CN112326759A - Preparation method and application of cadmium ion selective electrode based on MOF material - Google Patents
Preparation method and application of cadmium ion selective electrode based on MOF material Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The invention discloses a preparation method and application of a cadmium ion selective electrode based on an MOF material, which is characterized by comprising the following steps: 1) dropwise adding hydrazine hydrate into an ethanol solution containing 4-acetylpyridine, adding 2-3 drops of formic acid, refluxing for 6-10h at the temperature of 106-108 ℃, naturally cooling, filtering, washing with ethanol and drying to obtain 4-bpdh; dissolving zinc nitrate hexahydrate, 4-bpdh and 2-amino terephthalic acid in dimethylformamide, heating at 75-85 deg.C for 70-74 h, cooling to room temperature, washing with anhydrous ethanol for three times, and naturally air drying to obtain TMU-16-NH2(ii) a 2) Adding TMU-16-NH2The material, the carbon-based material and the graphite powder are dissolved and ultrasonically mixed by ethanol, and paraffin oil is added after the ethanol is volatilized to prepare the cadmium ion selective electrode based on the MOF material.
Description
Technical Field
The invention relates to an ion selective electrode and a detection method thereof, in particular to a preparation method and application of a cadmium ion selective electrode based on an MOF material.
Background
Cadmium, a heavy metal element, is low in content in nature, but has good properties, and is widely used in the industries of electroplating, batteries, automobiles, aviation, pigments, paints, printing and the like. Cadmium belongs to a highly toxic substance with persistent environmental pollution, cadmium ions can be accumulated in a human body through the enrichment effect of a food chain, the metabolism in the human body is very slow, the cadmium ions can inhibit the function of enzyme and interfere the synthesis of protein when being combined with the protein, so that the tissue metabolism disorder and the osteoporosis are caused, and the serious people can have kidney injury, cancer, osteomalacia, pain and the like. Therefore, the method can accurately and rapidly detect the content of cadmium ions in the environment and has important significance for human health. The existing cadmium ion detection technology mainly comprises the following steps: the colorimetric method is based on the traditional color developing agent. A spectrophotometer is used as a detection instrument, so that the method is cheap and convenient, but the selectivity is not high; ② a method based on a large-scale analytical instrument. Such as atomic spectrum (absorption, emission, fluorescence) method, chromatography (ion chromatography, capillary electrophoresis), various coupling technologies with mass spectrum, and the like, the detection limit is low, the sensitivity is high, the accuracy is high, the selectivity is good, but the instrument is expensive, the operation and maintenance cost is high, the operation is complicated, and the detection personnel is required to have certain professional knowledge, cannot be applied to on-site rapid detection, and is difficult to popularize; and thirdly, a method based on the portable equipment. In practice, most of such devices are 'simplified microplates' of colorimetric methods, and the sensitivity, selectivity and the like need to be improved; and fourthly, the on-site detection test strip based on the traditional color developing agent. Can carry out cheap and rapid on-site detection, but has poor sensitivity. Therefore, a rapid, convenient, sensitive and accurate method for detecting cadmium ions on site is still an important requirement.
The potential analysis method has the advantages of simple test method, low cost of required equipment, sensitive and accurate result, and the all-solid-state ion selective electrode has the advantages of convenient storage, easy miniaturization and the like, so the potential analysis method adopting the all-solid-state ion selective electrode is an important direction of the cadmium ion field detection method. As a coordination polymer, metal-organic framework Materials (MOFs) have a three-dimensional porous structure, are another important novel porous material besides zeolite and carbon nanotubes, are widely applied to catalysis, energy storage and separation, and have become important research directions of multiple chemical branches of inorganic chemistry, organic chemistry and the like. At present, no research report related to the preparation method and application of the cadmium ion selective electrode based on the MOF material exists at home and abroad.
Disclosure of Invention
The invention aims to provide a preparation method and application of a cadmium ion selective electrode based on an MOF material, which have the advantages of high sensitivity and specificity, reliable detection result, simple steps and high detection speed.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a cadmium ion selective electrode based on an MOF material comprises the following steps:
(1) preparation of MOF Material (TMU-16-NH)2)
a. Dropwise adding hydrazine hydrate into an ethanol solution containing 4-acetylpyridine, adding 2-3 drops of formic acid into the mixed solution, refluxing for 6-10h at the temperature of 106 ℃ and 108 ℃, naturally cooling to obtain a yellow solid after the reaction is finished, washing with ethanol after filtering, and drying to obtain 2, 5-bis (4-pyridyl) -3, 4-diaza-2, 4-hexadiene (4-bpdh);
b. zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), 2, 5-bis (4-pyridyl) -3, 4-diaza-2, 4-hexadiene (4-bpdh) and 2-aminoterephthalic acid (NH)2-BDC) is dissolved in Dimethylformamide (DMF), the mixture is put into a Teflon reactor and heated for 70 to 74 hours at the temperature of 75 to 85 ℃, after the mixture is cooled to the room temperature, the mixture is washed with absolute ethyl alcohol for three times and naturally dried, and the MOF material which has selective response to cadmium ions and is named as TMU-16-NH is obtained2；
(2) Preparation of cadmium ion selective electrode
The TMU-16-NH prepared in the step (1)2Dissolving carbon-based material and graphite powder in small beaker with ethanol, ultrasonic treating for 30 min for mixing, volatilizing ethanol, adding 2-3 drops of paraffin oil, grinding into pasteInjecting the electrode into a polytetrafluoroethylene tube with the inner radius of 4.5 mm, filling the tube with compact structure, filling graphite powder on the back of the tube, inserting copper wires, fixing the copper wires by conductive epoxy resin, and polishing the surface of the copper wires to obtain the cadmium ion selective electrode based on the MOF material.
The mixing volume ratio of the hydrazine hydrate to the ethanol solution containing 4-acetylpyridine in the step (1) a is 1: 15, wherein the mixing volume ratio of the ethanol to the 4-acetylpyridine in the ethanol solution containing the 4-acetylpyridine is 15: 2.2.
The mixing ratio of the zinc nitrate hexahydrate, the 2, 5-bis (4-pyridyl) -3, 4-diaza-2, 4-hexadiene, the 2-aminoterephthalic acid and the dimethylformamide in step (1) b was 1 mmol: 0.5 mmol: 1 mmol: 15 mL.
TMU-16-NH described in step (2)2The mixing ratio of the material, the carbon-based material, the graphite powder and the ethanol is 99 mg: 1 mg: 1 g: 5 ml.
The carbon-based material in the step (2) comprises multi-wall carbon nano tubes, graphene and microphone.
The method for detecting cadmium ions by using the cadmium ion selective electrode based on the MOF material comprises the following steps: the cadmium ion selective electrode prepared according to any one of claims 1 to 5 is used as an indicating electrode, and an Ag/AgCl electrode is used as a reference electrode; in a nitrate buffer solution with the pH value of 2.0, measuring the magnitude of battery electromotive force corresponding to a series of cadmium ions with different concentrations, and establishing a quantitative relation between the magnitude of the battery electromotive force and the concentration of the cadmium ions; and according to the quantitative relation, the concentration of cadmium ions in the unknown solution can be determined.
Compared with the prior art, the invention has the advantages that: the invention utilizes TMU-16-NH2The specific recognition of cadmium ions is combined with a carbon-based material with high specific surface area and good conductivity, so that the cadmium ion selective electrode based on the MOF material is constructed. MOF material TMU-16-NH2The method has a plurality of unique properties in selectively identifying cadmium ions: the ligand skeleton contains a large number of N, O atoms, a large number of unsaturated metal binding sites exist, and the ligand has strong coordination capacityAnd various coordination modes; a three-dimensional periodic net-shaped porous structure with a specific size can obtain a one-dimensional channel (with the pore diameter of 7.1 multiplied by 4.6A) with the specific size through double permeation adjustment, and the one-dimensional channel is matched with the size of cadmium ions, so that the cadmium ions are specifically identified; the electrode has large specific surface area, and effectively amplifies the surface area of the selective electrode together with the multi-wall carbon nano tube with large specific surface area and good conductivity to obtain good response signals.
Compared with the prior art, the invention has the advantages that:
(1) the invention has high sensitivity, the large-surface-area two-dimensional material has good electron transmission performance, the porous structure of the material realizes an amplification effect on the surface area of the electrode, and meanwhile, the ligand framework of the MOFs contains a plurality of N, O atoms and has strong coordination capacity and a plurality of coordination modes. The activity of the cadmium ions can be simply and conveniently measured by a potential method through the weak interaction caused by the coordination and attachment of the cadmium ions and the amino groups;
(2) high specificity. The method of the present invention has high specificity, and ions other than cadmium ions interfere less with the apparatus because of Zn (NO)3)2·6H2O with rigid bipyridine-type ligand (4-bpdh) and 2-aminoterephthalic acid (NH)2-BDC) providing a three-dimensional framework with pores that can be tuned by double infiltration to give one-dimensional channels (pore diameter 7.1 x 4.6 a) with a cadmium ion dimension similar to TMU-16-NH2The one-dimensional channel is proper, so that cadmium ions are easier to capture than other ions;
(3) the preparation and detection method has the advantages of less reagent dosage and high detection speed. After the MOF material and the carbon base are uniformly mixed to prepare the electrode, the electrochemical sensor can be constructed in one step, and the preparation method is extremely simple.
Drawings
FIG. 1 shows Cd2+A linear plot of concentration versus battery electromotive force;
FIG. 2 shows the concentration of the cadmium ion selective electrode of the present invention for 10-2~10-6mol/L of Pb2+、Cu2+、Ni2+、Hg2+And Cd2+The linear relationship between the concentration of the solution for measurement and the electromotive force of the cell is compared.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Detailed description of the preferred embodiment
Example 1
A preparation method of a cadmium ion selective electrode based on an MOF material comprises the following steps:
(1) preparation of MOF Material (TMU-16-NH)2)
a. Dropwise adding hydrazine hydrate into an ethanol solution containing 4-acetylpyridine, adding 2-3 drops of formic acid into the mixed solution, refluxing for 8 hours at 107 ℃, naturally cooling to obtain a yellow solid after the reaction is finished, washing with ethanol after filtering, and drying to obtain 2, 5-bis (4-pyridyl) -3, 4-diaza-2, 4-hexadiene (4-bpdh); wherein the mixing volume ratio of hydrazine hydrate to the ethanol solution containing 4-acetylpyridine is 1: 15, the mixing volume ratio of the ethanol and the 4-acetylpyridine in the ethanol solution containing the 4-acetylpyridine is 15: 2.2;
b. adding Zn (NO)3)2·6H2O, 4-bpdh and NH2-BDC is dissolved in Dimethylformamide (DMF), the mixture is put into a Teflon reactor and heated for 72 hours at the temperature of 80 ℃, after the mixture is cooled to the room temperature, the mixture is washed with absolute ethyl alcohol for three times and naturally dried, and the TMU-16-NH is obtained2The MOF material being selectively responsive to cadmium ions; zn (NO)3)2·6H2O、4-bpdh、NH2-the mixing ratio of BDC to dimethylformamide is 1 mmol: 0.5 mmol: 1 mmol: 15 mL;
(2) preparation of electrochemical sensor for cadmium ion
99 mg of TMU-16-NH21 mg of carbon-based material and 1g of graphite powder are mixed uniformly by using 5ml of ethanol in a small beaker through ultrasonic treatment for 30 min, after the ethanol is volatilized, a few drops of paraffin oil are added, the mixture is ground into paste, the paste is injected into a polytetrafluoroethylene tube with the inner radius of 4.5 mm, the graphite powder is filled on the part of the paste after the paste is filled compactly, a copper wire is inserted from the back and is fixed by conductive epoxy resin, and the surface of the paste is polishedAnd (3) after the light treatment, obtaining the cadmium ion selective electrode based on the MOF material, wherein the carbon-based material comprises a multi-wall carbon nano tube, graphene and microphone.
Example 2
The difference from the above example 1 is that: refluxing for 10h at 106 ℃ in the step (1); and (3) putting the mixture in the step (2) into a Teflon reactor, heating for 74 h at the temperature of 75 ℃, and cooling to room temperature.
Example 3
The difference from the above example 1 is that: refluxing for 6h at 108 ℃ in the step (1); and (3) putting the mixture in the step (2) into a Teflon reactor, heating for 70h at the temperature of 85 ℃, and cooling to room temperature.
Detailed description of the invention
A method for detecting cadmium ions by using the cadmium ion selective electrode in the above embodiment 1, comprising the following steps:
the cadmium ion selective electrode is used as an indicating electrode, and an Ag/AgCl electrode is used as a reference electrode; in a nitrate buffer solution with the pH value of 2.0, measuring the magnitude of battery electromotive force corresponding to a series of cadmium ions with different concentrations, and establishing a quantitative relation between the magnitude of the battery electromotive force and the concentration of the cadmium ions; and according to the quantitative relation, the concentration of cadmium ions in the unknown solution can be determined.
Detailed description of the preferred embodiment
Accurately weighing 0.2364 g (1 mmol) of cadmium nitrate solid by an electronic balance, and diluting to 100 mL in a 100 mL volumetric flask by using a nitrate buffer solution to obtain 10-2And M in cadmium ion solution. Taking 10 mL of the solution, taking another 100 mL volumetric flask, and diluting to 100 mL with nitrate buffer solution to obtain 10-3And M in cadmium ion solution. The same can be prepared with the concentration of 10-4、10-5、10-6、10-7、10-8Cadmium ion solution of M; before measurement, the prepared cadmium ion selective electrode is placed in HNO with the pH value of 2.03Activating the solution for 2 h, using the activated solution as an indicating electrode, using an Ag/AgCl electrode as a reference electrode, inserting the reference electrode into the solution to be measured to form an electrochemical cell, and measuring the electromotive force of the cell according to the second method of the embodiment.
As shown in FIG. 1, the electrode exhibited a near Nernst potential response with a slope of 27.8 mV/dec and a linear range of 10-7 mol/L~10-2mol/L. The linear equation is E = 10.3-27.8logC, the detection limit is 10-7 mol/L。
Detailed description of the invention
In order to verify the value of the method in practical application, tap water is selected as a water sample, and 6 mol/L HNO is used3Adjusting the pH value to 2.0, and adding Cd2+Taking the standard solution as an actual sample, and adopting a standard adding and recycling method to carry out Cd recovery on different concentrations in tap water2+Detection was performed. As shown in Table 1, the potential response RSD is 2.3% -3.5%, the recovery rate is 95.9% -104.3%, and the results are satisfactory. Shows that the invention can treat Cd in water sample2+The detection result is accurate and reliable.
TABLE 1 Cd in tap water2+Result of detection of
Detailed description of the preferred embodiment
As can be seen from FIG. 2, the sensors prepared according to the first embodiment each have a concentration of 10-2~10-6mol/L of Pb2+、Cu2 +、Ni2+、Hg2+The solution is subjected to electromotive force detection and is mixed with Cd2+Is compared and analyzed, the sensor is used for Pb2+、Cu2 +、Ni2+、Hg2+The plasma did not exhibit a significant electrochemical response, but was responsible for Cd2+But exhibits a significant electrochemical response, indicating that the sensor is sensitive to Cd2+Has specific detection.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (6)
1. A preparation method of a cadmium ion selective electrode based on an MOF material is characterized by comprising the following steps:
(1) preparation of MOF materials
a. Dropwise adding hydrazine hydrate into an ethanol solution containing 4-acetylpyridine, adding 2-3 drops of formic acid into the mixed solution, refluxing for 6-10h at the temperature of 106-108 ℃, naturally cooling to obtain a yellow solid after the reaction is finished, filtering, washing with ethanol, and drying to obtain 2, 5-bis (4-pyridyl) -3, 4-diaza-2, 4-hexadiene;
b. zinc nitrate hexahydrate, 2, 5-bis (4-pyridyl) -3, 4-diaza-2, 4-hexadiene and 2-amino terephthalic acid (NH)2-BDC) is dissolved in Dimethylformamide (DMF), the mixture is put into a Teflon reactor and heated for 70 to 74 hours at the temperature of 75 to 85 ℃, after the mixture is cooled to the room temperature, the mixture is washed with absolute ethyl alcohol for three times and naturally dried, and the MOF material which has selective response to cadmium ions and is named as TMU-16-NH is obtained2；
(2) Preparation of cadmium ion selective electrode
The TMU-16-NH prepared in the step (1)2Dissolving the material, the carbon-based material and graphite powder in a small beaker by using ethanol, carrying out ultrasonic treatment for 30 min to uniformly mix the materials, adding 2-3 drops of paraffin oil after the ethanol is volatilized, grinding the mixture into paste, injecting the paste into a polytetrafluoroethylene tube with the inner radius of 4.5 mm, filling the paste compactly, filling graphite powder on the back of the paste, inserting copper wires, fixing the paste by using conductive epoxy resin, and polishing the surface to obtain the cadmium ion selective electrode based on the MOF material.
2. The method of making a MOF material based cadmium ion selective electrode according to claim 1, wherein: the mixing volume ratio of the hydrazine hydrate to the ethanol solution containing 4-acetylpyridine in the step (1) a is 1: 15, wherein the mixing volume ratio of the ethanol to the 4-acetylpyridine in the ethanol solution containing the 4-acetylpyridine is 15: 2.2.
3. The method of making a MOF material based cadmium ion selective electrode according to claim 1, wherein: the mixing ratio of the zinc nitrate hexahydrate, the 2, 5-bis (4-pyridyl) -3, 4-diaza-2, 4-hexadiene, the 2-aminoterephthalic acid and the dimethylformamide in step (1) b was 1 mmol: 0.5 mmol: 1 mmol: 15 mL.
4. The method of making a MOF material based cadmium ion selective electrode according to claim 1, wherein: TMU-16-NH described in step (2)2The mixing ratio of the material, the carbon-based material, the graphite powder and the ethanol is 99 mg: 1 mg: 1 g: 5 ml.
5. The method of making a MOF material based cadmium ion selective electrode according to claim 1, wherein: the carbon-based material in the step (2) comprises multi-wall carbon nano tubes, graphene and microphone.
6. The method for detecting cadmium ions by using the cadmium ion selective electrode based on the MOF material is characterized by comprising the following steps: the cadmium ion selective electrode prepared according to any one of claims 1 to 5 is used as an indicating electrode, and an Ag/AgCl electrode is used as a reference electrode; in a nitrate buffer solution with the pH value of 2.0, measuring the magnitude of battery electromotive force corresponding to a series of cadmium ions with different concentrations, and establishing a quantitative relation between the magnitude of the battery electromotive force and the concentration of the cadmium ions; and according to the quantitative relation, the concentration of cadmium ions in the unknown solution can be determined.
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