL, and vertically placing the matrix obtained in the step (1) into the reaction mixed solution; placing the reaction kettle in an oven, adjusting the reaction temperature to 180 ℃ for reaction for 6 hours to form the PCB52/WO on the surface of the substrate 3 A composite material layer; after the reaction is finished, the surface is formed with PCB52/WO 3 The matrix of the composite layer was removed, repeatedly rinsed several times with distilled water, and then placed in a constant temperature oven at 60 ℃ for about 30mins.
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 And (3) placing the matrix of the composite material layer in a muffle furnace, and calcining at 650 ℃ for 3 hours to obtain the matrix of the composite material with the PCB52 molecular imprinting on the surface, namely the PCB52 molecular imprinting photoelectrochemical sensor.
Example 3
A method for preparing a PCB52 molecular imprinting photoelectrochemical sensor, which comprises the following steps:
(1) Cutting the purchased tungsten sheet into small tungsten sheets with the length of 3cm and the width of 1cm, respectively ultrasonically cleaning the tungsten sheets with acetone, ethanol and water for 3 times, and drying the tungsten sheets at 60 ℃ for 30mins; placing the dried tungsten sheet in a muffle furnace, and calcining for 40min at 450 ℃ to form a tungsten trioxide layer on the surface of the tungsten sheet;
(2) Preparing 0.02 mol.L -1 Na of (2) 2 WO 4 Taking 45mL of the solution into a small beaker with 100mL, adding 5mL of polyethylene glycol 200, and then adding 3mL of ethanol containing a certain amount of PCB52 molecules; the pH of the mixed solution was adjusted to 2.0 with 6M concentration hydrochloric acid, wherein the mass ratio of sodium tungstate, PCB52, polyethylene glycol 200 was 600000:1:12000000.
(3) Placing the mixed solution obtained in the step (2) into a reaction kettle with a polytetrafluoroethylene lining of 100mL, and placing the substrate obtained in the step (1)Vertically placing in a reaction mixed solution, placing a reaction kettle in an oven, adjusting the reaction temperature to 180 ℃ for reaction for 6 hours, and forming the PCB52/WO on the surface of the substrate 3 A composite material layer; after the reaction is finished, the surface is formed with PCB52/WO 3 The matrix of the composite layer was removed, repeatedly rinsed several times with distilled water, and then placed in a constant temperature oven at 60 ℃ for about 30mins.
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 And (3) placing the matrix of the composite material layer in a muffle furnace, and calcining at 550 ℃ for 3.5 hours to obtain the matrix of the composite material with the PCB52 molecular imprinting on the surface, namely the PCB52 molecular imprinting photoelectrochemical sensor.
Example 4
A method for preparing a PCB52 molecular imprinting photoelectrochemical sensor, which comprises the following steps:
(1) Cutting the purchased tungsten sheet into small tungsten sheets with the length of 3cm and the width of 1cm, respectively ultrasonically cleaning the tungsten sheets with acetone, ethanol and water for 3 times, and drying the tungsten sheets at 60 ℃ for 30min; placing the dried tungsten sheet in a muffle furnace, and calcining for 30mins at 550 ℃ to form a tungsten trioxide layer on the surface of the tungsten sheet;
(2) Preparing 0.02 mol.L -1 45mL of the sodium tungstate solution is taken in a small beaker with the volume of 100mL, 3mL of polyethylene glycol 200 is added, and then 5mL of ethanol containing a certain amount of PCB52 molecules is added; the pH of the mixed solution was adjusted to 2.0 with 6M hydrochloric acid, wherein the mass ratio of sodium tungstate, PCB52, polyethylene glycol 200 was 360000:1:4600000.
(3) Placing the mixed solution obtained in the step (2) into a reaction kettle with a polytetrafluoroethylene lining of 100mL, and vertically placing the matrix obtained in the step (1) into the reaction mixed solution; placing the reaction kettle in an oven, adjusting the reaction temperature to 180 ℃ for 4.5 hours, and forming the PCB52/WO on the surface of the substrate 3 A composite material layer; after the reaction is finished, the surface is formed with PCB52/WO 3 The matrix of the composite layer was removed, repeatedly rinsed several times with distilled water, and then placed in a constant temperature oven at 60 ℃ for about 30mins.
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 Placing the matrix of the composite material layer in a muffle furnaceCalcining at 650 ℃ for 3 hours, and forming a compound layer of the PCB52 molecular imprinting on the surface to obtain the PCB52 molecular imprinting photoelectrochemical sensor.
Example 5
A method for preparing a PCB52 molecular imprinting photoelectrochemical sensor, which comprises the following steps:
(1) Cutting the purchased tungsten sheet into small tungsten sheets with the length of 3cm and the width of 1cm, respectively ultrasonically cleaning the tungsten sheets with acetone, ethanol and water for 3 times, and drying the tungsten sheets at 60 ℃ for 30min; placing the dried tungsten sheet in a muffle furnace, and calcining for 30mins at 550 ℃ to form a tungsten trioxide layer on the surface of the tungsten sheet;
(2) Preparing 0.01 mol.L -1 45mL of the sodium tungstate solution is taken in a small beaker with the volume of 100mL, 5mL of polyethylene glycol 200 is added, and then 2.5mL of ethanol containing a certain amount of PCB52 molecules is added; the pH of the mixed solution was adjusted to 2.0 with 6M concentration hydrochloric acid, wherein the mass ratio of sodium tungstate, PCB52, polyethylene glycol 200 was 360000:1:15000000.
(3) Placing the mixed solution obtained in the step (2) into a reaction kettle with a polytetrafluoroethylene lining of 100mL, and vertically placing the matrix obtained in the step (1) into the reaction mixed solution; placing the reaction kettle in an oven, adjusting the reaction temperature to 180 ℃ for reaction for 5.5 hours to form the PCB52/WO on the surface of the substrate 3 A composite material layer; after the reaction is finished, the surface is formed with PCB52/WO 3 The matrix of the composite layer was removed, repeatedly rinsed several times with distilled water, and then placed in a constant temperature oven at 60 ℃ for about 30mins.
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 And (3) placing the matrix of the composite material layer in a muffle furnace, and calcining at 650 ℃ for 3.5 hours to obtain the matrix of the composite material with the PCB52 molecular imprinting on the surface, namely the PCB52 molecular imprinting photoelectrochemical sensor.
Example 6
A method for preparing a 2,2', 5' -tetrachlorobiphenyl molecular imprinting photoelectrochemical sensor, which comprises the following steps:
(1) Cutting the purchased tungsten sheet into small tungsten sheets with the length of 3cm and the width of 1cm, respectively ultrasonically cleaning the tungsten sheets with acetone, ethanol and water for 3 times, and drying the tungsten sheets at 60 ℃ for 30mins; placing the dried tungsten sheet in a muffle furnace, calcining for 30min at 550 ℃ to form a tungsten trioxide layer on at least the surface of the tungsten sheet to form a matrix;
(2) Preparing 0.03 mol.L -1 45mL of the sodium tungstate solution was placed in a 100mL beaker, 5mL of polyethylene glycol 200 was added, and then 5mL of ethanol containing a certain amount of PCB52 molecules was added. The pH of the mixed solution was adjusted to 2.0 with 6M hydrochloric acid, wherein the mass ratio of sodium tungstate, PCB52, polyethylene glycol 200 was 500000:1:7700000.
(3) Placing the mixed solution obtained in the step (2) into a reaction kettle with a polytetrafluoroethylene lining of 100mL, and vertically placing the matrix obtained in the step (1) into the reaction mixed solution; placing the reaction kettle in an oven, adjusting the reaction temperature to 180 ℃ for reaction for 6 hours to form the PCB52/WO on the surface of the substrate 3 A composite material layer; after the reaction is finished, the surface is formed with PCB52/WO 3 The matrix of the composite layer was removed, repeatedly rinsed several times with distilled water, and then placed in a constant temperature oven at 60 ℃ for about 30mins.
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 And (3) placing the matrix of the composite material layer in a muffle furnace, and calcining at 700 ℃ for 2 hours to obtain the matrix of the composite material with the PCB52 molecular imprinting on the surface, namely the PCB52 molecular imprinting photoelectrochemical sensor.
The PCB52 molecular imprinting photoelectrochemical sensors of the embodiments 2 to 6 are also observed through a scanning electron microscope, and the sensors prepared by the embodiments of the invention have good morphology.
The PCB52 contents in the river water were measured using the PCB52 molecular imprinting photoelectrochemical sensors of examples 2 to 6, and they were found to have a wide response range and a low detection limit.
In addition, the PCB52 molecular imprinting photoelectrochemical sensors of examples 2 to 6 were measured according to the above-mentioned PCB52 molecular imprinting photoelectrochemical sensor stability and reproducibility measurement method and PCB52 molecular imprinting photoelectrochemical sensor selectivity measurement method, and the results showed that they all had good stability, reproducibility, and selectivity.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and various modifications can be made to the above-described embodiment of the present invention. All simple, equivalent changes and modifications made in accordance with the claims and the specification of this application fall within the scope of the patent claims. The present invention is not described in detail in the conventional art.
Claims (10)
1. A PCB52 molecularly imprinted photoelectrochemical sensor, characterized in that the sensor comprises a substrate having WO on its surface 3 Tungsten platelet matrix of layers and UV-visible driven WO deposited on the surface of said matrix by hydrothermal synthesis technique 3 A layer of material, said WO 3 The material layer has PCB52 molecularly imprinted sites.
2. The method for manufacturing a PCB52 molecularly imprinted photoelectrochemical sensor of claim 1, comprising the steps of:
(1) Calcining the tungsten sheet at 300-600 ℃ for 20-50 minutes to form WO on the surface of the tungsten sheet 3 A layer, a surface having WO 3 A tungsten plate matrix of the layer;
(2) Na is mixed with 2 WO 4 Mixing the aqueous solution with polyethylene glycol, adding ethanol solution containing PCB52 molecules, and regulating the pH of the mixed solution to 2.0 by using inorganic acid;
(3) Forming WO on the surface prepared in the step (1) 3 The tungsten chip substrate of the layer is put into the mixed solution in the step (2) to react for 4 to 8 hours at the temperature of 150 to 210 ℃ so that the surface of the substrate forms the PCB52/WO 3 A composite material layer;
(4) Forming the surface obtained in the step (3) with a PCB52/WO 3 Calcining the matrix of the composite material layer at 450-700 ℃ for 2-4 hours to form WO (WO) with PCB52 molecular imprinting sites on the surface of the matrix 3 And (5) the material layer is used for obtaining the PCB52 molecular imprinting photoelectrochemical sensor.
3. The method of preparing a PCB52 molecularly imprinted photoelectrochemical sensor according to claim 2, wherein the polyethylene glycol is selected from polyethylene glycol 200.
4. The method of manufacturing a PCB52 molecularly imprinted photoelectrochemical sensor according to claim 2, wherein in step (2), na is by weight 2 WO 4 : PCB52 is 300000 ～ 900000:1, na 2 WO 4 : polyethylene glycol is 1:10 to 100.
5. The method for manufacturing a PCB52 molecularly imprinted photoelectrochemical sensor according to claim 2, wherein in step (3), WO is formed on the surface 3 The reaction temperature of the tungsten flakes of the layer and the mixed solution is 180 ℃ and the time is 4-8 hours.
6. The method for manufacturing a PCB52 molecularly imprinted photoelectrochemical sensor according to claim 2, wherein in the step (4), the temperature of the calcination of the tungsten sheet is 500-700 ℃ for 2-4 hours.
7. Use of a PCB52 molecularly imprinted photoelectrochemical sensor as claimed in claim 1 or a PCB52 molecularly imprinted photoelectrochemical sensor prepared by a method of preparation as claimed in any one of claims 2 to 5 in detecting PCB52 molecules in a medium.
8. The use according to claim 7, wherein the method for detecting PCB52 molecules in a medium using the PCB52 molecularly imprinted photoelectrochemical sensor comprises the steps of:
(1) Drawing a standard curve: by Na 2 SO 4 Preparing a series of standard solutions of the PCB52 with concentration by using an aqueous solution, preparing the standard solutions of the PCB52 with concentration, using the molecular imprinting photoelectrochemical sensor of the PCB52 as a working electrode, using a platinum sheet as a counter electrode, using Ag/AgCl as a reference electrode, using an ultraviolet-visible light source as an excitation light source, applying a bias voltage of 0.6V on a CHI660e electrochemical workstation by using an i-t technology, sequentially detecting the standard solutions of the PCB52 according to the sequence from low concentration to high concentration to obtain different photocurrent densities, and finally using the photocurrent densities and the concentration of the PCB52Creating a linear relation, and drawing a standard curve;
(2) Determining the content of PCB 52: adding a sample of the medium to be tested containing PCB52 to Na 2 SO 4 Obtaining a solution containing the PCB52 in the aqueous solution, testing the photocurrent density of the solution under the test condition of the step (1), and obtaining Na by using the standard curve 2 SO 4 The concentration of the PCB52 in the solution is determined, i.e., the concentration of the PCB52 in the medium.
9. The method according to claim 8, wherein in step (2), when the medium sample contains precipitate, the medium sample is filtered with a sand funnel for 3-5 times and then added to Na 2 SO 4 In an aqueous solution.
10. The use according to claim 8, wherein in step (1) and step (2) Na is used to configure the PCB52 solution 2 SO 4 The concentration of the aqueous solution was 0.1 mol.L -1 。
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