CN117740900B - Method for quantitatively detecting nano-plastics in water based on electrochemical sensor - Google Patents
Method for quantitatively detecting nano-plastics in water based on electrochemical sensor Download PDFInfo
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Abstract
The invention relates to a method for quantitatively detecting nano-plastics in water based on an electrochemical sensor, which is performed based on the electrochemical sensor, can sensitively and accurately collect and analyze information without extracting nano-plastics in water in advance and adopts trace water to realize in-situ detection, has the advantages of simple operation, low cost, wide nano-plastics detection range, low detection limit and high sensitivity, is a rapid, efficient, miniaturized and high-flux detection method, and realizes that the nano-plastics detection has higher sensitivity within the range of 1.5X10 ‑3~4.0×103μg L−1 and the detection limit is as low as 1.8X10 ‑5μg L‑1.
Description
Technical Field
The invention relates to a method for quantitatively detecting nano-plastics in water based on an electrochemical sensor, and belongs to the technical field of water detection.
Background
While the multifunctional use of plastics brings great benefits to life, there is concern about "plastic rejection". Once the plastic enters the natural circulation, it can cause substantial release of micro-plastics (1 μm-5 mm) and nano-plastics (< 1 μm) due to mechanical abrasion, uv radiation and (micro) biodegradation. The natural circulation of nano-plastics not only has adverse effects on agriculture and ecosystems, but also can be ingested by animals and humans along with the food chain (reticulation), and cause problems of cytotoxicity, immune response, oxidative stress, genetic toxicity, and the like. The high surface area of the nano-plastic makes it a good carrier for adsorbing organic or inorganic pollutants, and the formed composite pollutants can cause more serious harm to species.
Nano-plastics are considered an emerging contaminant that has the ability to adsorb organic and inorganic contaminants while circulating in the natural environment. To date, there have been some methods for detection and analysis of nanomaterials, mainly including spectrometry and mass spectrometry. Methods based on spectroscopic analysis include surface enhanced raman spectroscopy, multi-angle light scattering (MALS), etc., which have limitations on optical resolution, and when the nano-plastic size is below its optical resolution, practical detection is difficult to achieve. The mass spectrometry-based method is a widely used technology in the current nano-plastic analysis, mainly comprises single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS), matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), thermal cracking gas chromatography-mass spectrometry (Pyr-GC-MS) and the like, but the method is often dependent on a large instrument, is complex in operation and high in cost, and most of the method is required to add an adsorbent or an extractant to extract nano-plastic in water, and the complicated pretreatment steps are required to cause certain pollution to nano-plastic detection, so that in-situ analysis and detection cannot be performed, and the analysis result is inaccurate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for quantitatively detecting nano plastics in a water body based on an electrochemical sensor.
The detection method is based on an electrochemical sensor, can sensitively and accurately collect and analyze information without extracting nano plastic in water in advance and adopting trace water, realizes in-situ detection, has the advantages of simple operation, low cost, wide nano plastic detection range, low detection limit and high sensitivity, and is a rapid, efficient, miniaturized and high-flux detection method.
The technical scheme of the invention is as follows:
a method for quantitatively detecting nano-plastics in water based on an electrochemical sensor comprises the following steps:
1) Constructing an electrochemical sensor;
The electrochemical sensor is prepared by the following steps:
a. Polishing a screen printing electrode, performing ultrasonic cleaning, activating and drying at room temperature to obtain an activated screen printing electrode, wherein the screen printing electrode comprises a substrate, a working electrode, a reference electrode and a counter electrode;
b. Dropwise adding a Mg 2+ -MXene aerogel solution on the surface of a working electrode of the activated screen printing electrode, and drying at room temperature to obtain a screen printing electrode of modified Mg 2+ -MXene aerogel, namely an electrochemical sensor;
2) Preparing nano plastic standard sample liquids with different concentrations, and dripping the standard sample liquid into a working electrode area of an electrochemical sensor;
3) Immersing an electrochemical sensor dropwise added with standard sample liquid into electrolyte solution at room temperature for impedance spectrum measurement, and drawing a standard working curve by utilizing the relation between the measured electrochemical interface impedance value and the concentration of the nano plastic standard solution;
4) Dripping a water body to be detected into a working electrode area of an electrochemical sensor, immersing the water body into an electrolyte solution according to the method of the step 3) to perform impedance spectrum measurement of a sample, and measuring an impedance value of the sample; and (3) obtaining the content of the nano plastic in the water body to be detected according to the standard working curve of the step (3).
According to a preferred embodiment of the invention, in step a, the carbon is the counter electrode and the Ag/AgCl electrode is the reference electrode.
According to the invention, in the step b, the Mg 2+ -MXene aerogel solution is a suspension obtained by adding Mg 2+ -MXene aerogel into deionized water and stirring uniformly, and the concentration of the Mg 2+ -MXene aerogel solution is 1-3Mg/mL.
According to a preferred embodiment of the invention, in step b, the Mg 2+ -MXene aerogel solution is added dropwise in an amount of 1-5. Mu.L.
In a preferred embodiment of the invention, in step b, the Mg 2+ -MXene aerogel material is prepared as follows:
(1) Preparing a multilayer Ti 3C2Tx MXene by an acid etching method;
(2) Stripping by an ultrasonic method to form a single-layer Ti 3C2Tx MXene solution;
(3) The single-layer Ti 3C2Tx MXene solution is mixed with MgCl 2 solution, the single-layer Ti 3C2Tx MXene solution is induced to gel through Mg 2+, and the aerogel material is formed by freeze drying.
According to the preferred embodiment of the present invention, in the step (1), the acid etching method for preparing the multi-layer Ti 3C2Tx MXene is specifically:
And (3) slowly adding LiF into the concentrated HCl, stirring until the LiF is dissolved to obtain a mixed solution, slowly adding Ti 3AlC2 -MAX powder into the mixed solution in batches, etching for 20-30h at the temperature of 35-45 ℃, and centrifugally washing the etching solution until the pH value is more than or equal to 6 to obtain a colloid solution of Ti 3C2 -MXene.
Further preferably, the concentration of concentrated HCl is 9mol/L.
Further preferably, the temperature of LiF is 40 ℃, and the mass-volume ratio of LiF to concentrated HCl is (1-2): (10-30), g/mL; the stirring speed was 600rpm.
Further preferably, the mass volume ratio of Ti 3AlC2 -MAX powder to concentrated HCl is (0.5-2): (10-30), g/mL.
Further preferably, the centrifugal washing etching liquid is subjected to centrifugal washing etching liquid at a speed of 5000r/min, and the centrifugal washing is repeated for 1min each time until the pH is more than or equal to 6.
According to the invention, in the step (2), the ultrasonic stripping method is specifically used for forming a single-layer Ti 3C2Tx MXene solution:
introducing argon into the Ti 3C2 -MXene colloid solution prepared in the step (1) for protection, and performing ice bath ultrasonic dispersion for 40min under the power of 240W; centrifuging at 10000r/min for 60min, collecting supernatant, and diluting to 4-10mg/mL to obtain single-layer Ti 3C2Tx MXene solution.
According to a preferred embodiment of the invention, in step (3), the concentration of MgCl 2 solution is between 0.5 and 2mol/L.
According to a preferred embodiment of the invention, in step (3), the volume ratio of the single layer Ti 3C2Tx M Xene solution to the MgCl 2 solution is (20-30): 1.
According to the invention, in the step (3), after mixing and standing for 30 seconds, the hydrogel of Mg 2+ -MXene is prepared; then, the mixture was frozen overnight to prepare an ice gel of Mg 2+ -MXene, and the ice gel was dried in a vacuum freeze dryer for 24 hours to prepare Mg 2+ -MXene aerogel.
Mg 2+ ions disrupt the electrostatic repulsion of MXene by electrostatic interactions, and these Mg 2+ ions are used as linkers to promote crosslinking of MXene nanoplatelets. Compared with a two-dimensional material, the Mg 2+ -MXene aerogel material has good conductivity, and the three-dimensional space network structure of the Mg 2+ -MXene aerogel material has higher specific surface area and larger porosity, and is easier to contact with reactants, so that the detection sensitivity is improved.
According to the invention, in the step 2), the preparation of the nano plastic standard sample liquid is as follows: adding water into the nano plastic to prepare 2.5mg/mL concentrated solution, and adding water into the concentrated solution to dilute the concentrated solution to 0.0015μg L-1、0.0025μg L-1、0.003μg L-1、0.01μg L-1、0.015μg L-1、0.15μg L-1、1.5μg L-1、30μg L-1、100μg L-1、400μg L-1、1800μg L-1、4000μg L-1, to prepare nano plastic standard sample solutions with different concentrations.
According to a preferred embodiment of the present invention, in the step 3), the electrolyte solution is a potassium chloride solution containing potassium ferrocyanide at a concentration of 10mmol/L and potassium ferricyanide at a concentration of 10mmol/L, and the concentration of potassium chloride is 50 to 100mmol/L.
According to a preferred embodiment of the invention, in step 3), the electrochemical impedance spectrum is determined using an alternating sinusoidal voltage having a frequency in the range of 10 5~100 Hz and an amplitude of 5 to 15 mV.
According to the present invention, in order to make the detection more accurate, the drop amount of the standard sample liquid in step 2) is 4 μl, and the drop amount of the water body to be detected in step 4) is 4 μl.
In accordance with a preferred embodiment of the present invention, the impedance element values are derived using ZSimp Win software, and the resulting EIS data is modeled as an equivalent circuit.
According to the detection method, the detection range of the nano plastic content is 1.5X10 -3~4.0×103μg L−1, and the detection limit is 1.8X10 -5μg L−1.
The invention has the technical characteristics and advantages that:
1. The detection method is based on an electrochemical sensor, can sensitively and accurately collect and analyze information without extracting nano-plastic in water in advance, realizes trace in-situ detection of the nano-plastic with small size, has the advantages of simple operation, low cost, wide detection range of the nano-plastic, low detection limit and high sensitivity, and is a label-free, rapid, efficient, miniaturized and high-flux particle detection method.
2. The detection method of the invention realizes that the detection of the nano plastic in the range of 1.5 multiplied by 10 -3~4.0×103μg L−1 has higher sensitivity, and the detection limit is as low as 1.8 multiplied by 10 -5μg L-1.
3. The nano-plastic electrochemical sensor constructed by the detection method has excellent sensitivity and repeatability.
4. The detection method of the invention has the advantages of no need of complex instruments or complicated pretreatment, simple operation, low cost, capability of realizing in-situ analysis detection and high accuracy of results.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of Ti 3AlC2 powder, MXene NSs (MXene nanoplatelets) and Mg 2+-MXene aerogels （Mg2+ -MXene aerogel).
FIG. 2 is a Scanning Electron Microscope (SEM) image of Mg 2+ -MXene aerogel.
FIG. 3 is a pictorial view of a nano-plastic electrochemical sensor based on Mg 2+ -MXene aerogel;
a is a structural schematic diagram of an electrochemical sensor, namely a counter electrode, a working electrode, a reference electrode, a substrate and a working electrode, wherein the surface of the working electrode is coated with Mg 2+ -MXene aerogel;
and b is a physical diagram of the electrochemical sensor after bending.
Fig. 4 is a Scanning Electron Microscope (SEM) image of an electrochemical sensor after exposure to standard solutions of nanomaterials at concentrations of 1000, 100, and 25 μg mL -1.
FIG. 5 is a Nyquist plot of various treatments of SPE, E-MXene NSs, E-Mg 2+-MXene aerogels、E-MXene NSs-NPs、E-Mg2+ -MXene aerogels-NPs; the potential is 0.24V, the frequency domain range is 10 5~100 Hz, and the amplitude is 10 mV; the abscissa is the real impedance part (Z Re), and the ordinate is the imaginary impedance part (Z im);
wherein SPE is a blank screen printing electrode,
E-MXene NSs are electrochemical sensors constructed by dipping a single-layer Ti 3C2Tx MXene solution in the step (2) of the example 1 on the surface of a screen printing electrode;
E-Mg 2+ -MXene aerogels is the Mg 2+ -MXene aerogel based nano-plastic electrochemical sensor of example 2;
E-MXene NSs-NPs are electrochemical sensors constructed by dripping nano plastic standard sample liquid with the concentration of 25 mug mL -1 on the surface of the E-MXene NSs electrochemical sensor;
E-Mg 2+ -MXene aerogels-NPs are electrochemical sensors constructed by dripping nano plastic standard sample liquid with the concentration of 25 mug mL -1 on the surface of the E-Mg 2+ -MXene aerogels electrochemical sensor.
FIG. 6 is a Nyquist plot and operating curve of a sensor constructed from aqueous solutions of nano-plastics of different standard concentrations;
a is a Nyquist diagram of an electrochemical sensor constructed by nano plastic water solutions with different standard concentrations in an electrolyte solution, wherein the electrolyte solution is a potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferricyanide, and the concentration of the potassium chloride is 0.1mol/L; the potential is 0.24V, the frequency domain is 10 5~100 Hz, and the amplitude is 10mV; the abscissa is the real impedance part (Z Re), and the ordinate is the imaginary impedance part (Z im); the curve a is 0.0015 [ mu ] g L -1, b is 0.0025 [ mu ] g L -1, c is 0.003 [ mu ] g L -1, d is 0.01 [ mu ] g L -1, e is 0.015 [ mu ] g L -1, f is 0.15 [ mu ] g L -1, g is 1.5 [ mu ] g L -1, h is 30 [ mu ] g L -1, i is 100 [ mu ] g L -1, j is 400 [ mu ] g L -1, k is 1800 [ mu ] g L -1, and l is 4000 [ mu ] g L -1.
B is a working curve of the electrochemical sensor constructed by the nano plastic aqueous solutions with different standard concentrations; the abscissa is the nano-plastic concentration and the ordinate is the interfacial resistance.
FIG. 7 is a Nyquist diagram and a working curve of a sensor constructed from water samples with different nano-plastic contents in a marine water environment;
a is a Nyquist diagram of an electrochemical sensor constructed by water samples with different nano plastic contents in a marine water environment in an electrolyte solution, wherein the electrolyte solution is a potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferricyanide, and the concentration of the potassium chloride is 0.1mol/L; the potential is 0.24V, the frequency domain is 10 5~100 Hz, and the amplitude is 10mV; the abscissa is the real impedance part (Z Re), and the ordinate is the imaginary impedance part (Z im); curve a is 0.002 μ g L -1, b is 0.0025 μ g L -1, c is 0.003 μ g L -1, d is 0.01 μ g L -1, e is 0.015 μ g L -1;
b is a working curve (a) of an electrochemical sensor constructed by different nano-plastic contents in a marine water environment and a working curve (b) of the electrochemical sensor constructed by a nano-plastic solution in a deionized water environment with different standard concentrations; the abscissa is the nano-plastic concentration and the ordinate is the interfacial resistance.
Detailed Description
In order to more clearly illustrate the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of Mg 2+ -MXene aerogel:
(1) Placing a polytetrafluoroethylene bottle on a magnetic stirrer, firstly adding 20mL of concentrated HCl (9M, hydrochloric acid concentration is 36-38%), slowly adding 1.6g of LiF (lithium fluoride) at the rotation speed of 600rpm and the temperature of 40 ℃, stirring until the LiF is dissolved, and then slowly adding 1g of Ti 3AlC2 -MAX powder in batches; secondly, maintaining the temperature at 40 ℃ for etching for 24 hours; pouring the solution into a centrifuge tube, centrifugally washing the etching solution at 5000r/min, centrifuging for 1 min each time, and repeatedly centrifugally washing until the pH value is more than or equal to 6 to obtain a colloid solution of Ti 3C2 -MXene;
(2) Introducing argon into the Ti 3C2 -MXene colloid solution for protection, and performing ice bath ultrasonic dispersion for 40min; centrifuging at 10000r/min for 60min, collecting supernatant, and diluting high-concentration single-layer Ti 3C2Tx MXene dispersion to 5mg/mL to obtain single-layer Ti 3C2Tx MXene solution;
(3) The single-layer Ti 3C2Tx MXene solution is rapidly added into a glass bottle containing 20 mu L of 1mol/L MgCl 2 solution, mixed and stood for 30s, frozen overnight, and then placed in a vacuum freeze dryer for drying for 24 hours to prepare the Mg 2+ -MXene aerogel.
The resulting Mg 2+ -MXene aerogel XRD, see FIG. 1, shows that the (002) peak of MXene shifts left from 6.1 ° (original MXene nanoplatelets without Mg 2+ inserted) to 5.4 ° (Mg 2+ -MXene aerogel), corresponding to an interlayer expansion of 0.6A, approaching the size of Mg 2+ (0.7A). This suggests that Mg 2+ was successfully inserted between MXene nanoplatelets.
The SEM of the prepared Mg 2+ -MXene aerogel is shown in FIG. 2, and FIG. 2 shows that the Mg 2+ -MXene aerogel is a layered three-dimensional network structure formed by micro-mesoporous combination.
The Mg 2+ -MXene aerogel material has good conductivity, and compared with a two-dimensional material, the Mg 2+ -MXene aerogel material has a three-dimensional space network structure, so that the material has a higher specific surface area, and the specific surface area is about 51.1m 2g−1.
Example 2
Construction of a nano-plastic electrochemical sensor based on Mg 2+ -MXene aerogel:
1) Screen Printed Electrode (SPE) was ultrasonically cleaned and then activated by cyclic voltammetry in 0.5mol/L H 2SO4 solution with the following activation parameters: scanning range is 1.5-2.0V; the sweeping speed is 0.1V s -1.
2) The Mg 2+ -MXene aerogel prepared in example 1 was mixed in deionized water, stirred into a uniform suspension, 1.5Mg/mL of Mg 2+ -MXene aerogel solution was obtained, 4. Mu.L of Mg 2+ -MXene aerogel solution was added dropwise to the surface of the working electrode of the activated electrode, and the mixture was dried at room temperature, thus obtaining a nano-plastic electrochemical sensor based on the Mg 2+ -MXene aerogel, which was designated as E-Mg 2+ -MXene aerogels.
The physical diagram of the prepared nano-plastic electrochemical sensor based on the Mg 2+ -MXene aerogel is shown in fig. 3, and as can be seen from fig. 3, the electrochemical sensor prepared by the invention has good flexibility.
Exposing the prepared electrochemical sensor to nano plastic standard solutions with the concentrations of 1000, 100 and 25 mug mL -1 for 2min respectively, taking out a test SEM, and measuring the SEM to be shown in figure 4, wherein the surface of the working electrode is adsorbed with different amounts of nano plastic particles, the higher the concentration of the nano plastic standard solution is, the higher the content of the nano plastic particles on the surface of the electrode is, the nano plastic with different concentrations is strongly adsorbed on the working electrode, so that the effective reduction of the electroactive area of the working electrode can be caused, and different interface resistance values can be generated; the electrochemical sensor provided by the invention can be used for enriching the nano plastic in situ, so as to realize in-situ analysis and detection.
Different electrochemical sensors of SPE, E-MXene NSs and E-Mg 2+-MXene aerogels、E-MXene NSs-NPs、E-Mg2+ -MXene aerogels-NPs are immersed into electrolyte solution for testing Nyquist, wherein the electrolyte solution is potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferricyanide, and the concentration of the potassium chloride is 0.1mol/L; as a result of the test, as can be seen in FIG. 5, R ct of E-Mg 2+ -MXene aerogels is much smaller than E-MXene NSs, showing that the conductivity and electrochemical activity of E-Mg 2+ -MXene aerogels are superior to E-MXene NSs, as can be seen from FIG. 5.
After addition of the nanoflastic, both E-MXene NSs and R ct of E-Mg 2+ -MXene aerogels increased significantly, with the R ct increase of E-Mg 2+ -MXene aerogels being stronger. Impedance element analysis was deduced from ZSimp Win software due to the physical absorption of the nanomaterials on the aerogel by hydrogen bonding interactions, resulting in the inherent steric hindrance associated with the absorption of the nanomaterials preventing the iron/ferricyanide ions from reaching the electrode surface or the electrostatic barrier of the electrode surface preventing electrons from transferring at the electrode surface. And thus the formation of an insulating layer, which hinders electron transfer kinetics between interfaces.
Example 3
A method for quantitatively detecting nano-plastics in water based on an electrochemical sensor comprises the following steps:
I: preparing target nano plastic aqueous solutions with different standard concentrations, dripping 4 mu L of nano plastic standard samples with different concentrations in an electrochemical sensor working electrode area, drying at room temperature, and immersing the electrochemical sensor with the dripped standard sample solution into an electrolyte solution, wherein the electrolyte solution is a potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferrocyanide, and the concentration of the potassium chloride is 0.1mol/L;
II: the electrochemical impedance spectrum is used for driving, the electrochemical impedance spectrum is used for detecting the interface resistance change when the working electrode is in contact with the nano plastic in the frequency domain range of 10 5~100 Hz under the action of alternating current sinusoidal potential disturbance with the amplitude of 10mV, ZSimp Win software is used for deducing the value of an impedance element, and the obtained EIS data is modeled as an equivalent circuit.
III: drawing a standard working curve according to the relation between the electrode interface resistance (R ct) and the concentration of the nano-plastic concentration linear relation curve standard solution concentration;
IIII: seawater was collected from yellow sea in Qingdao, shandong, china with a glass bottle. Microplastic and other large particles in the water are removed by a pre-filtration step of the polytetrafluoroethylene membrane. Then preparing target nano plastic aqueous solutions with different standard concentrations in a seawater body, dripping 4 mu L of nano plastic seawater sample with different concentrations in an electrochemical sensor working electrode area, drying at room temperature, immersing the electrochemical sensor with the dripped standard sample solution into an electrolyte solution at room temperature, wherein the electrolyte solution is a potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferrocyanide, and the concentration of the potassium chloride is 0.1mol/L;
IIIII: dropwise adding a water sample to be detected into a working electrode area of an electrochemical sensor, drying at room temperature, and immersing the electrochemical sensor dropwise added with the sample to be detected into an electrolyte solution, wherein the electrolyte solution is a potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferrocyanide, and the concentration of the potassium chloride is 0.1mol/L;
The electrochemical impedance spectrum is adopted for driving, the electrochemical impedance spectrum is used for detecting interface resistance change when a working electrode is contacted with nano plastic in a frequency domain range of 10 5~100 Hz under the action of alternating current sinusoidal potential disturbance with the amplitude of 10mV, ZSimp Win software is used for deducing the value of an impedance element, and the obtained EIS data is modeled as an equivalent circuit; and (3) obtaining the concentration of the nano plastic in the environmental water sample to be detected according to the obtained interface resistance value and the working curve obtained in the step (II).
At room temperature, immersing an electrochemical sensor dropwise added with standard sample solutions with different concentrations into an electrolyte solution, wherein the electrolyte solution is a potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferrocyanide, and the concentration of the potassium chloride is 0.1mol/L; impedance spectroscopy was performed and the Nyquist plot in the electrochemical impedance spectrum is shown in fig. 6a.
When the concentration of the nano plastic is 0.0015 mu g L -1, two part curves of a real part Z Re and an imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve a in fig. 6a, and as can be seen from a curve a in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 serving as electrolyte.
When the concentration of the nano plastic is 0.0025 mu g L -1, two part curves of a real part Z Re and an imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve b in fig. 6a, and as can be seen from a curve b in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 serving as electrolyte.
When the concentration of the nano plastic is 0.003 mu g L -1, two part curves of a real part Z Re and an imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve c in fig. 6a, and as can be seen from the curve c in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 serving as electrolyte.
When the concentration of the nano plastic is 0.01 mu g L -1, two part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve d in fig. 6a, and as can be seen from the curve d in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 serving as electrolyte.
When the concentration of the nano plastic is 0.015 mu g L -1, two part curves of a real part Z Re and an imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve e in fig. 6a, and as can be seen from a curve e in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 serving as electrolyte.
When the concentration of the nano plastic is 0.15 mu g L -1, two part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve f in fig. 6a, and as can be seen from a curve f in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 serving as electrolyte.
When the concentration of the nano plastic is 1.5 mu g L -1, two part curves of a real part Z Re and an imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve g in fig. 6a, and as can be seen from the curve g in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 serving as electrolyte.
When the concentration of the nano plastic is 30 mu g L -1, the two-part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve h in fig. 6a, and as can be seen from a curve h in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 as electrolyte.
When the concentration of the nano plastic is 100 mu g L -1, two part curves of a real part Z Re and an imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve i in fig. 6a, and as can be seen from the curve i in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 as electrolyte.
When the concentration of the nano plastic is 400 mu g L -1, two part curves of a real part Z Re and an imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve j in fig. 6a, and as can be seen from the curve j in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 as electrolyte.
When the concentration of the nano plastic is 1800 mu g L -1, the two-part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve k in fig. 6a, and as can be seen from the curve k in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in the electrolyte which is 0.1mol/L KCl solution of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6.
When the concentration of the nano plastic is 4000 mu g L -1, the two-part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve L in fig. 6a, and as can be seen from the curve L in fig. 6a, the interface resistance value of the nano plastic electrochemical sensor can be collected in a solution of 0.1mol/L KCl of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6 as electrolyte.
As can be seen from fig. 6b, R ct is proportional to Log 10CNPs, which indicates that the constructed nano-plastic electrochemical sensor has high sensitivity, wide detection range, and detection range of 1.5×10 -3~4.0×103μg·L−1; it should be noted that the detection limit of the method is 1.8X10 -5μgL-1, and the method covers a wide range of microplastic and nano-plastic in a wide range of water-like media, so that the method has great practical application potential.
Experimental example 1
Immersing electrochemical sensors dropwise added with nano plastic seawater sample liquid with different concentrations into electrolyte solution at room temperature, wherein the electrolyte solution is potassium chloride solution containing 10mmol/L potassium ferrocyanide and 10mmol/L potassium ferricyanide, and the concentration of the potassium chloride is 0.1mol/L; impedance spectroscopy was performed and the Nyquist plot in the electrochemical impedance spectrum is shown in fig. 7a.
When the concentration of the liquid nano plastic of the seawater sample is 0.002 mu g L -1, two part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve a in fig. 7a, and as can be seen from a curve a in fig. 7a, the nano plastic electrochemical sensor can collect interface resistance values in the electrolyte which is 0.1mol/L KCl solution of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6.
When the concentration of the liquid nano plastic of the seawater sample is 0.0025 mu g L -1, two part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve b in fig. 7a, and as can be seen from a curve b in fig. 7a, the nano plastic electrochemical sensor can collect interface resistance values in the electrolyte with 0.1mol/L KCl solution of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6.
When the concentration of the liquid nano plastic of the seawater sample is 0.003 mu g L -1, two part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve c in fig. 7a, and as can be seen from the curve c in fig. 7a, the nano plastic electrochemical sensor can collect interface resistance values in the electrolyte of 0.1mol/L KCl solution of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6.
When the concentration of the liquid nano plastic of the seawater sample is 0.01 mu g L -1, two part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve d in fig. 7a, and as can be seen from a curve d in fig. 7a, the nano plastic electrochemical sensor can collect interface resistance values in the electrolyte which is 0.1mol/L KCl solution of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6.
When the concentration of the liquid nano plastic of the seawater sample is 0.0015 mu g L -1, two part curves of the real part Z Re and the imaginary part Z im of the impedance of the constructed electrochemical sensor are shown as a curve e in fig. 7a, and as can be seen from a curve e in fig. 7a, the nano plastic electrochemical sensor can collect interface resistance values in the electrolyte with 0.1mol/L KCl solution of 10mmol/L K 3Fe(CN)6/K4Fe(CN)6.
As can be seen from fig. 7b, R ct is proportional to Log 10CNPs in the ocean water, and shows a good and almost identical linear relationship with R ct and nano-plastic concentrations under laboratory deionized water conditions, indicating that the method is not interfered by other organic or inorganic substances that may be present in the ocean.
Claims (9)
1. A method for quantitatively detecting nano-plastics in water based on an electrochemical sensor comprises the following steps:
1) Constructing an electrochemical sensor;
The electrochemical sensor is prepared by the following steps:
a. Polishing a screen printing electrode, performing ultrasonic cleaning, activating and drying at room temperature to obtain an activated screen printing electrode, wherein the screen printing electrode comprises a substrate, a working electrode, a reference electrode and a counter electrode;
b. Dropwise adding a Mg 2+ -MXene aerogel solution on the surface of a working electrode of the activated screen printing electrode, and drying at room temperature to obtain a screen printing electrode of modified Mg 2+ -MXene aerogel, namely an electrochemical sensor;
The Mg 2+ -MXene aerogel solution is suspension prepared by adding Mg 2+ -MXene aerogel into deionized water and uniformly stirring, the concentration of the Mg 2+ -MXene aerogel solution is 1-3Mg/mL, and the dropwise adding amount of the Mg 2+ -MXene aerogel solution is 1-5 mu L;
2) Preparing nano plastic standard sample liquids with different concentrations, and dripping the standard sample liquid into a working electrode area of an electrochemical sensor;
3) Immersing an electrochemical sensor dropwise added with standard sample liquid into electrolyte solution at room temperature for impedance spectrum measurement, and drawing a standard working curve by utilizing the relation between the measured electrochemical impedance value and the concentration of the nano plastic standard solution;
4) Dripping a water body to be detected into a working electrode area of an electrochemical sensor, immersing the water body into an electrolyte solution according to the method of the step 3) to perform impedance spectrum measurement of a sample, and measuring an impedance value of the sample; and (3) obtaining the content of the nano plastic in the water body to be detected according to the standard working curve of the step (3).
2. The method of claim 1, wherein in step b, the Mg 2+ -MXene aerogel material is prepared as follows:
(1) Preparing a multilayer Ti 3C2Tx MXene by an acid etching method;
(2) Stripping by an ultrasonic method to form a single-layer Ti 3C2Tx MXene solution;
(3) The single-layer Ti 3C2Tx MXene solution is mixed with MgCl 2 solution, the single-layer Ti 3C2Tx MXene solution is induced to gel through Mg 2+, and the aerogel material is formed by freeze drying.
3. The method according to claim 2, wherein in the step (1), the acid etching method for preparing the multi-layer Ti 3C2Tx Mxene is specifically:
Slowly adding LiF into concentrated HCl with the concentration of 9mol/L, stirring until the LiF is dissolved to obtain a mixed solution, slowly adding Ti 3AlC2 -MAX powder into the mixed solution in batches, etching for 20-30h at the temperature of 35-45 ℃, and centrifugally washing etching solution until the pH value is more than or equal to 6 to obtain a colloid solution of Ti 3C2 -MXene; the temperature of LiF is 40 ℃, and the mass volume ratio of LiF to concentrated HCl is (1-2): (10-30), g/mL; the stirring speed is 600rpm, and the mass volume ratio of Ti 3AlC2 -MAX powder to concentrated HCl is (0.5-2): (10-30), g/mL, centrifuging, washing and etching liquid at 5000r/min, centrifuging for 1min each time, and repeatedly centrifuging and washing until the pH is more than or equal to 6.
4. The method of claim 2, wherein in step (2), the ultrasonic stripping to form a single layer of Ti 3C2Tx MXene solution is specifically:
Introducing argon into the Ti 3C2 -MXene colloid solution prepared in the step (1) for protection, and performing ice bath ultrasonic dispersion for 40min under the power of 240W; centrifuging at 10000r/min for 60min, collecting supernatant, and diluting to 4-10mg/mL to obtain single-layer Ti 3C2Tx MXene solution.
5. The method according to claim 2, wherein in the step (3), the concentration of the MgCl 2 solution is 0.5-2mol/L, the volume ratio (20-30) of the single-layer Ti 3C2Tx MXene solution to the MgCl 2 solution: 1, standing for 30s after mixing to prepare the Mg 2+ -MXene hydrogel; then, the mixture was frozen overnight to prepare an ice gel of Mg 2+ -MXene, and the ice gel was dried in a vacuum freeze dryer for 24 hours to prepare Mg 2+ -MXene aerogel.
6. The method according to claim 1, wherein in step 2), the nano-plastic standard sample solution is prepared by: adding water into the nano plastic to prepare 2.5mg/mL concentrated solution, and adding water into the concentrated solution to dilute the concentrated solution to 0.0015μg L-1、0.0025μg L-1、0.003μg L-1、0.01μg L-1、0.015μg L-1、0.15μg L-1、1.5μg L-1、30μg L-1、100μg L-1、400μg L-1、1800μg L-1、4000μg L-1, to prepare nano plastic standard sample solutions with different concentrations.
7. The method according to claim 1, wherein in step 3), the electrolyte solution is a potassium chloride solution containing potassium ferrocyanide at a concentration of 10mmol/L and potassium ferricyanide at a concentration of 10mmol/L, and the concentration of potassium chloride is 50 to 100mmol/L.
8. The method according to claim 1, wherein in step 3), the impedance spectrum measurement is performed using an ac sinusoidal voltage having a frequency range of 0.1 to 10 5 Hz and an amplitude of 5 to 15 mV.
9. The method according to claim 1, wherein the amount of the standard sample solution added in step 2) is 4. Mu.L, and the amount of the water to be measured in step 4) is 4. Mu.L.
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