CN114561020B - Metal-organic framework-Cu nano material for electrochemical sensor and preparation method and application thereof - Google Patents
Metal-organic framework-Cu nano material for electrochemical sensor and preparation method and application thereof Download PDFInfo
- Publication number
- CN114561020B CN114561020B CN202210185333.0A CN202210185333A CN114561020B CN 114561020 B CN114561020 B CN 114561020B CN 202210185333 A CN202210185333 A CN 202210185333A CN 114561020 B CN114561020 B CN 114561020B
- Authority
- CN
- China
- Prior art keywords
- chp
- organic framework
- dmp
- metal
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The present invention relates toA metal organic framework-Cu nano material for an electrochemical sensor and a preparation method and application thereof are provided, wherein the material is prepared by the following steps: (1) Dissolving a copper source in deionized water, adding phosphoric acid, reacting, centrifuging, washing and drying to obtain CHP; (2) Dispersing CHP in deionized water, adding DMF solution of trimesic acid, reacting, centrifuging, washing, and drying to obtain CHP@Cu 3 (BTC) 2 A material; (3) Taking CHP@Cu 3 (BTC) 2 Dispersing the material in anhydrous diethyl ether, adding DMTZ, reacting, centrifuging, washing and drying to obtain the target product. The material has the advantages of larger specific surface area, rich pore canal structure, capability of enhancing lead adsorption and accelerating electron transfer, stronger conductivity and capability of greatly reducing the detection limit. Compared with the prior art, the metal organic framework-Cu nano material and glassy carbon electrode composite material has the advantages of higher sensitivity, stronger anti-interference performance, better detection reproducibility and stability, small and simple required equipment and quick detection.
Description
Technical Field
The invention belongs to the technical field of electrochemical sensors, and relates to a metal-organic framework-Cu nano material for an electrochemical sensor, and a preparation method and application thereof.
Background
Lead is an accumulated heavy metal, and once discharged into the environment, the lead can cause serious pollution to air, land, water source and the like, and even lead is seriously harmful to various systems such as nerves, digestion, kidneys and the like of a human body after being enriched through the circulation of a food chain. It is notable that in the early stage of accumulation, the concentration of lead in the human body is low, no obvious clinical symptoms are present, and if the treatment is not carried out in time, the consequences are serious, and the hiding property of Pb is one of the factors causing the hazard. Therefore, the establishment of a rapid, sensitive and quantitative lead detection method is a good strategy for preventing lead poisoning.
Common Pb detection methods include atomic absorption spectrometry, inductively coupled plasma method, high performance liquid chromatography, etc., but the above methods have various disadvantages such as complex sample pretreatment, huge experimental equipment, high price, long operation time consumption, etc. In addition, the detection method of Pb in the prior art has lower sensitivity, is easily interfered by other substances, and has poor detection reproducibility and stability.
At present, no electrochemical sensor based on a metal organic framework-Cu nano material can be applied to quantitative analysis of heavy metal lead ions so as to realize high-sensitivity and rapid detection of the lead ions.
Disclosure of Invention
The invention aims to provide a metal-organic framework-Cu nano material for an electrochemical sensor, and a preparation method and application thereof, so as to overcome the defects of low sensitivity, easiness in interference by other substances, poor detection reproducibility and stability, huge required experimental equipment, complex sample pretreatment, high cost, long operation time consumption and the like of a Pb detection method in the prior art.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a metal-organic framework-Cu nano material for an electrochemical sensor, which comprises the following steps:
(1) Dissolving a copper source in deionized water, adding phosphoric acid, reacting, centrifuging, washing and drying to obtain CHP;
(2) Dispersing the obtained CHP in deionized water, adding N, N-Dimethylformamide (DMF) solution of trimesic acid, reacting, centrifuging, washing, and drying to obtain CHP@Cu 3 (BTC) 2 A material;
(3) Taking the obtained CHP@Cu 3 (BTC) 2 Dispersing the material in anhydrous diethyl ether, then adding 2, 5-Dimercaptothiadiazole (DMTZ), reacting, centrifuging, washing and drying to obtain the target product.
Further, in the step (1), the copper source is copper acetate.
Further, in the step (1), the ratio of the addition amounts of the copper source, deionized water and phosphoric acid is (2 to 4) g:80mL: (0.4-0.6) mL, optionally 3.2g:80mL:0.544mL.
Further, in the step (1), the reaction temperature is 120-160 ℃, optionally 140 ℃, and the reaction time is 2-6h, optionally 4h.
Further, in the step (1), a solid is obtained by centrifugation, and then the obtained solid is washed 3 times with deionized water and ethanol, and then dried at 25 ℃ for 12 hours.
Further, in the step (2), the concentration of the N, N-dimethylformamide solution of trimesic acid is 0.025 mol.L -1 。
Further, the ratio of the addition amounts of the CHP, deionized water and the N, N-dimethylformamide solution of trimesic acid is (1-2) g:51mL: (40-50) mL, optionally 1.3g:51mL:45mL.
Further, in the step (2), the pH of the mixed solution obtained after adding the N, N-dimethylformamide solution of trimesic acid before the reaction was adjusted to 6.
Further, in the step (2), the reaction temperature is 20-40 ℃, optionally 25 ℃, and the reaction time is 1-3h, optionally 1h.
Further, in the step (2), a solid is obtained by centrifugation, and then the obtained solid is washed 3 times with ethanol.
Further, in the step (2), the drying temperature was 40℃and the drying time was 12 hours.
Further, in the step (3), CHP@Cu 3 (BTC) 2 The ratio of the material, the anhydrous diethyl ether and the DMTZ is (0.1-0.3) g to 20mL (50-150) mg, and the ratio can be 0.2g to 20mL to 50mg, 0.2g to 20mL to 100mg or 0.2g to 20mL to 150mg.
Further, in the step (3), the reaction temperature is 20-40 ℃, optionally 25 ℃, and the reaction time is 12-36h, optionally 24h.
Further, in the step (3), a solid was obtained by centrifugation, and then the obtained solid was washed 3 times with water and ethanol, respectively.
Further, in the step (3), the drying temperature was 60℃and the drying time was 12 hours.
The second technical scheme of the invention provides a metal organic framework-Cu nano material for an electrochemical sensor, wherein the metal organic framework-Cu nano material is rod-shaped, and the average length is 10 mu m.
The third technical scheme of the invention provides application of the metal organic framework-Cu nano material, wherein the metal organic framework-Cu nano material is used for detecting heavy metal ions, and the detection process comprises the following steps:
s1: dispersing the metal-organic framework-Cu nano material in a solvent to obtain a mixed solution;
s2: dripping the obtained mixed solution on a glassy carbon electrode, and then drying to obtain a modified electrode;
s3: the obtained modified electrode is used as a working electrode, the calomel electrode is used as a reference electrode, the platinum wire electrode is used as a counter electrode, acetic acid-sodium acetate buffer solutions containing heavy metal ions with different concentrations are respectively used as electrolyte for electrodeposition, then SWV is used for measuring the dissolution peak current, then standard curve equation is established according to the dissolution peak current and the corresponding heavy metal ion concentration, the dissolution peak current of the sample to be measured is measured under the same condition, and then the content of the heavy metal ions in the sample to be measured is calculated according to the dissolution peak current and the standard curve equation.
Further, the heavy metal ions are lead ions.
Further, in step S1, the solvent is a mixture of chitosan solution and ethanol.
Further, the volume ratio of the chitosan solution to the ethanol is 1:1.
further, the concentration of the chitosan solution is 1 mg.ml -1 。
Further, in the step S1, the mass-volume ratio of the metal-organic framework-Cu nanomaterial to the solvent is 5mg: 200. Mu.L.
Further, in step S2, the drop-coating amount of the mixed solution is 0.57 to 1.13. Mu.L/mm 2 Preferably 0.71. Mu.L/mm 2 。
Further, in step S2, the glassy carbon electrode is further subjected to the following pretreatment before being dropped:
(1) Al for glassy carbon electrode 2 O 3 Grinding and polishing the powder on chamois leather until the surface of the powder is smooth, washing, drying and then placing the powder in H 2 SO 4 Soaking in the solution, scanning to be stable by using a cyclic voltammetry, and washing to obtain an activated glassy carbon electrode;
(2) Al for the activated glassy carbon electrode 2 O 3 And (3) grinding and polishing the powder on the chamois leather until the surface of the powder is smooth, and then washing and airing the powder to finish the pretreatment of the glassy carbon electrode.
Further, in step S3, the voltage is-1.3 to-0.8V, preferably-1V, and the deposition time is 130 to 330S, preferably 250S, during the electrodeposition.
Further, in step S3, the pH of the acetic acid-sodium acetate buffer is 4 to 6, preferably 5.0.
Further, in step S3, after the electrodeposition was completed, the solution was allowed to stand for 10 seconds and then eluted.
Further, in step S3, the potential scanning range is-1.0V-0V in the dissolution peak current test process.
Further, in step S3, the concentration of the heavy metal ion in the acetic acid-sodium acetate buffer is 0.01, 0.03, 0.05, 0.08, 0.1, 0.2, 0.4, 0.8, 3, 7, 10, 20, 30, 50 or 80 nmol.L -1 。
The metal organic framework-Cu nano material can be used for detecting heavy metal ions, and the detection method adopted by the method is an electrochemical analysis method, namely a stripping voltammetry (SWV), and has the advantages of small and simple required equipment, higher sensitivity, rapid detection, easy analysis of experimental results and the like, and has a large development space in the field of real-time field detection. The stripping voltammetry is to electrolyze for a certain time under the potential of the limiting current generated by the polarography of the substance to be tested for enrichment, then change the potential of the electrode to re-strip the substance enriched on the electrode, and quantitatively analyze according to the voltammogram obtained in the stripping process. The method has the characteristics of high sensitivity, rapid detection and capability of detecting various ions.
The metal-organic frameworks (MOFs) are made of inorganic metal centers and organicCrystalline porous materials of a class of network structures to which ligands are attached by interaction. The functional microparticle/nanoparticle metal organic framework (MP/NP@MOF) has great application potential in the aspects of adsorption, gas storage, catalysis, chemical sensing and the like because of rich metal active sites, strong adsorption capability, strong adjustable chemical property and good thermal stability and the advantages of magnetism, optics, catalysis and stability of the functional microparticle/nanoparticle (MP/NP) core. Especially, the controllable function MP/NP@MOF core/shell structure is constructed, so that not only is aggregation of cores avoided and the characteristics of the cores maintained, but also a synergistic effect is obtained by integrating the functions of the MOF shell and the MP/NP core, and the application potential is greatly improved. Trimesic acid copper (Cu) 3 (BTC) 2 ) The three-dimensional structure is composed of metal center copper and ligand trimesic acid, has the characteristics of high specific surface area, high pore volume and controllable morphology, and is very representative in metal organic framework materials.
The invention adopts an in-situ template method, utilizes an active shell of hydroxyl copper phosphate (CHP) as a source of metal ions, and converts the active shell into Cu with clear limit on a CHP inner core in situ at room temperature 3 (BTC) 2 The crystal shell effectively avoids self-nucleation of MOF in solution, successfully assembles well-defined crystal units MP@MOF, and uses DMTZ to functionalize MP@MOF to obtain MOFs composite material (DMP-Cu). Because the relatively stable core properties are retained during synthesis, the stability and adsorptivity of the final resulting material is greatly improved.
Since chitosan molecule is composed of acetamido, hydroxyl, amino, it has special adsorption and flocculation ability. In wastewater treatment, chitosan often utilizes flocculation to achieve the effect of efficiently capturing heavy metal ions, and in addition, chitosan can carry out coordination reaction with the metal ions to better fit with materials, so that the invention adopts chitosan as an adhesive to modify a GCE electrode, so that the materials are not easy to fall off in the detection process, and the stability of electrochemical detection of heavy metals is improved. In addition, chitosan has affinity to cells and is biodegradable, and the possibility of environmental pollution is avoided in the use process.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts an in-situ template method, utilizes an active shell of hydroxyl copper phosphate (CHP) as a source of metal ions, and converts the active shell into Cu with clear limit on a CHP inner core in situ 3 (BTC) 2 The crystal shell effectively avoids the self-nucleation of MOF in the solution, successfully assembles the crystal unit MP@MOF with clear limit, and uses DMTZ to functionalize MP@MOF to obtain MOFs composite material, and the stability and adsorptivity of the finally obtained metal-organic framework-Cu nano material are better due to the relatively stable inner core property reserved in the synthesis process;
(2) The modified electrode obtained by compounding the metal organic framework-Cu nano material and the glassy carbon electrode can be used as an electrochemical sensor for detecting lead ions, and the modified electrode is used for detecting Pb in a water sample 2+ The method has specific adsorption capacity, and has stronger anti-interference performance, reproducibility and stability;
(3) The metal organic framework-Cu nano material has larger specific surface area and rich pore canal structure, can strengthen lead adsorption and accelerate electron transfer, has stronger conductivity, can greatly reduce the detection limit of heavy metal lead, and has the detection limit as low as 0.003 nmol.L -1 (S: n=3:1), the sensitivity is high;
(4) The invention is based on metal organic framework-Cu nano material, adopts SWV to Pb 2+ Realizes high-efficiency and quantitative detection, and the lead concentration is 1 multiplied by 10 -11 ～8×10 -8 mol·L -1 In the range of (2), the size of the dissolution peak current and the concentration of lead ions show a good linear relation, the required equipment is small, simple and convenient, the detection is quick, the experimental result is easy to analyze, no complex sample pretreatment is needed, the cost is low, and the method has the advantages of no need of complex sample pretreatment, and no pollution to Pb 2+ Has certain application value in the rapid real-time detection.
Drawings
FIG. 1 is a standard card for CHP and CHP, CHP@Cu 3 (BTC) 2 XRD spectra of DMP-Cu-50;
fig. 2 is a Scanning Electron Microscope (SEM) image of the respective materials: (a) CHP; (B) Chp@cu 3 (BTC) 2 ；(C)DMP-Cu-50；(D)DMP-Cu-100；(E)DMP-Cu-150；
Fig. 3 is a scanning electron microscope-X-ray energy spectrum of each material: (a) CHP; (B) Chp@cu 3 (BTC) 2 ；(C)DMP-Cu-50；
Fig. 4 is a cyclic voltammogram: (A) CHP/GCE, CHP@Cu 3 (BTC) 2 The ratio of the/GCE to the DMP-Cu-50/GCE is 5 mmol.L - 1 K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]0.1 mol.L of (C) -1 Cyclic voltammograms in KCl solution; (B) DMP-Cu-50/GCE, DMP-Cu-100/GCE, DMP-Cu-150/GCE at 5 mmol.L -1 K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]0.1 mol.L of (C) -1 Cyclic voltammograms in KCl solution;
FIG. 5 shows that the GCE, DMP-Cu-50/GCE, DMP-Cu-100/GCE, DMP-Cu-150/GCE is 2.5 μm.L -1 SWV diagram in lead solution;
FIG. 6 shows DMP-Cu-50/GCE at 5 mmol.L -1 K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]0.1 mol.L of (C) -1 Sweep rate cyclic voltammograms in KCl solution;
fig. 7: (A) DMP-Cu-50/GCE was enriched at different times for 2.5. Mu. Mol.L -1 Pb of (2) 2+ Is a SWV plot of (2); (B) a plot of enrichment time versus SWV peak current;
fig. 8: (A) DMP-Cu-50/GCE was enriched at different potential pairs of 2.5. Mu. Mol.L -1 Pb of (2) 2+ Is a SWV plot of (2); (B) a plot of enrichment potential versus SWV peak current;
fig. 9: (A) DMP-Cu-50/GCE pairs of 2.5. Mu. Mol.L prepared from different drop-on amounts of DMP-Cu-50 solution -1 Pb of (2) 2+ SWV diagram of solution; (B) a plot of DMP-Cu-50 drop-on versus SWV peak current;
fig. 10: (A) DMP-Cu-50/GCE was used for 2.5. Mu. Mol.L in acetic acid-sodium acetate buffer solutions of different pH values -1 Pb of (2) 2+ Is a SWV plot of (2); (B) A plot of pH versus SWV peak current for acetic acid-sodium acetate buffer solution;
fig. 11: (A) DMP-Cu-50/GCE in Pb 2+ The concentration is 0.01 nmol.L -1 ～0.4nmol·L -1 A current response stripping voltammetry (SWV) plot; (B) DMP-Cu-50/GCE in Pb 2+ The concentration is0.8nmol·L -1 ～80nmol·L -1 A current response stripping voltammetry (SWV) plot; (C) At a low concentration of Pb 2+ Within the range (0.01 nmol.L) -1 ～0.4nmol·L -1 )Pb 2+ A standard curve of concentration versus current; (D) At high concentration Pb 2+ Within the range (0.8 nmol.L) -1 ～80nmol·L -1 )Pb 2+ Concentration versus current standard curve.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise specified, the raw materials or processing techniques are indicated as being conventional commercially available raw material products or conventional processing techniques in the art.
In the following examples, 5 mmol.L was used -1 K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]0.1 mol.L of (C) -1 KCl solution of (B) is prepared, wherein K 3 [Fe(CN) 6 ]And K is equal to 4 [Fe(CN) 6 ]Purchased from Shanghai Taitan technologies Co., ltd., molar ratio of 1:1.
example 1:
synthesis of CHP:
to 80mL of water was added 3.2g of copper acetate, and the mixture was stirred uniformly, and after 0.544mL of phosphoric acid was slowly added dropwise, the mixture was stirred for 1 hour. After the suspension is mixed uniformly, the mixture is added into a reaction kettle, and the reaction kettle is put into an oven and heated for 4 hours at the constant pressure and the temperature of 140 ℃. After the reaction is finished, the precipitate is obtained by centrifugation, deionized water and ethanol are respectively used for washing for 3 times, and the precipitate is dried at room temperature for 12 hours to obtain green solid which is CHP.
Example 2:
CHP@Cu 3 (BTC) 2 synthesis of materials:
1.3g of the CHP obtained in example 1 was added to 51mL of water and stirred, and 45mL of a solution of trimesic acid in N, N-Dimethylformamide (DMF) (0.025 mol. L) -1 ) Obtaining a mixed solution, using 4Adjusting pH of the obtained mixture to 6 with% NaOH solution, stirring at 25deg.C for 1 hr, centrifuging to recover precipitate, washing with ethanol for 3 times, and drying at 40deg.C for 12 hr to obtain CHP@Cu product 3 (BTC) 2 A material.
Example 3:
synthesis of DMP-Cu material:
0.2g of CHP@Cu prepared in example 2 was taken 3 (BTC) 2 The material was placed in a 50mL round bottom flask, 20mL of anhydrous diethyl ether was added, followed by DMTZ of different mass (A: 50mg; B:100mg; C:150 mg) respectively. Stirring at 25deg.C for 24 hr, centrifuging to obtain solid, washing with water and ethanol for 3 times, and oven drying in vacuum oven at 60deg.C for 12 hr to obtain DMP-Cu materials (named DMP-Cu-50, DMP-Cu-100, and DMP-Cu-150 respectively, wherein DMP-Cu-50 is prepared by adding 50mg DMTZ, and so on).
For the CHP obtained in example 1 and the CHP@Cu obtained in example 2 3 (BTC) 2 Materials, DMP-Cu materials obtained in example 3 were characterized:
to determine the phase of the prepared DMP-Cu material, analytical characterization was performed using X-ray diffraction (XRD) at angles of 2-theta ranging from 10 DEG to 50 deg. As shown in FIG. 1, the diffraction peak of the template CHP was synthesized with a standard card [ Cu ] 2 (OH)PO 4 ，JCPDS:No.36-0404]In contrast, the peak heights, peak shapes and peak angles are basically consistent, and the characteristic diffraction peaks are basically coincident. In situ conversion to Cu 3 (BTC) 2 After the shell, a new diffraction peak appears in the crystal (as indicated by the arrow in fig. 1). The main peak of the DMP-Cu material (DMP-Cu-50) obtained after DMTZ functionalization is consistent with the main peak before modification, because of the existence of a stable template core of CHP, diffraction peaks of the CHP can still be observed in the DMP-Cu-50 map, which indicates that the structure of the MOF is kept good.
The morphology of the material was characterized and analyzed by Scanning Electron Microscopy (SEM). A, B, C, D, E in FIG. 2 is CHP, CHP@Cu, respectively 3 (BTC) 2 Material characterization diagrams of DMP-Cu-50, DMP-Cu-100 and DMP-Cu-150 materials under a scanning electron microscope. As shown in FIG. 2 (A), the crystal of CHP has a typical columnar structure, and is small and compactThe aggregated nanorods have a rough shell. Chp@cu 3 (BTC) 2 Is prepared by in situ conversion of CHP template shells into well-defined MOF crystal shells. When a solution of trimesic acid in N, N-Dimethylformamide (DMF) was added to an aqueous solution in which the CHP template was dispersed at room temperature, the color of the solution changed from green to bluish indicating Cu 3 (BTC) 2 Is generated. As shown in fig. 2 (B), the CHP template shell is converted in situ into a well-defined crystal shell. As shown in fig. 2 (C), (D) and (E), the dmz-modified composite material can be observed that the DMP-Cu material obtained by dmz functionalization has similar dimensions, but has a coarser surface, and the newly generated material has a flower-like surface morphology, so that the specific surface area is greatly increased, the pore structure is enriched, the effects of enhancing adsorption and accelerating electron transfer can be achieved in the lead enrichment process, the conductivity is enhanced, and the detection limit of heavy metal lead can be greatly reduced. Therefore, in the synthesis process of the DMP-Cu material, the relatively stable inner core structure is maintained, so that the stability and the effective adsorption performance of the material are greatly improved.
To further confirm Cu 3 (BTC) 2 And DMTZ was successfully assembled to CHP surfaces, and elemental weight distribution and atomic content of DMP-Cu materials were analyzed by SEM-EDS. As shown in fig. 3 and table 1, the atomic content of Cu gradually decreased as CHP was subjected to a two-step functionalization reaction, consistent with the expected results. Meanwhile, in DMP-Cu-50, the presence of S element was detected. Again, DMTZ functionalization proved successful.
TABLE 1 CHP, CHP@Cu 3 (BTC) 2 SEM-EDS analysis data summary table of DMP-Cu-50 material
Example 4:
sequentially using glass carbon electrode (GCE, diameter of 3 mm) and Al with particle diameter of 0.3 μm and 0.05 μm 2 O 3 Polishing the powder on chamois leather to a mirror surface, washing with water, sequentially ultrasonic cleaning in absolute ethanol and water for 1min, and air drying to obtain clean GCE.Placing clean GCE at 1 mol.L -1 H of (2) 2 SO 4 Soaking in the solution for 5min, and treating with cyclic voltammetry at 0.05V.s -1 Scanning the electrode within the range of-0.2-2.0V until the scanning speed is stable, taking out the electrode, and respectively ultrasonically cleaning the electrode in ethanol and water for 1min to obtain the activated glassy carbon electrode (A-GCE). A-GCE was treated with 0.3 μm and 0.05 μm Al 2 O 3 The powder is ground and polished on chamois leather until the mirror surface is smooth, and is washed clean by secondary distilled water and then dried for later use. 5mg of the DMP-Cu-50, DMP-Cu-100 and DMP-Cu-150 prepared in example 3 were separately taken in separate centrifuge tubes, and 100. Mu.L of ethanol and 100. Mu.L of chitosan solution (1 mg. Ml were then added respectively -1 1mg chitosan is dissolved in 1ml 10wt% acetic acid solution), and the mixture is evenly mixed by ultrasonic to obtain DMP-Cu-50 solution, DMP-Cu-100 solution and DMP-Cu-150 solution with the concentration of 0.025 mg/mu L, and 5 mu L of the obtained solution is respectively dripped on the center of the treated glassy carbon electrode (the dripping area is 7.065 mm) 2 The drop-coating amount was 0.71. Mu.L/mm 2 ) And (3) drying and cooling to obtain three MOF material modified GCEs which are named as DMP-Cu-50/GCE, DMP-Cu-100/GCE and DMP-Cu-150/GCE respectively. CHP and CHP@Cu were prepared as above 3 (BTC) 2 GCE modified by materials and respectively named CHP/GCE and CHP@Cu 3 (BTC) 2 /GCE。
Example 5:
performance characterization of the modified electrode prepared in example 4:
by studying the different electrodes at 5 mmol.L -1 K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]0.1 mol.L of (C) -1 Fe present in KCl solution of (C) 2+ /Fe 3+ The difference of the electric pair oxidation-reduction peak current and the peak potential can judge the electrochemical performance of the material. FIG. 4 (A) is CHP/GCE, CHP@Cu 3 (BTC) 2 CV scans of/GCE, and DMP-Cu-50/GCE. It can be seen that with further functionalization of the MOF material, fe 2+ /Fe 3+ The oxidation-reduction peak current of the pair on the DMP-Cu material is larger, the oxidation-reduction peak potential difference (DeltaEp) is smaller, which shows that the DMP-Cu-50/GCE electrode has stronger catalysis effect on the oxidation-reduction reaction and the oxidation-reduction reaction on the electrode surfaceThe reversibility is better.
In order to investigate the effect of DMTZ of different addition amounts on the modified electrode during the synthesis of DMP-Cu, CV scans of DMP-Cu-50/GCE, DMP-Cu-100/GCE, and DMP-Cu-150/GCE were compared as shown in FIG. 4 (B). The results show that Fe 2+ /Fe 3+ The maximum redox peak current of the pair on the DMP-Cu-50/GCE electrode is consistent with the characterization results of XRD and SEM. Therefore, DMP-Cu-50/GCE can be selected as the optimal modified electrode for Pb 2+ Is detected.
FIG. 5 is a graph showing the results of bare GCE and DMP-Cu-50/GCE, DMP-Cu-100/GCE, DMP-Cu-150/GCE obtained in example 4 in a lead solution (2.5 μm L -1 ) As can be seen from FIG. 5, the composite electrode of DMP-Cu and GCE is used for detecting Pb 2+ Although the elution bit of (a) is shifted, the elution peak current is significantly higher than that of the bare GCE. The method is characterized in that DMF and water form shell layer crystals with clear structures on the surface of a CHP template in the synthesis process, so that self-nucleation of MOF in a solution can be effectively avoided, most nanorod cores of the CHP template are still reserved and the specific surface area is increased after being modified by DMTZ, thereby enhancing conductivity and electron transfer, facilitating adsorption and enrichment of heavy metal ion lead and improving Pb determination 2+ Is a high sensitivity. In addition, the peak current of DMP-Cu-50/GCE eluted was maximized, and the result was 5 mmol/L by CV method -1 K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]0.1 mol.L of (C) -1 The scanning results of KCl solution of (C) are consistent, so DMP-Cu-50/GCE can be used as electrochemical sensor for Pb 2+ High sensitivity detection of the solution.
Example 6:
effect of scan rate:
by studying the effect of scan rate on electrochemical response, the surface reaction mechanism of the modified electrode prepared in example 4 was presumed. FIG. 6 shows DMP-Cu-50/GCE at 5 mmol.L -1 K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]0.1 mol.L of (C) -1 Cyclic voltammograms scanned at different scan rates in KCl solutions. When the sweeping speed is from 60 mV.s -1 ～180mV·s -1 The redox peak current response increases with increasing magnitudeThe large, but gradual increase in the oxidation-reduction potential difference (Δep) suggests that too fast a scan rate may deteriorate the reversibility of the oxidation-reduction reaction occurring at the electrode surface. On the other hand, the calculation found (see the inset in fig. 6) that the reduction peak current (Ipa) and the sweep rate (v) were in a linear relationship, and the linear regression equation was ipa= 0.02948 v+19.00. This illustrates that the process is an adsorption-controlled electrochemical process on DMP-Cu-50/GCE. As the scan rate decreases, the current response decreases and the sensitivity deteriorates. Conversely, as the scan rate increases, the current response increases and the sensitivity increases, but the reversibility of the redox reaction deteriorates, the optimum scan rate is 100 mV.s -1 。
Example 7:
enrichment time to Pb 2+ Influence of elution peak current:
in this example, the enrichment time vs. Pb was investigated using DMP-Cu-50/GCE prepared in example 4 as a subject 2+ The effect of the elution peak current. Enrichment time is one of the important factors affecting heavy metal detection limit and sensitivity. Since the modified electrode is first required to be subjected to Pb under stirring 2+ Enrichment in solution, thus prolonging the enrichment time is beneficial to Pb on the electrode surface 2+ Is adsorbed by the adsorbent. FIG. 7 (A) shows the result of the concentration of DMP-Cu-50/GCE at different enrichment times for 2.5. Mu. Mol.L -1 Pb of (2) 2+ As shown in fig. 7 (B), the peak current has a dependence on the lead enrichment time of the metal ions, and the dissolution peak current increases with increasing enrichment time from 130s to 250s. But as the enrichment time is increased, the dissolution peak current decreases. The adsorption time is increased in the initial stage of adsorption, which is favorable for Pb 2+ Enrichment on the electrode surface, but after saturation of the electrode surface metal ion concentration, the metal active site can not adsorb Pb any more 2+ Simultaneously with the stirring, pb adsorbed on the surface of the material 2+ Is easy to fall off, thereby influencing the detection limit and ensuring the optimal enrichment time to be 250s.
Example 8:
deposition potential pair Pb 2+ Influence of elution peak current:
this example was prepared as in example 4DMP-Cu-50/GCE is taken as an experimental object, and the deposition potential pair Pb is explored 2+ The effect of the elution peak current. In the elution analysis of heavy metal ions, the choice of the deposition potential is important to obtain the best sensitivity. Thus, the effect of the deposition potential on the dissolution peak current after 250s enrichment was studied in 0.1M acetic acid-sodium acetate buffer at pH 5.0. FIG. 8 (A) shows the concentration of DMP-Cu-50/GCE at different concentration potential pairs of 2.5. Mu. Mol.L -1 Pb of (2) 2+ As shown in FIG. 8 (B), pb when the deposition potential was lowered from-0.8V to-1.0V 2+ Gradually increasing the peak current of (c). This is because the more difficult the oxidation reaction occurs and the more likely the reduction reaction occurs as the deposition potential moves negatively, resulting in an increase in the reduction peak current. However, when the deposition potential continued to decrease, less than-1.0V, pb was observed 2+ Is reduced. This is because hydrogen evolution reaction occurs on the electrode surface, and hydrogen bubbles generated during the reaction adhere to the electrode surface to block Pb 2+ The peak current after dissolution is reduced, and simultaneously, the co-deposition of other metal ions in the real sample analysis can be avoided. Thus, the optimal deposition potential is-1.0V.
Example 9:
drop-coating quantity of Pb 2+ Influence of elution peak current:
the MOF material modified GCE in example 4 was prepared by dropping DMP-Cu material onto GCE electrode, so the dropping amount of DMP-Cu material determines the number of metal active sites on electrode surface and has great influence on electrochemical detection of lead. This example was carried out by taking the DMP-Cu-50 solution (0.025 mg. Mu.L) prepared in example 4 -1 ) The modified electrode materials are prepared by dripping 4 mu L, 5 mu L, 6 mu L, 7 mu L and 8 mu L on the surface of the GCE electrode (the dripping areas are 7.065 mm) 2 The corresponding dripping amounts are respectively 0.57, 0.71, 0.85, 0.99 and 1.13 mu L/mm 2 ) Electrochemical detection is then performed. FIG. 9 (A) shows the DMP-Cu-50 solution pair of 2.5. Mu. Mol.L for different dispensing amounts -1 Pb of (2) 2+ The SWV plot of the solution, as shown in FIG. 9 (B), shows that the peak current obtained was maximum when the volume of the solution dispensed was 5. Mu.L. The dripping amount is too small, the GCE central mirror surface cannot be covered, the number of metal active sites is small,the electrochemical response is poor; the coating amount is too large, the electrode surface is covered with the finishing material too thick, and the electron transfer is blocked, the conductivity is reduced, and the response is weakened. In addition, during stirring enrichment, the excessive dropping amount easily causes the dropping of the dropping material in a lump, so that the detection effect becomes poor, thus 0.71. Mu.L/mm 2 Is the most suitable dripping amount.
Example 10:
buffer pH value to Pb 2+ Influence of elution peak current:
in this example, the pH value of the buffer solution was investigated against Pb using DMP-Cu-50/GCE prepared in example 4 as a subject 2+ The effect of the elution peak current. The pH value of the buffer solution has great influence on peak current, so that a proper pH value is selected to have a great influence on Pb 2+ Is of vital importance in the measurement of (a). FIG. 10 (A) shows the result of a 2.5X10-way reaction of DMP-Cu-50/GCE in 0.1M acetic acid-sodium acetate buffer at different pH values - 6 mol·L -1 As shown in FIG. 10 (B), it is understood that Pb was found as the pH value increased from 4.0 to 5.0 2+ The peak current of (2) increases to a maximum value at a pH of 5.0, and the dissolution current decreases as the pH continues to increase. This is because, since too high a pH easily causes hydrolysis reaction of lead ions, pH5.0 is the optimal pH of the buffer solution.
Example 11:
reproducibility, stability and tamper resistance of the DMP-Cu-50/GCE prepared in example 4:
reproducibility and stability of an electrochemical sensor are important criteria for judging whether the detection capability of the electrochemical sensor is good or bad. The DMP-Cu-50/GCE prepared in example 4 was placed at 2.5. Mu.m.L -1 The measurement was repeated 10 times, and the relative standard deviation of the elution peak current was 3.25%. Next, DMP-Cu-50/GCE prepared in the same manner was taken and subjected to multiple measurements under the same experimental conditions, with a relative error of 4.03% (n=10). In addition, after 10 days of storage of the modified electrode, there was only 8.2% peak current loss. The DMP-Cu-50/GCE has good reproducibility and stability and good detection capability as an electrochemical sensor.
In actual sample analysis, the dry matter of the unknown substanceInterference is unavoidable, so that modifying the interference resistance of the electrode is one of the important detection criteria. At a lead ion concentration of 2.5 μm.L -1 At the same time add Na into the solution of + ，Cl - ，Mg 2+ ，SO 4 2- ，Fe 2+ ，CO 3 2- ，K + ，PO 4 2- ，Hg 2+ ，Cr 3+ And (2) competing ions of urea, glucose, aniline, vitamin C, and evaluation of DMP-Cu-50/GCE versus Pb 2+ The amounts and concentrations of the substances competing for ions, urea, glucose, aniline, vitamin C are all the same. Experimental results show that the interference of each ion on SWV peak current is smaller and is smaller than 5%, and the DMP-Cu-50/GCE proves that the ions have a small interference on Pb in a water sample 2+ The DMP-Cu-50/GCE has specific adsorption capacity, so that the DMP-Cu-50/GCE can be used as an electrochemical sensor to be more efficiently and sensitively applied to detection of lead ions in an actual sample.
Example 12:
examples 7-10 lead solutions with certain concentrations were measured using SWV to determine the position and size of the lead peak, optimizing the enrichment time (130 s-330 s), the deposition potential (-1.3V to-0.8V), the drop-in amount (4. Mu.l-8. Mu.l), the pH of the acetic acid-sodium acetate buffer (4-6), and determining the optimal enrichment time (250 s), the optimal deposition potential (-1.0V), the optimal drop-in amount (5. Mu.l) and the pH of the acetic acid-sodium acetate buffer (5.0).
Detection linearity and minimum detection limit of heavy metal lead:
firstly, a three-electrode system for electrochemical detection is built for heavy metal lead determination. The reference electrode was a calomel electrode, the counter electrode was a platinum wire electrode, the working electrode was DMP-Cu-50/GCE prepared in example 4, and a three electrode system was placed in a Pb-containing state 2+ In acetic acid-sodium acetate buffer (ph=5, 0.1mol·l) -1 ) The current-time method is adopted, stirring and depositing are carried out for 250s under the potential of-1V, stirring is stopped, standing is carried out for 10s, then the SWV is used for leaching, the scanning range is-1.0V-0V, and the leaching peak position and the current of lead are obtained. Finally, the potential was adjusted to 0.1V, and the electrode surface was cleaned for 120 seconds to clean the lead remaining on the electrode surface for the next detection. The whole experiment comprises a series of enrichment, dissolution and cleaning stepsThe structure is formed, and repeated detection is carried out for a plurality of times. Finally, a standard curve is established according to the peak current of the dissolution curve and the concentration of the lead solution so as to quantitatively determine lead. Pb 2+ The concentration gradient is 0.01 nmol.L from low to high -1 ，0.03nmol·L -1 ，0.05nmol·L -1 ，0.08nmol·L -1 ，0.1nmol·L -1 ，0.2nmol·L -1 ，0.4nmol·L -1 ，0.8nmol·L -1 ，3nmol·L -1 ，7nmol·L -1 ，10nmol·L -1 ，20nmol·L -1 ，30nmol·L -1 ，50nmol·L -1 And 80 nmol.L -1 。
As shown in fig. 11 (a) and 11 (B), with Pb 2+ The higher the concentration, the higher the elution peak of lead, the analysis results are shown in fig. 11 (C) and 11 (D): pb 2+ At a concentration of 0.01 nmol.L -1 ～0.4nmol·L -1 And 0.8 nmol.L -1 ～80nmol·L -1 Within the range of (A), DMP-Cu-50/GCE is in Pb 2+ Ipa and Pb in solution 2+ The concentration (c) has a good linear relationship. At a low concentration (0.01 nmol.L) -1 ～0.4nmol·L -1 ) The linear regression equation is Ipa (μA) =17.27c (nmol.L) -1 )+7.12(R 2 =0.9779); at a high concentration (0.8 nmol.L) -1 ～80nmol·L -1 ) The linear regression equation is Ipa (μA) = 0.5219c (nmol.L) -1 )+17.34(R 2 = 0.9896). The detection limit is 0.003 nmol.L -1 (S:N＝3:1)。
According to the limit index of lead specified in national food safety standard, namely the limit of pollutants in food, wherein the minimum limit of lead in packaged drinking water is 0.01mg.L -1 I.e. 4.826×10 -8 mol·L -1 . The blood lead level in human body exceeds 100 ug.L -1 (4.826×10 -7 mol·L -1 ) The lead is likely to exceed the standard, and the DMP-Cu-50/GCE has practical application capability of detecting ultra-low concentration lead ions, can reach national food safety detection standards, and has great application potential in the aspect of detecting heavy metals in real time on site in the future.
Example 13:
actual measurement of tap water sample and seaweed water sample:
in this example, the DMP-Cu-50/GCE obtained in example 4 was used as an electrochemical sensor for detecting a water sample. Wherein, the tap water sample is taken from a medicine laboratory of Shanghai health medical college, the seaweed water sample is taken from the Changjiang river entrance of Chongming island, and the lead content is measured by using a labeled recovery method. Pb obtained in example 12 according to the peak current levels of elution peaks of both 2+ The concentration-current relation curve shows that the concentration of each group is 104.00% -123.67% and the recovery rate range shows that the DMP-Cu-50/GCE can realize the rapid and quantitative determination of lead ions in the environment and has a large development space in the aspect of real-time on-site detection.
Example 14:
most of them are the same as in example 1 except that the addition amount of copper acetate in this example was changed to 2g.
Example 15:
most of them are the same as in example 1 except that the addition amount of copper acetate in this example was changed to 4g.
Example 16:
most of them were the same as in example 1 except that the amount of phosphoric acid added was changed to 0.4mL in this example.
Example 17:
most of them were the same as in example 1 except that the amount of phosphoric acid added was changed to 0.6mL in this example.
Example 18:
in comparison with example 1, the same operation was carried out except that in this example, the "heating at 140℃under normal pressure for 4 hours" was changed to "heating at 120℃under normal pressure for 4 hours".
Example 19:
in comparison with example 1, the same applies to the vast majority except that in this example, the "heating at 140℃under normal pressure for 4 hours" is changed to the "heating at 160℃under normal pressure for 4 hours".
Example 20:
in comparison with example 1, the same operation was carried out except that in this example, the "heating at 140℃under normal pressure for 4 hours" was changed to "heating at 140℃under normal pressure for 2 hours".
Example 21:
in comparison with example 1, the same operation was carried out except that in this example, the "heating at 140℃under normal pressure for 4 hours" was changed to "heating at 140℃under normal pressure for 6 hours".
Example 22:
most of them are the same as in example 2 except that the addition amount of CHP in this example was changed to 1g.
Example 23:
most of them were the same as in example 2 except that the addition amount of CHP was changed to 2g in this example.
Example 24:
most of the same as in example 2, except that in this example, an N, N-dimethylformamide solution of trimesic acid (0.025 mol. L -1 ) The addition amount of (C) was 40mL.
Example 25:
most of the same as in example 2, except that in this example, an N, N-dimethylformamide solution of trimesic acid (0.025 mol. L -1 ) The addition amount of (C) was changed to 50mL.
Example 26:
in the present example, the stirring at 25℃for 1 hour was changed to the stirring at 20℃for 1 hour, and the same as in example 2 was repeated for the most part.
Example 27:
in the present example, the stirring at 25℃for 1 hour was changed to the stirring at 40℃for 1 hour, and the same as in example 2 was repeated for the most part.
Example 28:
in the present example, the stirring at 25℃for 1 hour was changed to the stirring at 25℃for 2 hours, and the same as in example 2 was repeated for the most part.
Example 29:
in the present example, the stirring at 25℃for 1 hour was changed to the stirring at 25℃for 3 hours, and the same as in example 2.
Example 30:
most of them are the same as in example 3, except that in this example CHP@Cu 3 (BTC) 2 The addition amount of the material was changed to 0.1g.
Example 31:
most of them are the same as in example 3, except that in this example CHP@Cu 3 (BTC) 2 The addition amount of the material was changed to 0.3g.
Example 32:
in comparison with example 3, the same procedure was repeated except that in this example, the "stirring at 25℃for 24 hours" was changed to "stirring at 20℃for 24 hours".
Example 33:
in comparison with example 3, the same procedure was repeated except that in this example, the "stirring at 25℃for 24 hours" was changed to "stirring at 40℃for 24 hours".
Example 34:
in comparison with example 3, the same procedure was repeated except that in this example, the "stirring at 25℃for 24 hours" was changed to "stirring at 25℃for 12 hours".
Example 35:
in comparison with example 3, the same procedure was repeated except that in this example, the "stirring at 25℃for 24 hours" was changed to "stirring at 25℃for 36 hours".
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (7)
1. The application of the metal organic framework-Cu nano material for the electrochemical sensor is characterized in that the metal organic framework-Cu nano material is used for detecting heavy metal ions, and the detection process comprises the following steps:
s1: dispersing a metal organic framework-Cu nano material in a solvent to obtain a mixed solution;
s2: dripping the obtained mixed solution on a glassy carbon electrode, and then drying to obtain a modified electrode;
s3: the obtained modified electrode is used as a working electrode, the calomel electrode is used as a reference electrode, the platinum wire electrode is used as a counter electrode, acetic acid-sodium acetate buffer solutions containing heavy metal ions with different concentrations are respectively used as electrolyte for electrodeposition, then SWV is used for measuring dissolution peak current, standard curve equation is established according to the dissolution peak current and the corresponding heavy metal ion concentration, dissolution peak current of a sample to be measured is measured under the same condition, and then the content of heavy metal ions in the sample to be measured is calculated according to the dissolution peak current and the standard curve equation;
the heavy metal ions are lead ions;
the preparation process of the metal organic framework-Cu nano material specifically comprises the following steps:
(1) Dissolving a copper source in deionized water, adding phosphoric acid, and performing reaction, centrifugation, washing and drying to obtain hydroxy copper phosphate (CHP);
(2) Dispersing the obtained hydroxy copper phosphate CHP in deionized water, adding N, N-dimethylformamide solution of trimesic acid, reacting, centrifuging, washing, and drying to obtain CHP@Cu 3 (BTC) 2 A material;
(3) Taking the obtained CHP@Cu 3 (BTC) 2 Dispersing the material in anhydrous diethyl ether, adding 2, 5-dimercaptothiadiazole, reacting, centrifuging, washing and drying to obtain the target product.
2. The use of a metal-organic framework-Cu nanomaterial for electrochemical sensors according to claim 1, wherein in step (1), the copper source is copper acetate;
in the step (1), the ratio of the addition amounts of the copper source, the deionized water and the phosphoric acid is (2-4) g:80mL: (0.4-0.6) mL;
in the step (1), the reaction temperature is 120-160 ℃ and the reaction time is 2-6h.
3. The use of a metal-organic framework-Cu nanomaterial for electrochemical sensors according to claim 1, characterized in that in step (2) the concentration of the trimesic acid in N, N-dimethylformamide solution is 0.025 mol-L -1 And the addition ratio of the N, N-dimethylformamide solution of CHP, deionized water and trimesic acid is (1-2) g:51mL: (40-50) mL;
in the step (2), the reaction temperature is 20-40 ℃ and the reaction time is 1-3h;
in the step (2), the pH of the mixed solution obtained after adding the N, N-dimethylformamide solution of trimesic acid before the reaction was adjusted to 6.
4. The use of a metal-organic framework-Cu nanomaterial for electrochemical sensors according to claim 1, characterized in that in step (3) chp@cu 3 (BTC) 2 The ratio of the addition amount of the material to the anhydrous diethyl ether to the addition amount of the 2, 5-dimercaptothiadiazole is (0.1-0.3) g to 20mL (50-150) mg;
in the step (3), the reaction temperature is 20-40 ℃ and the reaction time is 12-36h.
5. The application of the metal-organic framework-Cu nanomaterial for an electrochemical sensor according to claim 1, wherein in step S1, the solvent is a mixture of a chitosan solution and ethanol, and the volume ratio of the chitosan solution to the ethanol is 1:1.
6. the use of a metal-organic framework-Cu nanomaterial for an electrochemical sensor as claimed in claim 1, wherein in step S2, the drop-coating amount of the mixed solution is 0.57-1.13. Mu.L/mm 2 。
7. The application of the metal-organic framework-Cu nanomaterial for an electrochemical sensor according to claim 1, wherein in the step S3, the voltage is-1.3 to-0.8V in the electrodeposition process, and the deposition time is 130 to 330S;
in the step S3, the pH value of the acetic acid-sodium acetate buffer solution is 4-6;
in the step S3, in the test process of the dissolution peak current, the potential scanning range is-1.0V-0V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210185333.0A CN114561020B (en) | 2022-02-28 | 2022-02-28 | Metal-organic framework-Cu nano material for electrochemical sensor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210185333.0A CN114561020B (en) | 2022-02-28 | 2022-02-28 | Metal-organic framework-Cu nano material for electrochemical sensor and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114561020A CN114561020A (en) | 2022-05-31 |
| CN114561020B true CN114561020B (en) | 2023-06-02 |
Family
ID=81716527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210185333.0A Active CN114561020B (en) | 2022-02-28 | 2022-02-28 | Metal-organic framework-Cu nano material for electrochemical sensor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114561020B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101134920B1 (en) * | 2011-06-03 | 2012-04-17 | 한국기초과학지원연구원 | Polymer resin-copper bonded component and method for preparing the same |
| EP2608218B1 (en) * | 2011-12-21 | 2014-07-30 | Agfa-Gevaert | A dispersion comprising metallic, metal oxide or metal precursor nanoparticles, a polymeric dispersant and a thermally cleavable agent |
| WO2015116679A1 (en) * | 2014-01-29 | 2015-08-06 | Advanced Technology Materials, Inc. | Post chemical mechanical polishing formulations and method of use |
| US10189458B2 (en) * | 2015-02-11 | 2019-01-29 | The Boeing Company | Thiol based resin system for removal of copper ions from hydraulic fluid |
| CN111948265A (en) * | 2020-08-14 | 2020-11-17 | 哈尔滨工业大学 | Electrochemical method for detecting heavy metal ions based on UIO-66 modified electrode |
-
2022
- 2022-02-28 CN CN202210185333.0A patent/CN114561020B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114561020A (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Controllable synthesis of an intercalated ZIF-67/EG structure for the detection of ultratrace Cd2+, Cu2+, Hg2+ and Pb2+ ions | |
| Zhang et al. | Covalent organic framework as a novel electrochemical platform for highly sensitive and stable detection of lead | |
| Yang et al. | Electrochemical detection of trace arsenic (III) by nanocomposite of nanorod-like α-MnO2 decorated with∼ 5 nm Au nanoparticles: considering the change of arsenic speciation | |
| Chu et al. | Enhanced stripping voltammetric response of Hg2+, Cu2+, Pb2+ and Cd2+ by ZIF-8 and its electrochemical analytical application | |
| Liu et al. | Sensitive electrochemical detection of Hg (II) via a FeOOH modified nanoporous gold microelectrode | |
| Xiong et al. | Electrochemical detection of ultra-trace Cu (II) and interaction mechanism analysis between amine-groups functionalized CoFe2O4/reduced graphene oxide composites and metal ion | |
| CN109100404B (en) | Hydrotalcite-like nanosheet @ ZIF-67 composite material modified electrode and preparation method and detection application thereof | |
| Han et al. | Mesoporous MnFe2O4 nanocrystal clusters for electrochemistry detection of lead by stripping voltammetry | |
| CN110672684B (en) | Electrochemical sensor for detecting nitrite with high sensitivity and preparation method and application thereof | |
| Xiao et al. | An Fe-MOF/MXene-based ultra-sensitive electrochemical sensor for arsenic (III) measurement | |
| Terbouche et al. | Evaluation of adsorption capacities of humic acids extracted from Algerian soil on polyaniline for application to remove pollutants such as Cd (II), Zn (II) and Ni (II) and characterization with cavity microelectrode | |
| Li et al. | A simple strategy for the detection of Pb (II) and Cu (II) by an electrochemical sensor based on Zn/Ni-ZIF-8/XC-72/Nafion hybrid materials | |
| Liang et al. | Influences of surface-coated fulvic and humic acids on the adsorption of metal cations to SiO2 nanoparticles | |
| Li et al. | A three-dimensional bimetallic oxide NiCo2O4 derived from ZIF-67 with a cage-like morphology as an electrochemical platform for Hg2+ detection | |
| CN111398385B (en) | Composite electrode for heavy metal ion detection and preparation method thereof | |
| Javanbakht et al. | Determination of picomolar silver concentrations by differential pulse anodic stripping voltammetry at a carbon paste electrode modified with phenylthiourea-functionalized high ordered nanoporous silica gel | |
| CN108982641B (en) | Preparation method of electrochemical sensor for trace lead ion detection | |
| Pei et al. | A novel covalent-organic framework for highly sensitive detection of Cd2+, Pb2+, Cu2+ and Hg2+ | |
| Liu et al. | Novel cysteic acid/reduced graphene oxide composite film modified electrode for the selective detection of trace silver ions in natural waters | |
| Tashkhourian et al. | Ascorbic acid determination based on electrocatalytic behavior of metal-organic framework MIL-101-(Cr) at modified carbon-paste electrode | |
| CN109187687B (en) | Preparation of conjugated organic microporous material modified electrode and application of modified electrode as peroxynitroso anion electrochemical sensor | |
| CN107328834B (en) | Composite material modified electrode for detecting lead ions in livestock and poultry drinking water and preparation method thereof | |
| CN113311043A (en) | Detect Pb2+And Hg2+Electrochemical sensor and preparation method and application thereof | |
| CN114561020B (en) | Metal-organic framework-Cu nano material for electrochemical sensor and preparation method and application thereof | |
| CN114538530B (en) | Basic cobalt carbonate nano material for electrochemical sensor and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |