CN111751421A - Electrochemical sensor for quickly and efficiently detecting lead ions - Google Patents
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Abstract
The invention discloses an electrochemical sensor for rapidly and efficiently detecting lead ions, which is characterized in that Bi-MOFs and Graphene Oxide (GO) layers are constructed on the surface of a Glassy Carbon Electrode (GCE) by a layer-by-layer (LbL) assembly technology, then the GO in a composite material is subjected to electrical reduction, and two insulating Bi-MOFs/GO layers are converted into two conductive Bi-MOFs/rGO layers. Bi-MOFs/rGO modified glassy carbon electrode GCE/[ Bi-MOFs/rGO]2For electrochemical sensors, for Pb in electrolyte solutions2+And carrying out electrochemical detection. GCE/[ Bi-MOFs/GO]2For Pb2+Shows good detection sensitivity. The electrochemical sensor constructed by the invention can realize the aim of adjusting Pb2+And can be used for the quantitative analysis of Pb2+And carrying out rapid detection.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to an electrochemical sensor for quickly and efficiently detecting lead ions.
Background
Pb2+Is one of the most well known toxic heavy metals and can damage the function of the nervous system, brain, hematopoietic system and liver even at low concentrations, with various serious or fatal consequences. Infants and young children face a greater risk of lead poisoning than adults. Therefore, the development of sensitive Pb is urgently required2+And (3) a detection method. So far, various Pb2+Analytical strategies have been developed such as inductive microprobes, atomic absorption/emission spectroscopy, voltammetric sensors, X-ray fluorescence spectroscopy, surface enhanced raman scattering, and colorimetric spectroscopy. Particularly, voltammetry is Pb because of its simplicity of operation, high sensitivity, low cost and portability2+Good strategy for detection. For voltammetry, the ability to dynamically assess low concentrations of metals in aqueous solutions is critical for effective monitoring of trace heavy metal ions. Therefore, it is very important to design advanced electrode materials having good adsorption capacity.
The bismuth electrode has the advantages of low toxicity, easy alloy formation, high adjacent peak resolution and the like, and is widely researched in heavy metal ion electroanalysis. Bi nanoparticles (BiNPs) have high electrocatalytic activity due to their large specific surface area and abundant active sites. However, due to the higher surface free energy, BiNPs tend to form aggregates, resulting in reduced performance. Compared with nano-form materials, a metal-organic framework (MOFs) system formed by self-assembling coordination bonds between organic ligands and metal ions has the advantages of good crystallinity, good structural diversity, strong tailorability, large specific surface area, adjustable pore diameter, easiness in preparation and the like. In particular, the porous structure of the MOFs and the organic ligand thereof can promote high-level enrichment of heavy metal ions, which is beneficial to improving the sensitivity of electrochemical sensing detection.
Pure MOFs have limited their application in electrocatalysis due to their poor stability, poor conductivity, etc. Researchers have studied cyclic voltammetry for measuring lead ions by using a Co/MOFs-pT modified electrode (volume 4 of the university of North and Central (Nature science edition) 2017, volume 38, Huanghua by authors, etc.), a glassy carbon electrode modified by compounding Co/MOFs and nano platinum particles is used, and the concentration of the lead ions is measured in an acetate buffer solution by using the cyclic voltammetry, but the detection sensitivity of the electrode is low, the detection limit is 0.12 mu M, and the cost of the electrode is too high by modifying the platinum particles. Therefore, it is now necessary to prepare an electrochemical sensor containing MOFs, so that the detection sensitivity is high and the sensor manufacturing cost is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an electrochemical sensor for quickly and efficiently detecting lead ions, a Bi-MOFs/GO film is constructed on the surface of a glassy carbon electrode by a layer-by-layer (LbL) assembly technology, the Bi-MOFs/GO is reduced to the Bi-MOFs/rGO film, and the Bi-MOFs/rGO electrode is directly used as an electrochemical sensing platform for measuring Pb2+. The detection method has the advantages of simple operation, high response speed, high sensitivity and good stability, and makes the on-site and on-line rapid detection of the heavy metal ions possible.
The invention is realized by the following technical scheme:
in a first aspect of the present invention, an electrochemical sensor for rapidly and efficiently detecting lead ions is provided, wherein the sensor is prepared by the following method:
(1) adding Bi (NO)3·5H2O and H3Adding BTC into mixed solution of DMF and methanol, performing ultrasonic treatment to obtain mixed solution, performing hydrothermal treatment on the mixed solution under sealed condition, and performing treatment with DMF and CH3OH is washed, centrifuged and dried to obtain Bi-MOFs (bismuth-metal organic framework compound);
(2) dispersing the Bi-MOFs obtained in the step (2) in DMF to obtain a Bi-MOFs solution, dispersing GO (graphene oxide) in DMF to obtain a GO solution, dripping the Bi-MOFs solution on the surface of GCE (glass carbon electrode), drying to obtain GCE/Bi-MOFs, dripping the GO solution on GCE/Bi-MOFs, drying again to obtain GCE/Bi-MOFs/GO, repeating the steps, preparing a Bi-MOFs/GO layer on GCE/Bi-MOFs/GO, and obtaining GCE/[ Bi-MOFs/GO ] by]2The GCE/[ Bi-MOFs/GO is electrochemically converted]2Reducing to obtain GCE/[ Bi-MOFs/rGO]2An electrochemical sensor.
Preferably, in the step (1), the volume ratio of DMF to methanol is 4: 1; said Bi (NO)3·5H2O and H3Quality of BTCThe ratio is 1: 5; said Bi (NO)3·5H2O and H3The ratio of the total mass of BTC to the total volume of the mixed solution of DMF and methanol was 0.9 g: 60 mL.
Preferably, in the step (1), the temperature of the hydrothermal treatment is 110-130 ℃, and the treatment time is 24 hours.
Preferably, in the step (1), the drying temperature is 80 ℃ and the drying time is 5-7 h.
Preferably, in the step (2), the concentration of the Bi-MOFs solution is 0.5 mg/mL-1The concentration of the GO solution is 1 mg/mL-1。
Preferably, in the step (2), the potential of the electrochemical method is-1.3V, and the reduction time is 300 s.
In a second aspect of the present invention, there is provided a use of the above electrochemical sensor for detecting lead ions.
In a third aspect of the present invention, there is provided a method for detecting lead ions by the electrochemical sensor, including the steps of:
adding an electrolyte solution into a solution containing lead ions, uniformly mixing to obtain a mixed test solution, connecting the electrochemical sensor with a test circuit, immersing the electrochemical sensor into the mixed test solution, performing deposition for 210s at-1.3V by using a magnetic stirring method, detecting the stripping peak current value of the sensor by using a differential pulse stripping voltammetry method, establishing a standard curve according to the concentration of the lead ions and the stripping peak current value, and calculating the concentration of the lead ions in the solution to be tested according to the standard curve.
Preferably, the electrolyte solution is 0.1M acetate buffer at pH 5.0.
Preferably, the detection range is 0.3 nM-9.0. mu.M, with a detection limit of 0.1 nM.
The invention has the beneficial effects that:
1. GCE/[ Bi-MOFs/GO prepared by the invention]2The multilayer structure not only promotes the full exposure of active sites, but also improves the electrical contact with the active edge parts, thereby greatly improving the electrochemical sensing performance.
2. The method for detecting the concentration of the lead ions has the advantages of simple operation, high response speed, high sensitivity and good stability, and makes the on-site and on-line rapid detection of the heavy metal ions possible.
3. The electrochemical sensor prepared by the method has the advantages of low cost, simple process and simple operation, and not only can be successfully used for Pb2+And also has high sensitivity (Pb)2+Lower limit of detection is 0.1nM), and strong selectivity (Ca)2+，Mg2+，Ag+，Na+，Co2 +，Mn2+，K+，Al3+，Ni2+，Hg2+，Cd2+，Cu2+The materials have no response), the stability is good, and the prepared Bi-MOFs/rGO material modified electrode can be used for Pb in the environment2+And (4) measuring the content.
Drawings
FIG. 1: (A) scanning Electron Microscope (SEM) of Bi-MOFs material, (B) Scanning Electron Microscope (SEM) of Bi-MOFs/rGO material, and (C) Scanning Electron Microscope (SEM) cross section of Bi-MOFs/rGO;
FIG. 2 shows rGO/GCE electrodes, GCE/Bi-MOFs electrodes, and electrochemical sensor pairs prepared in example 1 for 5.0 μ MPb2+The differential pulse stripping voltammetry response graph of (1);
FIG. 3(a) is a graph showing that the electrochemical sensor prepared in example 1 detects Pb at various concentrations2+The differential pulse stripping voltammetry response graph of (1); the curves are from bottom to top: detecting differential pulse stripping voltammetry response curves of lead ion solutions with the concentrations of 0.3nM, 7.0nM, 30.0nM, 0.5 muM, 0.7 muM, 0.9 muM, 1.0 muM, 2.0 muM, 3.0 muM, 5.0 muM, 7.0 muM and 9.0 muM;
(b) is a standard graph.
FIG. 4 shows 50-fold concentration of Ca under optimized conditions2+，Mg2+，Ag+，Na+，Co2+，Mn2+，K+，Al3+，Ni2+，Hg2+，Cd2+，Cu2+Metal ion pair of 5.0 μ M Pb2+Stripping off the interference of peak current.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As mentioned in the background, the porous structure of MOFs and its organic ligand can promote high level enrichment of heavy metal ions, but its poor stability, poor conductivity and other problems limit its application in electrocatalysis. Therefore, the design and synthesis of the MOFs material with high heavy metal adsorption capacity meets the requirement of selective detection of heavy metal ions, and is the key for improving the sensitivity and selectivity of electrochemical detection. Based on the electrochemical sensor, the invention provides the electrochemical sensor for quickly and efficiently detecting the lead ions. The method comprises the step of constructing Bi-MOFs and Graphene Oxide (GO) sheets on the surface of a Glassy Carbon Electrode (GCE) by a layer-by-layer (LbL) assembly technology to obtain GCE/[ Bi-MOFs/GO)]2In the invention, the effective specific surface area of the electrode is increased by the dropping amount, but the effective specific surface area of the electrode is reduced by the excessive amount, so that the Bi-MOFs/GO layer is optimally dropped to obtain two layers. And then carrying out electrical reduction on GO in the composite material, converting the insulated Bi-MOFs/GO multilayer film into a conductive Bi-MOFs/rGO film, and carrying out reduction for 300s at-1.3V for thorough reduction. With GCE/[ Bi-MOFs/GO]2For electrochemical sensors, the reaction of Pb in a solution with acetate as supporting electrolyte2+And carrying out electrochemical detection.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments. If the experimental conditions not specified in the examples are specified, the conditions are generally conventional or recommended by the reagent company; reagents, consumables, and the like used in the following examples are commercially available unless otherwise specified.
Description of the drawings: terephthalic acid (H) used in the examples3BTC) was purchased from shanghai alatin biochemical science ltd.
Example 1:
preparation of electrochemical sensor
1. First, 0.15g of Bi (NO)3·5H2O and 0.75g H3BTC was added to 60mL of a mixed solution of DMF and methanol. After 10 minutes of sonication, the mixture was sealed in a 100mL stainless steel autoclave lined with Teflon and hydrothermally treated at 120 ℃ for 24 hours. Then with DMF and CH3OH washes were centrifuged three times. Drying at 80 ℃ for 6 hours to obtain the Bi-MOFs.
2.GCE/[Bi-MOFs/GO]2The preparation of (1): Bi-MOFs were dispersed in DMF at a concentration of 0.5 mg. multidot.mL-1. GO is dispersed in DMF at a concentration of 1 mg. mL-1.5 mu L of Bi-MOFs solution is dripped on the surface of GCE, and after being dried in an oven at 45 ℃ for 5min, 5 mu L of GO solution is dripped on the surface of GCE/Bi-MOFs. After drying, a layer of Bi-MOFs/GO composite membrane is formed on the GCE. And repeating the steps once to obtain the GCE modified by the two layers of Bi-MOFs/GO composite materials. Finally, GCE/[ Bi-MOFs/GO is electrochemically treated]2Reducing to obtain GCE/[ Bi-MOFs/rGO]2。
The Scanning Electron Microscope (SEM) image of the Bi-MOFs/rGO prepared in example 1 is shown in FIG. 1, the Bi-MOFs have a long broom-like structure consisting of several rods (FIG. 1A), and in the Bi-MOFs/rGO (FIG. 1B), the Bi-MOFs like broom are dispersed in the folded rGO. The layer-by-layer structure can be found from the cross-sectional image (fig. 1C). The rGO layer shows a sheet structure, and the Bi-MOFs is sandwiched between layers, which indicates the successful combination of the multi-layer Bi-MOFs/rGO.
Example 2
Detecting the concentration of lead ions
Different concentrations (0.3nM, 7.0nM, 30.0nM, 0.5. mu.M, 0.7. mu.M, 0.9. mu.M, 1.0. mu.M, 2.0. mu.M, 3.0. mu.M, 5.0. mu.M, 7.0. mu.M, 9.0. mu.M) of Pb were added2+The solutions were added to acetic acid buffer solution with pH 5.0, the electrochemical sensor prepared in example 1 was connected to a test circuit, and Pb was measured by differential pulse stripping voltammetry2+Concentration is measured as Pb2+Concentration is plotted on the abscissa (in. mu.M) and the value of the peak current is plotted on the ordinate (in. mu.A), and a calibration curve y of 2.19+9.28x (R) is established2＝0.996)。
As shown in FIG. 3, the modified electrode pair is Pb2+Has good linear relation (R)20.996) and has wider linesThe range of the property (0.3nM-9.0 μ M) and the higher sensitivity and the lower detection limit (0.1nM) fully indicate that the sensing electrode can successfully detect the Pb with unknown concentration2+。
Differential pulse stripping voltammetry is used for Pb by using rGO and Bi-MOFs modified glassy carbon electrodes (namely rGO/GCE and GCE/Bi-MOFs) and the sensor prepared in example 12+Detecting, and testing different modified electrode pairs for Pb2+The results are shown in FIG. 2.
As can be seen from FIG. 2, the sensor prepared in example 1 can cope with extremely low Pb compared with rGO and Bi-MOFs modified glassy carbon electrodes and glassy carbon electrodes (i.e., Bare GCE)2+The concentration responds, and the detection sensitivity is better than that of the rGO and Bi-MOFs modified glassy carbon electrode.
Detection of Pb in the electrochemical sensor prepared in example 12+Concentration specificity study: investigation of Pb before and after addition of interfering ions2+The specific results are shown in FIG. 3; as can be seen from FIG. 3, each Pb was 5.0. mu.M2+Ca is added into the solution in 50 times of concentration2+，Mg2+，Ag+，Na+，Co2+，Mn2+，K+，A13+，Ni2+，Hg2+，Cd2+，Cu2+Then, Pb2+The dissolution peak current of (a) is not significantly changed (error range of + -5.0%), thereby excluding interference of some common ions.
Detection of Pb in the electrochemical sensor prepared in example 12+Concentration accuracy study: tap water was mixed with 0.1M acetate buffer in equal volume by standard addition method, and then Pb was added at different concentrations2+The solution was added and the above solution was subjected to detection analysis using the sensor prepared in example 1, and the results are shown in Table 2.
TABLE 1
| Standard concentration of μ M | 0.10 | 0.50 | 1.00 | 2.00 | 5.00 |
| Detection concentration of μ M | 0.098 | 0.520 | 0.993 | 2.122 | 5.01 |
As can be seen from Table 1, the accuracy of the above detection is between 98.00% and 106.10%, and the relative standard deviation is between 2.07% and 2.56%, indicating that the sensor is constructed for Pb2+Detection analysis of the actual sample is feasible.
In conclusion, the electrochemical sensor of the invention can successfully detect Pb2+And has the characteristics of high sensitivity, quick detection, good stability and the like, and the electrochemical sensor can be used for Pb2+Concentration and Pb in tap water2+Measuring the content of (A); the preparation method of the electrochemical sensor has the advantages of low preparation cost, simple process and simple and easy operation.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. An electrochemical sensor for rapidly and efficiently detecting lead ions is characterized by being prepared by the following steps:
(1) adding Bi (NO)3·5H2O and terephthalic acid (H)3BTC) is added into a mixed solution of DMF and methanol, mixed solution is obtained after ultrasonic treatment, the mixed solution is subjected to hydro-thermal treatment under a sealing condition, and DMF and CH are used after the treatment3OH washing, centrifuging and drying to obtain Bi-MOFs;
(2) dispersing the Bi-MOFs obtained in the step (2) in DMF to obtain a Bi-MOFs solution, dispersing GO in DMF to obtain a GO solution, dripping the Bi-MOFs solution on the surface of GCE, drying to obtain GCE/Bi-MOFs, dripping the GO solution on GCE/Bi-MOFs, drying again to obtain GCE/Bi-MOFs/GO, repeating the steps, preparing a Bi-MOFs/GO layer on GCE/Bi-MOFs/GO, and obtaining GCE/[ Bi-MOFs/GO ] by]2The GCE/[ Bi-MOFs/GO is electrochemically converted]2Reducing to obtain GCE/[ Bi-MOFs/rGO]2The electrochemical sensor is an electrochemical sensor for rapidly and efficiently detecting lead ions.
2. The electrochemical sensor according to claim 1, wherein in the step (1), the Bi (NO)3·5H2O and H3The mass ratio of BTC is 1: 5; the volume ratio of DMF to methanol is 4: 1; said Bi (NO)3·5H2O and H3The ratio of the total mass of BTC to the total volume of the mixed solution of DMF and methanol was 0.9 g: 60 mL.
3. The electrochemical sensor according to claim 1, wherein in the step (1), the temperature of the hydrothermal treatment is 110-130 ℃ and the treatment time is 24 h.
4. The electrochemical sensor according to claim 1, wherein in the step (1), the drying temperature is 80 ℃ and the drying time is 5-7 h.
5. The electrochemical sensor according to claim 1, wherein in step (2), the Bi-MOFs solutionHas a concentration of 0.5 mg/mL-1The concentration of the GO solution is 1 mg/mL-1。
6. The electrochemical sensor according to claim 1, wherein in the step (2), the potential of the electrochemical method is-1.3V, and the reduction time is 300 s.
7. Use of an electrochemical sensor according to any one of claims 1 to 6 for detecting lead ions.
8. The method for detecting lead ions by an electrochemical sensor according to any one of claims 1 to 6, comprising the steps of:
adding an electrolyte solution into a solution containing lead ions, uniformly mixing to obtain a mixed test solution, connecting the electrochemical sensor according to any one of claims 1 to 6 with a test circuit, immersing the electrochemical sensor into the mixed test solution, performing deposition for 210s at-1.3V by using a magnetic stirring method, detecting the stripping peak current value of the sensor by using a differential pulse stripping voltammetry method, establishing a standard curve according to the concentration of the lead ions and the stripping peak current value, and calculating the concentration of the lead ions in the solution to be tested according to the standard curve.
9. The method of claim 8, wherein the electrolyte solution is 0.1M acetate buffer at pH 5.
10. The method of claim 8, wherein the detection range is 0.3nM to 9.0 μ M, and the detection limit is 0.1 nM.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010677921.7A CN111751421B (en) | 2020-07-14 | 2020-07-14 | Electrochemical sensor for detecting lead ions |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010677921.7A CN111751421B (en) | 2020-07-14 | 2020-07-14 | Electrochemical sensor for detecting lead ions |
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| CN111751421A true CN111751421A (en) | 2020-10-09 |
| CN111751421B CN111751421B (en) | 2021-06-04 |
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| CN113899796A (en) * | 2021-09-26 | 2022-01-07 | 江西农业大学 | High-sensitivity detection of Pb2+Ratiometric electrochemical sensors and their use |
| CN114397340A (en) * | 2021-12-18 | 2022-04-26 | 江西农业大学 | Electrochemical sensor for detecting benomyl and preparation method thereof |
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