CN113155919A - Based on MnO2Method for detecting pentachlorophenol in wood product by using nano-rod - Google Patents
Based on MnO2Method for detecting pentachlorophenol in wood product by using nano-rod Download PDFInfo
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Abstract
The invention discloses a method based on MnO2A method for detecting pentachlorophenol in a wood product by using nanorods belongs to the field of analysis and detection. The method firstly prepares MnO2Nano material, then preparing MnO2Nanorod dispersion modified screen-printed electrode using differential pulse voltammetry with MnO2Detecting pentachlorophenol Tris-HCl buffer solutions with different concentrations by using a nanorod dispersion modified screen printing electrode to obtain the relation between the pentachlorophenol oxidation peak current and the concentration; and then, pretreating the sample to be detected, and performing a standard addition recovery test to obtain the content of the sample to be detected. The electrochemical detection method established by the invention has the advantages of high sensitivity, safety, simple operation and low requirement on operators, and can be used for quickly detecting pentachlorophenol in wood products.
Description
Technical Field
The invention relates to the field of analysis and detection, in particular to a method based on MnO2Method for detecting pentachlorophenol in wood products by using nanorods.
Background
Pentachlorophenol (PCP for short) is an important preservative used for preventing the growth of fungi and inhibiting the corrosion of bacteria, and is widely used as a wood preservative in indoor and outdoor building construction; can also be used for the preservation of natural fibers such as cotton, wool and the like in the processes of storage and transportation; can also be used as a stabilizer for preventing printing paste from corrosion and mildew and used for textile processing. It not only has strong carcinogenic, teratogenic and mutagenic effects, but also releases dioxin-like compounds during combustion, causing permanent damage to the environment, and is blacklisted by priority pollutants and permanent organic pollutants in many countries including China. Also, due to the stable halogenated aromatic ring structure and high chlorine content of pentachlorophenol, its biodegradation rate is relatively slow. Related researches show that the wide use of pentachlorophenol causes environmental pollution and interference on secretion in human bodies, and pentachlorophenol remained in wood products can migrate into human bodies along with the contact of the pentachlorophenol with human skins, so that biological accumulation is caused and the human health is harmed. Therefore, the establishment of a sensitive, rapid and accurate pentachlorophenol detection method has important significance for human health and environmental safety.
Although various methods for detecting pentachlorophenol have been developed, such as gas chromatography, high performance liquid chromatography, liquid chromatography-mass spectrometry, etc., there are still disadvantages of complicated operation, large equipment, long detection period, high cost, etc.
Disclosure of Invention
The invention provides a MnO-based method aiming at the existing technical problems2Method for detecting pentachlorophenol in wood products by using nanorods.
The purpose of the invention can be realized by the following technical scheme:
based on MnO2The method for detecting pentachlorophenol in a wood product by using the nanorods comprises the following steps:
(1)MnO2and (3) synthesis of nano materials: mixing MnSO4·H2O and (NH)4)2S2O8Dissolving in water, introducing N2And stirring uniformly to obtain a mixed solution; transferring the mixed solution into a reaction kettle, heating and reacting for 20-30 hours at 100-160 ℃, centrifuging and washing and drying after the reaction is finished to obtain MnO2A nanorod material;
(2) preparing an electrode: MnO of2Dissolving the nano rod material and polyethyleneimine into water, and performing ultrasonic dispersion to obtain MnO2A suspension; remeno2Slowly dripping the suspension on a working electrode of a screen printing electrode, and drying to obtain MnO2A screen-printed electrode modified by the nano-rod dispersion liquid;
(3) detection of pentachlorophenol: using differential pulse voltammetry, using MnO2Detecting pentachlorophenol Tris-HCl buffer solutions with different concentrations by using a nanorod dispersion modified screen printing electrode to obtain the relation between the pentachlorophenol oxidation peak current and the concentration; and then, pretreating the sample to be detected, and performing a standard addition recovery test to obtain the content of the sample to be detected.
The technical scheme of the invention is as follows: MnSO in step (1)4·H2O and (NH)4)2S2O8The mass ratio of (1): 1.5 to 2.5.
The technical scheme of the invention is as follows: the reaction temperature of the step (1) is 135-145 ℃, and the reaction time is 22-26 hours.
The technical scheme of the invention is as follows: MnO in step (2)2The mass ratio of the nano material to the polyethyleneimine to the water is 1 mg: (3-8) mg: (0.5 to 1.5) g.
The technical scheme of the invention is as follows: in the step (3), the concentration of the Tris-HCl buffer solution is 0.1mol/L, and the pH value is 2-12.
In some preferred embodiments: and (4) the pH value of the Tris-HCl buffer solution in the step (3) is 7.0.
In some preferred embodiments: MnO in step (3)2MnO in suspension2The concentration of the nano-rods is 1.0 mg/mL.
The technical scheme of the invention is as follows: MnO in step (3)2And slowly dripping the suspension on a working electrode of the screen printing electrode, wherein the dripping amount is 3-6 mu L.
In some preferred embodiments: MnO in step (3)2The suspension was slowly dropped onto the working electrode of the screen-printed electrode in an amount of 5. mu.L.
The technical scheme of the invention is as follows: diameter of working electrode is 3mm, reference electrode: silver/silver chloride.
The technical scheme of the invention is as follows: in the step (3), the oxidation peak current I (mu A) and the concentration c (mg/L) of the pentaphenol are in good linear relation in the range of 0.1-80 mg/L, and the regression equations are respectively that I is 0.0.1164c +0.3895 (R)20.996), detection limit is as low as 0.028 mg/L.
The invention has the beneficial effects that:
the invention discloses simple MnO2The preparation method of the SPE modified electrode optimizes conditions which can affect peak current, including pH of a buffer solution, concentration of a dispersion solution and modification amount of the dispersion solution, and the modified electrode shows good signal response to detection of pentachlorophenol under the optimal conditions. Differential pulse method research shows that the response peak current value and the concentration of pentachlorophenol on the modified electrode have good linear relation. The reason may be that the material may increase the active sites on the electrode surface and may increase the transfer rate of pentachlorophenol. In addition, a good result is obtained in the detection of an actual sample, which shows that the established electrochemical detection method has high sensitivity, safety, simple operation and low requirement on operators, and can be used for quickly detecting pentachlorophenol in a wood product.
Drawings
FIG. 1 shows MnO obtained in example 12Scanning electron microscopy of nanorods.
FIG. 2 illustrates pentachlorophenol at SPE (a) and MnO2CV curve on SPE (b).
FIG. 3 is a graph of Tris-HCl buffer solutions at various pH values as a function of relative current.
FIG. 4 shows MnO2Concentration versus relative current change.
FIG. 5 shows MnO2Modification versus change in relative current.
FIG. 6 is a differential pulse voltammetry detection of pentachlorophenol.
FIG. 7 shows MnO2Differential pulse voltammogram of the nanorod modified electrode in pentachlorophenol solutions with different concentrations.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
Test instrument and consumable
MnSO4·H2O、(NH4)2S2O8Absolute ethyl alcohol, polyethyleneimine, tris (hydroxymethyl) aminomethane, hydrochloric acid (aladdin chemical company); pentachlorophenol (Sigma chemical Co.). The electrochemical experiment is carried out on an electrochemical workstation CHI-650E (Shanghai Chenghua instruments Co., Ltd.), and all reagents used by a Screen Printing Electrode (SPE) are analytically pure; the experimental water was ultrapure water.
MnO2Synthesis of nanomaterials
6.70g of MnSO4·H2O and 13.69g of (NH)4)2S2O8Dissolved in 40mL of distilled water, and N was introduced thereinto at room temperature2And stirred for 1 hour. The resulting mixed solution was then transferred to a polytetrafluoroethylene-lined stainless steel autoclave (40 ml) and heated at 140 ℃ for reaction for 24 hours. After the reaction, the mixture was cooled to room temperature. The product was centrifuged again, washed with distilled water and ethanol and then dried in an oven at 50 ℃. FIG. 1 shows MnO2Scanning electron microscopy of nanorods. By analysis of a scanning electron microscope, the synthetic MnO can be seen2The microstructure and the specific morphology of the nano material. As clearly observed from the figure, MnO synthesized2Is in rod-like form and has high densityThe structure is favorable for improving the conductivity of the material, thereby improving the electrochemical performance of the electrode.
Electrode preparation
Weighing 1mg of MnO2The nanorods and 5mg of polyethyleneimine were dissolved in 1mL of ultrapure water, and subjected to ultrasonic treatment for 5 minutes to obtain a uniform dispersion. Then 5 mu L of MnO was added dropwise2(1mg/mL) suspension on SPE, and working electrode diameter 3mm, reference electrode: silver/silver chloride. Then drying at room temperature to obtain MnO2The screen printing electrode modified by the nano-rod dispersion is used for electrochemical detection.
Testing of pentachlorophenol
MnO of2The screen printing electrode modified by the nano-rod dispersion liquid is placed in Tris-HCl buffer solution containing pentachlorophenol with the pH value of 7.0, Cyclic Voltammetry (CV) scanning is carried out, the scanning range is-0.2V-1.4V, and MnO is verified2Electrochemical detection of pentachlorophenol by SPE. In order to determine the linear response range of pentachlorophenol with different concentrations, differential pulse scanning is carried out by using the modified SPE in Tris-HCl buffer solution containing pentachlorophenol with different concentrations, wherein the scanning range is 0V-1.2V, and the scanning speed is 50 mV/s.
Electrochemical behavior of pentachlorophenol at different electrodes
Comparison of pentachlorophenol in bare SPE and MnO2Electrochemical behavior on SPE, results are shown in FIG. 2. As can be seen from the observation of FIG. 2, the CV curve shows a distinct oxidation peak and no reduction peak, indicating that the reaction of the substance under electrocatalysis is irreversible. Pentachlorophenol in bare SPE and MnO2the/SPE scans all showed an oxidation peak, but on bare screen printed electrodes, a weaker response to pentachlorophenol was seen. In MnO2The peak current of the SPE is obviously larger than that of the bare SPE, and a larger oxidation peak appears around 0.773V. MnO can be seen2The SPE has obvious catalytic action on the oxidation reaction of pentachlorophenol and uses MnO2The nanorod modified electrode surface can enhance the electrochemical oxidation response of pentachlorophenol.
Optimization of Tris-HCl buffer solution pH
The pH of the buffer has some effect on the electrochemical response and therefore the appropriate pH needs to be selected. FIG. 3 shows 1mg/mL MnO using differential pulse voltammetry2The nanorod modified electrode is in 0.1mol/L Tris-HCl buffer solution, and the pH value is changed within the range of 2.0-12.0. The peak current detected in Tris-HCl buffer at pH7.0 was set to 1. As can be seen, the relative current increased and then decreased with increasing pH, and the maximum current was observed at pH 7.0. Therefore, Tris-HCl buffer at pH7.0 was used as the electrolyte solution for pentachlorophenol detection.
MnO2Optimization of nanorod concentration
MnO2The concentration of the nano-rod on the screen printing electrode has certain influence on the electrochemical response, so that proper MnO needs to be selected2The concentration of the nano-rods. FIG. 6 shows differential pulsed voltammetry with MnO in 0.1mol/LTris-HCl buffer at pH7.02The change of oxidation peak current of the nano-rod in the range of 0.5-4.0 mg/mL. MnO of2The peak current corresponding to the nanorod of 1mg/mL was set to 1. As can be seen from FIG. 4, the relative current increases when the concentration is between 0.5 and 1.0mg/mL, reaches the maximum current when the concentration reaches 1.0mg/mL, and then follows the MnO2The increase in nanorod concentration decreased until 4 mg/mL. Thus, MnO is selected2The concentration of the nano-rods is 1.0mg/mL, and the nano-rods are used as the optimal modification concentration of the screen printing electrode.
MnO2Optimization of nanorod modification amount
MnO2The modification amount of the nano-rod on the screen printing electrode has certain influence on the electrochemical response, so that the proper modification amount needs to be selected. FIG. 5 shows the use of differential pulse voltammetry with MnO in 0.1mol/L Tris-HCl buffer pH7.02(1mg/mL) modification amount is changed within a range of 1-7 μ L relative to oxidation peak current. MnO of2The corresponding peak current detected when the nanorod modification amount was 5 μ L was set to 1. As is clear from the graph, the modification amount is in the range of 1 to 5. mu.L, and the relative current increases with the increase of the modification amount, that is, the oxidation peak gradually increases, and reaches the maximum at the modification amount of 5. mu.L. But follow byThe modification amount is continuously increased and the relative current change begins to be in a descending trend, which shows that the electron transfer is blocked by excessive modification on the surface of the electrode, and then the oxidation catalytic effect on the pentachlorophenol begins to be reduced. Therefore, 5. mu.L was selected as the optimum modification amount.
2.4 detection of pentachlorophenol
As shown in FIG. 7, MnO2The oxidation reduction reaction of pentachlorophenol in the nanorod catalytic solution accelerates the oxidation process, an oxidation peak is generated at 0.773V, and the current intensity value of the oxidation peak is positively correlated with the concentration (0.1-80 mg/L) of pentachlorophenol in the solution, so that quantitative detection can be carried out. Differential Pulse Voltammetry (DPV) was used under optimal experimental conditions (Tris-HCl buffer pH7.0, MnO2Concentration of 1.0mg/mL and modification amount of 5 μ L) was detected for pentachlorophenol at different concentrations (0.1, 4, 10, 20, 40, 60, 80mg/L) to obtain the relationship between the oxidation peak current and the concentration of pentachlorophenol, and as a result, as shown in fig. 6, the oxidation peak current I (μ a) and the concentration c (mg/L) of pentachlorophenol were in good linear relationship in the range of 0.1 to 80mg/L, and their regression equations were I-0.0.1164 c +0.3895 (R) (R: 0.0.1164c +0.3895, respectively)20.996), detection limit is as low as 0.028 mg/L.
Determination of pentachlorophenol in wood products
At least 5 pieces of the sample for analysis are randomly extracted from all the wood materials to be tested, the middle section of the wood is cut transversely, and the sample is planed by a wood plane or drilled in the middle of the wood sample to be tested by a hollow drill. Pulverizing the sample, sieving with a metal sieve, mixing thoroughly, weighing 1g, adding into 10mL Tris-HCl buffer solution containing pentachlorophenol with different concentrations, mixing thoroughly, performing ultrasonic treatment for 30min, and adding the prepared MnO2the/SPE electrode was placed in the cell for spiking recovery. And (3) shearing the positive sample, adding the sheared positive sample into 10mL of Tris-HCl buffer solution, and carrying out ultrasonic treatment for 30min to directly carry out testing. As can be seen from Table 1, the recovery rate of the spiked sample in the method is between 87% and 92.6%, the positive sample and the GC/MS result have better consistency, and the recovery rate and the reliability of the method can meet the detection requirement of the actual sample.
TABLE 1 measurement results of spiked recovery and measurement results of Positive samples
Table 1 Determination results of standard addition recovery and positive samples
Claims (10)
1. Based on MnO2The method for detecting pentachlorophenol in a wood product by using the nanorods is characterized in that: the method comprises the following steps:
(1)MnO2and (3) synthesis of nano materials: mixing MnSO4·H2O and (NH)4)2S2O8Dissolving in water, introducing N2And stirring uniformly to obtain a mixed solution; transferring the mixed solution into a reaction kettle, heating and reacting for 20-30 hours at 100-160 ℃, centrifuging and washing and drying after the reaction is finished to obtain MnO2A nanorod material;
(2) preparing an electrode: MnO of2Dissolving the nano rod material and polyethyleneimine into water, and performing ultrasonic dispersion to obtain MnO2A suspension; remeno2Slowly dripping the suspension on a working electrode of a screen printing electrode, and drying to obtain MnO2A screen-printed electrode modified by the nano-rod dispersion liquid;
(3) detection of pentachlorophenol: using differential pulse voltammetry, using MnO2Detecting pentachlorophenol Tris-HCl buffer solutions with different concentrations by using a nanorod dispersion modified screen printing electrode to obtain the relation between the pentachlorophenol oxidation peak current and the concentration; and then, pretreating the sample to be detected, and performing a standard addition recovery test to obtain the content of the sample to be detected.
2. The method of claim 1, wherein: MnSO in step (1)4·H2O and (NH)4)2S2O8The mass ratio of (1): 1.5 to 2.5.
3. The method of claim 1, wherein: the reaction temperature of the step (1) is 135-145 ℃, and the reaction time is 22-26 hours.
4. The method of claim 1, wherein: MnO in step (2)2The mass ratio of the nano material to the polyethyleneimine to the water is 1 mg: (3-8) mg: (0.5 to 1.5) g.
5. The method of claim 1, wherein: in the step (3), the concentration of the Tris-HCl buffer solution is 0.1mol/L, and the pH value is 2.0-12; preferably: and (4) the pH value of the Tris-HCl buffer solution in the step (3) is 7.
6. The method of claim 4, wherein: MnO in step (2)2MnO in suspension2The concentration of the nano-rods is 1.0 mg/mL.
7. The method of claim 1, wherein: MnO in step (2)2And slowly dripping the suspension on a working electrode of the screen printing electrode, wherein the dripping amount is 3-6 mu L.
8. The method of claim 7, wherein: MnO in step (2)2The suspension was slowly dropped onto the working electrode of the screen-printed electrode in an amount of 5. mu.L.
9. The method of claim 7, wherein: diameter of working electrode is 3mm, reference electrode: silver/silver chloride.
10. The method of claim 1, wherein: in the step (3), the oxidation peak current I (mu A) and the concentration c (mg/L) of the pentaphenol are in good linear relation in the range of 0.1-80 mg/L, and the regression equations are respectively that I is 0.0.1164c +0.3895 (R)20.996), detection limit is as low as 0.028 mg/L.
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