CN114609223A - Electrochemical sensor for simultaneously or respectively detecting zinc ions, lead ions and cadmium ions and preparation method thereof - Google Patents

Electrochemical sensor for simultaneously or respectively detecting zinc ions, lead ions and cadmium ions and preparation method thereof Download PDF

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CN114609223A
CN114609223A CN202210195458.1A CN202210195458A CN114609223A CN 114609223 A CN114609223 A CN 114609223A CN 202210195458 A CN202210195458 A CN 202210195458A CN 114609223 A CN114609223 A CN 114609223A
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bismuth
biomass graphene
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CN114609223B (en
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单炜军
李思雨
冯小庚
于海彪
王月娇
崔俊硕
高婧
娄振宁
熊英
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Liaoning University
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Abstract

The invention relates to an electrochemical sensor for simultaneously or respectively detecting zinc ions, lead ions and cadmium ions and a preparation method thereof, belonging to the field of electrochemical detection. The electrochemical sensor comprises an electrochemical workstation, an electrolytic cell, a counter electrode, a reference electrode and a working electrode, wherein the working electrode is a bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode, the effective component is a bismuth-based metal organic framework/biomass graphene composite material, green and environment-friendly biomass graphene is obtained by high-temperature cracking of microcrystalline cellulose, then thermal reflux treatment is carried out, and then methanol is used as a solvent to be added with bismuth nitrate and trimesic acid for reaction, so that the composite material of the bismuth-based metal organic framework, which is uniformly loaded with the biomass graphene, is obtained. The invention is applied to simultaneously or respectively detecting zinc ions, cadmium ions and lead ions, shows better capability of electrically detecting metal ions and lower detection limit, and has simple synthesis method, high detection speed and certain practical applicability.

Description

Electrochemical sensor for simultaneously or respectively detecting zinc ions, lead ions and cadmium ions and preparation method thereof
Technical Field
The invention relates to an electrochemical sensor for simultaneously or respectively detecting zinc ions, lead ions and cadmium ions and a preparation method thereof, belonging to the technical field of electrochemical detection.
Background
With the rapid advance of industrialization, heavy metal pollution has become a significant environmental problem threatening human health and life safety. Cadmium metal is a highly toxic heavy metal and even at very low concentrations can cause various health problems, including heart disease, cancer, and diabetes. The metal lead ion is a toxic heavy metal which has great harm to human body, and can cause great damage to nervous system, hematopoietic system, visceral organs and endocrine system after entering into the body, and lead poisoning can be caused if the content is too high. The method has very important practical significance for reducing the harm of heavy metal ions to the environment and human beings in the ecological environment and realizing the rapid and accurate detection of the heavy metal ions in the fields of environment, food safety and the like. The content of zinc ions in blood is an important index for judging diseases such as Alzheimer disease, prostate cancer and the like, so that the detection of the content of zinc ions has an important role in biomedicine. There are many methods for metal ion detection, such as atomic absorption spectroscopy, atomic emission spectroscopy, fluorescence detection, inductively coupled plasma mass spectrometry, etc., but these analytical techniques are relatively complex. The electrochemical detection method has the advantages of simple operation, rapid response, high sensitivity and the like, has unique advantages in the aspect of heavy metal detection, and is developed into one of important means for heavy metal detection.
In the selection of electrode materials, carbon-based composite materials, noble metal nanoparticles, metal oxides, conductive polymers and the like exist, and the selection of different materials has great influence on the detection effect, so that the exploration of electrode materials used by the novel electrochemical sensor is of great significance. The metal organic framework Material (MOF), also called porous coordination polymer, has a porous structure, a relatively large specific surface area, excellent chemical tunability, etc., so that it has unique application potential in the electrochemical field, and has attracted much attention of researchers in recent years.
The bismuth-based metal organic framework takes the non-toxic bismuth with good biocompatibility as the metal central ion, so that the bismuth-based metal organic framework is relatively more environment-friendly. Bismuth is a new metal, has been widely noticed in recent years, and is often present in various forms such as bismuth nanoparticles and bismuth thin films. The bismuth nanoparticles have higher electrocatalytic activity due to the larger specific surface area and rich active sites. However, nanoparticles of bismuth tend to agglomerate, resulting in reduced performance. And the metal organic framework formed by the organic ligand and the metal ions through coordination effectively avoids the problem of self aggregation of the metal particles due to the existence of coordination bonds between the organic ligand and the metal ions. In addition, the metal organic framework has advantages such as structural diversity, high surface area, adjustable pore size, easy preparation and the like. However, MOFs have poor conductivity, and thus it is considered to compound them with conductive materials to improve the conductivity of MOFs. The biomass graphene is one of the alternatives of carbon materials due to the simple preparation method, environmental protection and low manufacturing cost. Therefore, in consideration of the characteristics of strong conductivity and high carrier rate of the biomass graphene, the biomass graphene is compounded with the bismuth-based metal organic framework, so that an electrochemical sensing platform is constructed and used for simultaneously or respectively detecting various metal ions.
For example, Chinese patent CN102798657A discloses a method for rapidly detecting heavy metals such as copper, zinc, lead and cadmium in seawater on site, and the preparation method of the composite material comprises (1) mechanically grinding conductive carbon black or superconductive carbon black and ionic liquid in a certain proportion for 50min under the protection of nitrogen; (2) putting the mixture into a polytetrafluoroethylene tube, putting the polytetrafluoroethylene tube into the tube, compacting and molding the polytetrafluoroethylene tube, and taking a copper column as a lead; (3) the electrode system was assembled with an electrochemical analyzer for measurement. Compared with the invention, the detection time is 20min, and the detection time is relatively long. Meanwhile, the price of the raw materials (ionic liquid) for preparing the composite material is relatively high.
Disclosure of Invention
The invention aims to provide an electrochemical sensor for simultaneously or respectively detecting zinc ions, cadmium ions and lead ions and a preparation method thereof, and a novel composite material is added to the electrode material applied to the existing electric detection. In order to achieve the purpose, the invention adopts the technical scheme that:
an electrochemical sensor for simultaneously or respectively detecting zinc ions, lead ions and cadmium ions comprises an electrochemical workstation, an electrolytic cell, a silver/silver chloride reference electrode, a platinum sheet counter electrode and a working electrode, and is characterized in that the working electrode is a glassy carbon electrode of a bismuth-based metal organic framework/biomass graphene/Nafion.
Further, in the electrochemical sensor, the preparation method of the glassy carbon electrode of the bismuth-based metal organic framework/biomass graphene/Nafion comprises the following steps:
1) preparing Ni-doped biomass graphene: adding nickel metal salt into water to obtain Ni (II) catalyst solution, adding the Ni (II) catalyst solution into microcrystalline Cellulose (CS), stirring for 30min, then putting the solution into an oil bath kettle at 85 ℃, heating and stirring for 4-6h to a semi-dry state, putting the semi-dry product into a porcelain boat, carrying out high-temperature pyrolysis in a tubular furnace, washing the reacted product with deionized water for three times, and carrying out vacuum drying at 60 ℃ to obtain Ni-doped biomass graphene CSG-Ni;
2) preparing biomass graphene: carrying out thermal reflux treatment on the CSG-Ni prepared in the step 1) by using 2-4mol/L hydrochloric acid, washing the solid powder obtained after the thermal reflux treatment to be neutral by using deionized water, and carrying out vacuum drying at 60 ℃ to obtain a nickel-removed biomass graphene CSG which is a small-size sheet structure with the thickness of 100-200 nm;
3) preparing a bismuth-based metal organic framework/biomass graphene composite material: adding bismuth nitrate pentahydrate (Bi)(NO3)3·5H2O) is dissolved and dispersed in 60-90mL of anhydrous methanol, and then organic ligand trimesic acid (H) is added3BTC), adding 50-600 mg of CSG prepared in the step 2), stirring for 0.5-1h at the rotating speed of 2500 plus 5000rpm, transferring to a hydrothermal reaction kettle, reacting for 24h at 120 ℃, centrifuging and washing for 3 times by using anhydrous methanol, wherein the centrifugal rotating speed is 6000 rpm, the centrifugal time is 5-15min, and drying in a 60 ℃ drying oven to obtain the Bi-based metal organic framework/biomass graphene composite material Bi-MOF/CSG;
4) preparing a bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode: dispersing the Bi-MOF/CSG prepared in the step 3) into 100 mu L of Nafion solution and 900 mu L of deionized water according to the concentration ratio of 1mg/mL-3mg/mL, performing ultrasonic treatment to a completely dispersed state, and then dropping 5 mu L of the obtained mixture on a glassy carbon electrode to obtain the bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode.
Furthermore, in the preparation method of the bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode, in the step 1), the mass ratio of the microcrystalline cellulose to the Ni (II) catalyst is 1: 0.5-2.
Furthermore, in the preparation method of the bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode, in the step 1), the pyrolysis temperature in the tubular furnace is 800-1000 ℃, the heating rate is 2-5 ℃/min, and the reaction time is 2-3 h.
Furthermore, in the preparation method of the bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode, in the step 2), the thermal reflux treatment is performed for 3-5 times, the reflux time is 3-5h each time, and the heating temperature is 80-100 ℃.
Furthermore, in the preparation method of the bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode, in the step 3), the input molar ratio of the bismuth nitrate pentahydrate to the trimesic acid is 1: 10-12.
Furthermore, in the preparation method of the bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode, in the step 3), the adding mass of the biomass graphene subjected to nickel removal is 500 mg.
Use of an electrochemical sensor for simultaneous or separate detection of zinc, lead and cadmium ions, comprising the steps of:
1) the electrochemical sensor for simultaneously or respectively detecting zinc ions, cadmium ions and lead ions is constructed, a silver/silver chloride reference electrode, a platinum sheet counter electrode and a working electrode are respectively connected to an electrochemical workstation, and an electrolyte in an electrolytic cell is HAC-NaAC buffer solution with the pH value of 3-7;
2) selecting i-t on an electrochemical workstation for pre-enrichment, wherein the enrichment potential is-1.5 to-1.0V, the enrichment time is 250-450s, stirring the electrolyte during enrichment at the stirring speed of 400-600rpm, and after the enrichment is finished, enriching the simple substances of zinc, cadmium and lead on a working electrode;
3) selecting a differential pulse anodic stripping voltammetry on an electrochemical workstation, loading a forward scanning voltage with a voltage range of-1.3-0.2V on a working electrode, oxidizing zinc, cadmium and lead simple substances enriched on the working electrode into zinc, cadmium and lead ions, stripping the zinc, cadmium and lead ions into an electrolyte, recording the change condition of current-voltage by the electrochemical workstation to obtain a current-voltage curve, measuring anodic stripping peak currents under different concentrations, and carrying out quantitative analysis based on the linear relation between the metal ion concentration and the peak current so as to obtain the concentration of the zinc, cadmium and lead ions to be measured, wherein the total consumption time is 10-14 min.
Preferably, in the above application, step 1), the HAC-NaAC buffer solution has a pH value of 5.
Preferably, in the above application, step 2), the enrichment potential is-1.2V, and the enrichment time is 400 s.
The invention has the beneficial effects that:
1. the bismuth-based metal organic framework/biomass graphene composite material prepared by the invention fully utilizes the advantages of structural diversity, high surface area, adjustable pore diameter, easiness in preparation and the like of the metal organic framework, and obtains the rod-shaped bismuth-based metal organic framework by virtue of the advantages of no toxicity and good biocompatibility of bismuth. The biomass graphene is coated to improve the disadvantage of poor conductivity of the bismuth-based metal framework. The bismuth-based metal organic framework/biomass graphene composite material prepared by the invention has a structure of a wrapping rod, namely a structure of uniformly loading biomass graphene on the metal organic framework, so that the conductivity of the metal organic framework is better improved.
2. The electrochemical sensor prepared by the invention can be used for the independent detection of metal ions and the simultaneous detection of a plurality of metal ions, and has good detection effect; can carry out rapid detection to heavy metal, and the accessible detects the content of metal ion in the blood and reaches the effect of predicting certain disease, all has very important practical meaning in fields such as environment, food safety, biomedicine.
3. According to the bismuth-based metal organic framework/biomass graphene composite material prepared by the invention, in the preparation process, the bismuth-based metal organic framework is wrapped by the biomass graphene, the biomass graphene is uniformly loaded on the surface of the bismuth-based metal organic framework, and the formed composite material can be dripped on a glassy carbon electrode to be used as a working electrode, so that the bismuth-based metal organic framework/biomass graphene composite material is convenient to apply and test subsequently.
4. The Bi-MOF/CSG-500 composite material prepared by the invention has good effect when applied to electrochemical detection, and Zn is added when the pH is 5, the enrichment potential is-1.2V and the enrichment time is 400s2+、Cd2+、Pb2+The detection limits of (A) were 34.62nM, 10.3nM and 9.12nM, respectively. Compared with other materials, such as composite material Mn (TPA) -SWCNTS to Pb2+Has a detection limit of 38 nM; composite Poly (chromorope 2B)/GCE for Cd2+The detection limit of the material is 33nM, the material of the invention has lower detection limit and wider linear range, which shows better electrochemical detection performance and improves the problem of high detection limit of electrochemical detection.
5. The material obtained by adopting specific reaction conditions and raw materials through a one-pot hydrothermal method has a good electrochemical detection effect, and the preparation method is simple, low in cost, high in detection speed and easy to realize industrial production.
Drawings
FIG. 1a is an XRD pattern of Bi-MOF/CSG with different CSG content ratios.
FIG. 1b is an infrared spectrum of Bi-MOF/CSG with different CSG content ratios.
FIG. 2a is a scanning electron micrograph of Bi-MOF.
FIG. 2b is a scanning electron micrograph of the CSG.
FIG. 2c is a scanning electron micrograph of Bi-MOF/CSG-500.
FIG. 2d is a transmission electron micrograph of Bi-MOF/CSG-500.
FIG. 3a Bi-MOF/CSG vs. Pb for different CSG content ratios2+、Zn2+、Cd2+DPV test chart of (1).
FIG. 3b is Bi-MOF/CSG-500 for Pb2+、Zn2+、Cd2+DPV test chart of (1).
FIG. 4a shows that Bi-MOF/CSG-500 detects Pb2+Linear plot of metal ion concentration.
FIG. 4b is a Bi-MOF/CSG-500 detection of Zn2+Linear plot of metal ion concentration.
FIG. 4c shows Bi-MOF/CSG-500 detection of Cd2+Linear plot of metal ion concentration.
FIG. 4d is a Bi-MOF/CSG-500 assay for Cd simultaneously2+、Pb2+、Zn2++Linear plots of the concentrations of the three metal ions.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Example 1
1) Preparing Ni-doped biomass graphene: 2.67g of NiCl were weighed2·6H2Placing O in a 100mL volumetric flask, adding deionized water to a constant volume to obtain a Ni (II) catalyst solution, weighing 5.00g of microcrystalline Cellulose (CS) and placing in a 150mL beaker, adding 80mL of the Ni (II) catalyst solution, and stirring for 30 min; and then putting the semi-dry product into an oil bath kettle at 85 ℃ for heating and stirring for 4-6h to a semi-dry state, putting the semi-dry product into a porcelain ark, putting the porcelain ark into a tubular furnace, controlling the heating rate to be 4 ℃/min, heating to 900 ℃, carrying out pyrolysis reaction for 2h at 900 ℃, washing the reacted product with deionized water for three times, and carrying out vacuum drying at 60 ℃ to obtain the Ni-doped biomass graphene CSG-Ni.
2) Preparing nickel-removed biomass graphene: and thermally refluxing the obtained CSG-Ni for 3 times at 85 ℃ by using 3mol/L hydrochloric acid, wherein the refluxing time is 4h each time, washing the solid powder obtained after the thermal refluxing treatment to be neutral by using deionized water, and drying in vacuum at 60 ℃ to obtain the nickel-removed biomass graphene CSG.
3) Preparing a bismuth-based organic metal framework/biomass graphene composite material: weigh 150mg Bi (NO)3)3·5H2O in a 100mL beaker, 30mL of absolute methanol was pipetted into the beaker using a pipette gun, and 750mg of H was weighed3BTC is added into the solution, 30mL of anhydrous methanol is added, 500mg of CSG is weighed, the mixture is poured into the solution finally, the mixture is stirred for 0.5h at the rotating speed of 3000rpm, then the mixture is moved into a Teflon-lined reaction kettle and reacts for 24h at the temperature of 120 ℃, the reaction kettle is cooled to room temperature after the reaction is finished and then is taken out, the obtained product is filtered and centrifugally washed for 3 times by the anhydrous methanol, the centrifugal rotating speed is 6000 rpm, the centrifugal time is 10min, then the mixture is dried in a 60 ℃ oven, and after the mixture is completely dried, the bismuth-based metal organic framework/biomass graphene composite material Bi-MOF/CSG-500(500 represents the using amount of the CSG) is obtained.
Example 2
According to the steps 1) -3) in the embodiment 1), the adding amount of the CSG in the step 3) is controlled to be 50mg, 100mg, 200mg, 300mg and 600mg respectively, and Bi-based metal organic framework/biomass graphene composite materials Bi-MOF/CSG-50, Bi-MOF/CSG-100, Bi-MOF/CSG-200, Bi-MOF/CSG-300 and Bi-MOF/CSG-600 are prepared.
Example 3
1) Preparing Ni-doped biomass graphene: 5.34g of NiCl are weighed2·6H2Placing O in a 100mL volumetric flask, adding deionized water for constant volume to obtain a Ni (II) catalyst solution, weighing 5.00g of microcrystalline Cellulose (CS) and placing in a 150mL beaker, then adding 80mL of the Ni (II) catalyst solution, and stirring for 30 min; and then placing the mixture into an oil bath kettle, heating and stirring the mixture for 4-6 hours at 85 ℃ to a semi-dry state, then placing the semi-dry product into a porcelain square boat, placing the porcelain square boat into a tubular furnace, controlling the heating rate to be 4 ℃/min, heating the porcelain square boat to 900 ℃, carrying out pyrolysis reaction for 2 hours at 900 ℃, washing the reacted product with deionized water for three times, and carrying out vacuum drying at 60 ℃, wherein the obtained product is Ni-doped biomass graphene CSG-Ni.
2) Preparing nickel-removed biomass graphene: and thermally refluxing the obtained CSG-Ni with 3mol/L hydrochloric acid at 80 ℃ for 4 times, wherein the refluxing time is 3h each time, washing the solid powder obtained after the thermal refluxing treatment to be neutral with deionized water, and performing vacuum drying at 60 ℃ to obtain the nickel-removed biomass graphene CSG.
3) Preparing a bismuth-based organic metal framework/biomass graphene composite material: 150mg of Bi (NO) are weighed3)3·5H2O in a 100mL beaker, 30mL of absolute methanol was pipetted into the beaker using a pipette gun, and 750mg of H was weighed3BTC is added into the solution, 30mL of anhydrous methanol is added, 500mg of CSG is weighed, the mixture is poured into the solution finally, the mixture is stirred for 0.5h at the rotation speed of 3500rpm, then the mixture is moved into a Teflon-lined reaction kettle and reacts for 24h at the temperature of 120 ℃, the reaction kettle is cooled to room temperature after the reaction is finished and then is taken out, the obtained product is filtered and centrifugally washed for 3 times by the anhydrous methanol, the centrifugal rotation speed is 6000 rpm, the centrifugal time is 5min, then the mixture is dried in a 60 ℃ oven, and after the mixture is completely dried, the bismuth-based metal organic framework/biomass graphene composite material Bi-MOF/CSG-500(500 represents the using amount of the CSG) is obtained.
Example 4
1) 3mg of Bi-MOF/CSG-500 prepared in example 1, Bi-MOF/CSG-50 prepared in example 2, Bi-MOF/CSG-100, Bi-MOF/CSG-200, Bi-MOF/CSG-300 and Bi-MOF/CSG-600 are respectively weighed, dispersed in 100 muL of Nafion solution and 900 muL of deionized water mixed solution, ultrasonically treated to a completely dispersed state, and then 5 muL of the obtained mixture is dripped on a glassy carbon electrode to obtain the glassy carbon electrode of the bismuth-based metal organic framework/biomass graphene/Nafion with different CSG content ratios.
2) Constructing a standard three-electrode system, taking a bismuth-based metal organic framework/biomass graphene/Nafion glassy carbon electrode as a working electrode, taking a platinum electrode as a counter electrode, taking silver/silver chloride as a reference electrode, respectively connecting the electrodes to an electrochemical workstation, placing 0.1mol/L of electrolyte in an electrolytic cell, namely HAC-NaAC buffer solution with the pH value of 5, placing the working electrode in the electrolytic cell filled with 10mL of HAC-NaAC buffer solution, adding the prepared Zn2+、Cd2+、Pb2+at-1.2V of the standard solution ofIn order to deposit potential, 400s of deposition is carried out on the surface of a material, then the solution of an electrolytic cell is replaced, the detection is carried out based on a differential pulse anodic stripping voltammetry, a forward scanning voltage with a voltage range of-1.3-0.2V is loaded on a working electrode, the zinc, cadmium and lead simple substances enriched on the working electrode are oxidized into zinc, cadmium and lead ions, the zinc, cadmium and lead ions are stripped into an electrolyte, an electrochemical workstation records the change condition of current-voltage to obtain a current-voltage curve, the anodic stripping peak current under different concentrations is measured, and quantitative analysis is carried out based on the linear relation between the metal ion concentration and the peak current, so that the concentration of the zinc, cadmium and lead ions to be measured is obtained, and the total consumption time is 10-14 min.
Example 5 detection
FIG. 1a is an XRD (X-ray diffraction) diagram of Bi-MOF/CSG with different CSG content ratios, and the comparison of XRD diagrams shows that the framework of the Bi-MOF is still clear along with the increase of the CSG content ratio, and simultaneously, the peak of carbon at a position of 26 degrees is gradually enhanced, which shows that the content of graphene in the composite material is continuously improved, thereby proving that the Bi-MOF/CSG composite material is successfully synthesized.
FIG. 1b is an infrared spectrum of Bi-MOF/CSG with different CSG content ratios, and the comparison of the infrared spectrum shows that the peak intensity of functional groups such as hydroxyl groups is gradually reduced along with the increase of the CSG content ratio.
FIG. 2a is a scanning electron micrograph of Bi-MOF, which clearly shows the rod-like structure of Bi-MOF and the surface is very smooth.
Fig. 2b is a scanning electron microscope image of CSG, which exists in a relatively obvious lamellar structure, and the lamellar is relatively small.
FIG. 2c is a scanning electron micrograph of Bi-MOF/CSG-500 showing that the CSG of the sheet layer is supported on the rod-shaped Bi-MOF and uniformly distributed on and around the surface of the rod-shaped Bi-MOF.
FIG. 2d is a transmission electron micrograph of Bi-MOF/CSG-500, which shows that the particle size of the material after the composition is relatively small, the Bi-MOF is a solid rod-shaped structure, and the CSG is a relatively small sheet-shaped structure and is uniformly distributed on the surface of the rod.
FIG. 3a Bi-MOF/CSG vs. Pb for different CSG content ratios2+、Zn2+、Cd2+Electrical Detection Performance (DP)V) test graph, and in the graph, the composite material can reach the detection of Pb2+、Zn2+、Cd2+The purpose of detection is that the addition of different contents of the biomass graphene is compared at the same time, and the response current achieved by electrochemical detection is optimal when the content of CSG is 500 mg.
FIG. 3b is Bi-MOF/CSG-500 for Pb2+、Zn2+、Cd2+DPV test chart of (1), the composite material is against Pb2+、Zn2+、Cd2+The detection effect is better.
FIGS. 4a-4d show the peak current and Pb in the DPV test method2+、Zn2+、Cd2+The linear curve of the metal ion concentration shows a better linear relation. Wherein, the graph a shows the peak current and Pb2+The detection range of the linear curve of the metal ion concentration is 0.05-3 mu mol, and the detection limit is 14.54 nM; graph b shows peak current and Zn2+The detection range of the linear curve of the metal ion concentration is 1-16 mu mol, and the detection limit is 59.52 nM; graph c shows the peak current and Cd2+The detection range of the linear curve of the metal ion concentration is 0.03-3 mu mol, and the detection limit is 12.92 nM; FIG. d is a diagram of simultaneous detection of Cd2+、Pb2+、Zn2+The metal ions in the figure are Cd in turn2+、Pb2+、Zn2+Linear curve of concentration, Cd2+、Pb2+、Zn2+The detection ranges of (1) are 0.01-2. mu. mol, 0.03-2. mu. mol and 0.3-10. mu. mol, and the detection limits are 8.81nM, 10.74nM and 29.62nM, respectively. In contrast, the composite material Mn (TPA) -SWCNTS in Pb in the prior art2+Has a detection limit of 38nM, and the composite material Poly (chromorope 2B)/GCE for Cd2+The detection limit of the bismuth-based metal organic framework/biomass graphene composite material is 33nM, which is higher than the detection limit of the bismuth-based metal organic framework/biomass graphene composite material, and the bismuth-based metal organic framework/biomass graphene composite material has a wider linear range and a lower detection limit, which shows that the bismuth-based metal organic framework/biomass graphene composite material has a better electrical detection effect and shows higher detection capability.

Claims (10)

1. An electrochemical sensor for simultaneously or respectively detecting zinc ions, lead ions and cadmium ions comprises an electrochemical workstation, an electrolytic cell, a silver/silver chloride reference electrode, a platinum sheet counter electrode and a working electrode, and is characterized in that the working electrode is a glassy carbon electrode of a bismuth-based metal organic framework/biomass graphene/Nafion.
2. The electrochemical sensor according to claim 1, wherein the preparation method of the glassy carbon electrode of bismuth-based metal organic framework/biomass graphene/Nafion comprises the following steps:
1) preparing Ni-doped biomass graphene: adding nickel metal salt into water to obtain a Ni (II) catalyst solution, adding the Ni (II) catalyst solution into microcrystalline cellulose, stirring for 30min, then putting the solution into an oil bath pan at 85 ℃, heating and stirring for 4-6h to a semi-dry state, putting the semi-dry product into a porcelain boat, carrying out high-temperature pyrolysis in a tubular furnace, washing the reacted product with deionized water for three times, and carrying out vacuum drying at 60 ℃ to obtain Ni-doped biomass graphene CSG-Ni;
2) preparing biomass graphene: carrying out thermal reflux treatment on the CSG-Ni prepared in the step 1) by using 2-4mol/L hydrochloric acid, washing solid powder obtained after the thermal reflux treatment to be neutral by using deionized water, and carrying out vacuum drying at 60 ℃ to obtain nickel-removed biomass graphene CSG;
3) preparing a bismuth-based metal organic framework/biomass graphene composite material: dissolving and dispersing bismuth nitrate pentahydrate in 60-90mL of anhydrous methanol, then adding organic ligand trimesic acid, then adding 50-600 mg of CSG prepared in the step 2), stirring at the rotating speed of 2500 plus 5000rpm for 0.5-1h, then transferring to a hydrothermal reaction kettle, reacting at 120 ℃ for 24h, centrifugally washing for 3 times by using the anhydrous methanol, wherein the centrifugal rotating speed is 6000 rpm, the centrifugal time is 5-15min, and drying in a 60 ℃ oven to obtain a bismuth-based metal organic framework/biomass graphene composite Bi-MOF/CSG;
4) preparing a glassy carbon electrode of a bismuth-based metal organic framework/biomass graphene/Nafion: dispersing the Bi-MOF/CSG prepared in the step 3) into a mixed solution of 100 mu L of Nafion solution and 900 mu L of deionized water according to the concentration ratio of 1mg/mL-3mg/mL, carrying out ultrasonic treatment until the mixture is in a completely dispersed state, and then dripping 5 mu L of the obtained mixture on a glassy carbon electrode to obtain the glassy carbon electrode of the bismuth-based metal organic framework/biomass graphene/Nafion.
3. The electrochemical sensor according to claim 2, wherein in step 1), the mass ratio of microcrystalline cellulose to Ni (ii) catalyst is 1: 0.5-2.
4. The electrochemical sensor as claimed in claim 2, wherein in step 1), the pyrolysis temperature in the tubular furnace is 800-.
5. The electrochemical sensor according to claim 2, wherein in the step 2), the number of times of the thermal reflow treatment is 3-5, each time of the reflow treatment is 3-5h, and the heating temperature is 80-100 ℃.
6. The electrochemical sensor according to claim 2, wherein in step 3), the bismuth nitrate pentahydrate and trimesic acid are charged in a molar ratio of 1:10 to 12.
7. The electrochemical sensor according to claim 2, wherein the added mass of the CSG in step 3) is 500 mg.
8. Use of an electrochemical sensor according to claim 1 for simultaneous or separate detection of zinc, lead and cadmium ions, comprising the steps of:
1) the electrochemical sensor for simultaneously or respectively detecting zinc ions, cadmium ions and lead ions is constructed, a silver/silver chloride reference electrode, a platinum sheet counter electrode and a working electrode are respectively connected to an electrochemical workstation, and an electrolyte in an electrolytic cell is HAC-NaAC buffer solution with the pH value of 3-7;
2) selecting i-t on an electrochemical workstation for pre-enrichment, wherein the enrichment potential is-1.5 to-1.0V, the enrichment time is 250-450s, the electrolyte is stirred during enrichment at the stirring speed of 400-600rpm, and after the enrichment is finished, the simple substances of zinc, cadmium and lead can be enriched on a working electrode;
3) selecting a differential pulse anodic stripping voltammetry on an electrochemical workstation, loading a forward scanning voltage with a voltage range of-1.3-0.2V on a working electrode, oxidizing zinc, cadmium and lead simple substances enriched on the working electrode into zinc, cadmium and lead ions, stripping the zinc, cadmium and lead ions into an electrolyte, recording the change condition of current-voltage by the electrochemical workstation to obtain a current-voltage curve, measuring anodic stripping peak currents under different concentrations, and carrying out quantitative analysis based on the linear relation between the metal ion concentration and the peak current so as to obtain the concentration of the zinc, cadmium and lead ions to be measured, wherein the total consumption time is 10-14 min.
9. The use according to claim 8, wherein the HAC-NaAC buffer solution in step 1) has a pH of 5.
10. The use according to claim 8, wherein in step 2), the enrichment potential is-1.2V and the enrichment time is 400 s.
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