CN115109262A - Metal organic framework nanosheet, preparation method, working electrode and sensor - Google Patents

Metal organic framework nanosheet, preparation method, working electrode and sensor Download PDF

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CN115109262A
CN115109262A CN202210656983.9A CN202210656983A CN115109262A CN 115109262 A CN115109262 A CN 115109262A CN 202210656983 A CN202210656983 A CN 202210656983A CN 115109262 A CN115109262 A CN 115109262A
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calcium carbonate
copper
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CN115109262B (en
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韦晨慧楠
王卓
李善宇
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Hubei University of Technology
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Abstract

The invention discloses a metal organic framework nanosheet, a preparation method, a working electrode and a sensor, and belongs to the technical field of nanomaterials and electrochemistry. The metal organic framework nanosheet, comprising: the two-dimensional CuBDC nanosheets are assembled into a multistage structure in a long-range mode, the orientations of the two-dimensional CuBDC nanosheets are consistent, and no agglomeration exists among the two-dimensional CuBDC nanosheets, wherein the two-dimensional CuBDC nanosheets are triangular and have the thickness of 10-40 nm. The invention improves the defect that the two-dimensional nano-sheet is easy to agglomerate, and improves the performance of the enzyme-free electrochemical ascorbic acid sensor as a sensing electrode, so that the sensor has the advantages of high sensitivity, good selectivity, good stability, low detection limit and the like.

Description

Metal organic framework nanosheet, preparation method, working electrode and sensor
Technical Field
The invention relates to the technical field of nano materials and electrochemistry, in particular to a metal organic framework nanosheet, a preparation method, a working electrode and a sensor.
Background
Vitamin C is a necessary nutrient substance for human body, and can treat scurvy, enhance human immunity, promote absorption of minerals such as calcium, phosphorus, iron, and the like, and help metabolism of skin tissues, and the like. Excessive or insufficient intake of ascorbic acid can lead to various types of diseases, the most well known being scurvy. Because the human body can not synthesize the ascorbic acid by itself, how to monitor the concentration of the ascorbic acid in the human body is very important for preventing and treating various diseases such as scurvy and the like. The electrochemical method has the outstanding advantages of simple operation, rapid and accurate detection, low cost and easy miniaturization of an instrument and a device, and becomes a great hot spot in the development of the portable sensor for detecting the ascorbic acid in the human sweat. The ascorbic acid sensor provided on the market at present adopts biological enzyme as a sensing material, but natural enzyme is used as protein, the activity is very easily interfered by the outside world (pH, temperature and the like), the stability is poor, the measurement is inaccurate, even the detection function is completely lost, the cost is very high, and the fixing step is complicated. Compared with an enzyme type ascorbic acid sensor, the enzyme-free ascorbic acid sensor technology can realize catalytic oxidation of ascorbic acid on the surface of an electrode, and the detection of human ascorbic acid is realized through the correlation between a current signal and the concentration of ascorbic acid.
Among a plurality of sensing materials, the metal organic framework is widely applied to the field of electrochemical sensing due to large specific surface area, many active sites and adjustable pore sizes. The metal organic framework with the two-dimensional nanosheet shape has more low-coordination atoms on the surface, and the low-coordination atoms can be used as active sites for electrocatalytic oxidation reduction, so that the adsorption and oxidation of an object to be detected on the surface are greatly facilitated, and the sensing performance of the object is improved. However, the metal organic framework nanosheet prepared in the prior art is extremely easy to agglomerate, so that the defect that the active site cannot be fully utilized is caused, and the electrochemical sensor based on the metal organic framework has low detection accuracy and poor detection repeatability on the ascorbic acid.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problems that the metal organic framework material is easy to agglomerate and the sensing electrode performance is insufficient, and aims to provide a multilevel structure metal organic framework CuBDC nanosheet with simple process, low cost and excellent electrochemical performance, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect, the invention provides a metal organic framework material nanosheet, which comprises a plurality of two-dimensional CuBDC nanosheets, wherein the two-dimensional CuBDC nanosheets are assembled into a multistage structure in a long-range mode, the orientations of the two-dimensional CuBDC nanosheets are consistent, and no agglomeration exists among the two-dimensional CuBDC nanosheets, wherein the two-dimensional CuBDC nanosheets are triangular and have a thickness of 10-40 nm.
In a second aspect, the invention also provides a preparation method of the metal organic framework nanosheet, which is characterized by comprising the following steps: the method comprises the following steps:
s1: soaking calcium carbonate paper in a copper nitrate solution to obtain hydroxyl copper nitrate-calcium carbonate paper;
s2: etching the copper hydroxyl nitrate-calcium carbonate paper by using a potassium hydroxide solution to obtain copper hydroxide-calcium carbonate paper; and
s3: and soaking the copper hydroxide-calcium carbonate paper in an organic solution of terephthalic acid, and carrying out water bath heat preservation to obtain the metal organic framework nanosheet.
As a preferred embodiment, among others, the water-soluble polymer,
removing the residual copper nitrate solution on the surface of the copper hydroxyl nitrate-calcium carbonate paper before soaking the copper hydroxyl nitrate-calcium carbonate paper by the potassium hydroxide solution in the step S2; and
removing the residual potassium hydroxide solution on the surface of the copper hydroxide-calcium carbonate paper before soaking the copper hydroxide-calcium carbonate paper by the organic solution of terephthalic acid in step S3.
Further, in the step S1, the concentration of the copper nitrate solution is 0.09 g/ml to 0.26 g/ml; the soaking time of the calcium carbonate paper by the copper nitrate solution is 12 to 48 hours.
Further, in the step S2, the concentration of the potassium hydroxide solution is 0.03-0.08 g/ml; the soaking time of the copper hydroxyl nitrate-calcium carbonate paper by the potassium hydroxide solution is 1 to 12 hours.
Further, in the step S3, the concentration of the terephthalic acid solution is 0.001-0.003 g/ml; soaking the copper hydroxide-calcium carbonate paper in an organic solution of terephthalic acid for 2 to 9 hours; the temperature of the water bath is 30-60 ℃.
Further, in the step S3, the organic solvent of the organic solution of terephthalic acid is a solution of N, N-dimethylformamide.
In a third aspect, the present invention provides a working electrode for an electrochemical workstation, characterized by: the metal organic framework nanosheet comprises the metal organic framework nanosheet or the nanosheet prepared by the preparation method of any one of the above.
In a fourth aspect, the present invention provides a sensor, characterized in that: a working electrode of an electrochemical workstation as described above is included to detect ascorbic acid in human sweat by enzyme-free electrochemical detection.
Compared with the prior art, the invention has the following advantages:
the prepared CuBDC nanosheet of the metal organic framework material has uniform appearance and simple preparation conditions, the agglomeration of the nanosheets is effectively avoided by the long-range assembled multi-stage structure of the CuBDC nanosheet of the metal organic framework prepared by the method, more active sites are exposed by the multi-stage structure, the electrochemical performance of the CuBDC nanosheet is greatly improved, and the CuBDC nanosheet is used as a working electrode of a sensor, so that the sensor has higher sensitivity, lower detection limit and better selectivity.
Drawings
Fig. 1 is an SEM image of metal organic framework CuBDC nanoplates of example 1 of the present invention;
fig. 2 is an XRD pattern of a metal organic framework CuBDC nanosheet of example 3 of the present invention;
fig. 3 is a response curve of a metal organic framework CuBDC nanosheet/glassy carbon electrode enzyme-free sensor and a linear relationship curve of current density-ascorbic acid concentration when ascorbic acid of different concentrations is dripped in example 6 of the present invention;
fig. 4 shows the influence of various agents to be tested on the detection of the metal organic frame CuBDC nanosheet/glassy carbon electrode non-enzyme sensor in embodiment 6 of the present invention;
fig. 5 shows the stability of the metal organic framework material CuBDC nanosheet/glassy carbon electrode enzyme-free electrochemical ascorbic acid sensor of example 6 of the present invention.
Detailed Description
The following describes a specific embodiment of a method for preparing a multilevel structure metal organic framework CuBDC enzyme-free electrochemical detection ascorbic acid sensor according to the technical scheme of the invention in detail with reference to the accompanying drawings.
Example 1 Metal organic framework Material nanosheets
The present embodiment provides a metal organic framework material nanosheet, including a plurality of two-dimensional CuBDC (BDC ═ 1, 4-dicarboxylate benzene) nanosheets. The long-range assembly of the plurality of two-dimensional CuBDC nanosheets into a multistage structure, the orientation of the plurality of two-dimensional CuBDC nanosheets is consistent, and no agglomeration exists among the plurality of two-dimensional CuBDC nanosheets, wherein the two-dimensional CuBDC nanosheets are triangular, and the thickness is 10-40 nm.
Fig. 1 is an SEM image of a multilevel-structure metal-organic framework CuBDC nanosheet of the present embodiment. As shown in FIG. 1, the surface of a CuBDC nanosheet of a prepared multilevel-structure metal-organic framework material is clearly observed in a Scanning Electron Microscope (SEM) to have a plurality of triangular tips which are vertically and orderly arranged, the thickness of the single nanosheet is 10-40nm, and the length of the tip is 50-200 nm. The orientation of the two-dimensional CuBDC nanosheets is known, and the two-dimensional CuBDC nanosheets are free of agglomeration, so that the defect that the two-dimensional nanosheets are easy to agglomerate is overcome.
Embodiment 2 preparation method of metal organic framework nanosheet
The embodiment provides a preparation method for preparing the metal organic framework nanosheets of the above embodiments, including soaking calcium carbonate paper with a copper nitrate solution to obtain copper hydroxyl nitrate-calcium carbonate paper; etching the copper hydroxyl nitrate-calcium carbonate paper by using a potassium hydroxide solution to obtain copper hydroxide-calcium carbonate paper; and soaking the copper hydroxide-calcium carbonate paper in an organic solution of terephthalic acid, and carrying out water bath heat preservation to obtain the metal organic framework nanosheet.
In this example, the concentration of the copper nitrate solution was in the range of 0.09 to 0.26g/ml, and the soaking time for soaking the calcium carbonate paper by the copper nitrate solution was in the range of 12 to 48 hours. The concentration range of the potassium hydroxide solution is 0.03-0.08g/ml, and the soaking time for soaking the copper hydroxyl nitrate-calcium carbonate paper by the potassium hydroxide solution is 1-12 hours. The concentration range of the terephthalic acid solution is 0.001-0.003g/ml, the soaking time range of the copper hydroxide-calcium carbonate paper soaked by the terephthalic acid organic solution is 2-9 hours, and the temperature range of water bath heat preservation is 30-60 ℃. The organic solvent of the organic solution of terephthalic acid is a solution of N, N-dimethylformamide.
In this example, the copper nitrate solution remaining on the surface of the copper oxynitrate-calcium carbonate paper was removed before the copper oxynitrate-calcium carbonate paper was soaked in the potassium hydroxide solution, and the potassium hydroxide solution remaining on the surface of the copper hydroxide-calcium carbonate paper was removed before the copper hydroxide-calcium carbonate paper was soaked in the organic solution of terephthalic acid.
Embodiment 3 preparation method of multilevel-structure metal organic framework CuBDC nanosheet
The invention provides an embodiment of a preparation method of a multilevel-structure metal organic framework CuBDC nanosheet.
The preparation method of the multilevel-structure metal organic framework material CuBDC nanosheet comprises the following steps:
1) weighing 4.8-5.7 g of solid copper nitrate, dissolving the solid copper nitrate with 40ml of ultrapure water, cutting 5cm multiplied by 5cm of calcium carbonate paper, and soaking to obtain copper hydroxyl nitrate/calcium carbonate paper; the soaking time is 18-36 hours. 2) Washing the surface residues of the copper hydroxyl nitrate/calcium carbonate paper obtained in the step 1) with ultrapure water, weighing 2.18-2.88 g of potassium hydroxide solid, dissolving 40ml of ultrapure water, and soaking the copper hydroxyl nitrate/calcium carbonate paper to obtain copper hydroxide/calcium carbonate paper; the soaking time is 8-20 hours.
3) Washing the copper hydroxide/calcium carbonate paper obtained in the step 2) with ultrapure water to remove surface residues, weighing 0.11-0.23 g of terephthalic acid solid, dissolving with an organic solvent, soaking the copper hydroxide/calcium carbonate paper, and carrying out water bath heat preservation; the organic solvent is a mixture of 20ml of ultrapure water and 20ml of N, N-dimethylformamide, the water bath heating temperature is 50 ℃, and the heat preservation time is 3-7 hours.
Fig. 2 is an XRD pattern of the multilevel structure metal-organic framework CuBDC nanosheet of the present embodiment. As shown in fig. 2, the prepared multilevel-structure metal organic framework material CuBDC nanosheet is high in purity and has no other impurities.
Embodiment 4 preparation method of multilevel-structure metal organic framework CuBDC nanosheet
The embodiment provides a preparation method of a multilevel-structure metal organic framework CuBDC nanosheet.
The preparation method of the multilevel-structure metal organic framework material CuBDC nanosheet comprises the following steps:
1) weighing 4.8g of solid copper nitrate, dissolving the solid copper nitrate by using 40ml of ultrapure water, cutting 5cm multiplied by 5cm of calcium carbonate paper, and soaking to obtain hydroxyl copper nitrate/calcium carbonate paper; the soaking time was 36 hours.
2) Washing the surface residues of the copper hydroxyl nitrate/calcium carbonate paper obtained in the step 1) with ultrapure water, weighing 2.18g of potassium hydroxide solid, dissolving 40ml of ultrapure water, and soaking the copper hydroxyl nitrate/calcium carbonate paper to obtain copper hydroxide/calcium carbonate paper; the soaking time of (3) is 18 hours.
3) Washing the copper hydroxide/calcium carbonate paper obtained in the step 2) with ultrapure water to remove surface residues, weighing 0.27g of terephthalic acid solid, dissolving with an organic solvent, soaking the copper hydroxide/calcium carbonate paper, and carrying out water bath heat preservation; the organic solvent is a mixture of 20ml of ultrapure water and 20ml of N, N-dimethylformamide, and the mixture is heated in a water bath at the temperature of 50 ℃ and is kept for 9 hours.
The multi-level structure metal organic framework material CuBDC nanosheet obtained in the embodiment is used as a sensing electrode material to assemble an enzyme-free electrochemical ascorbic acid detection sensor, and an electrochemical workstation is adopted for testing. The test result shows that the sensitivity of the sensor is 0.257 mA.mM -1 ·cm -2
The surface of the multilevel-structure metal organic framework CuBDC nanosheet of the embodiment presents a plurality of crystal agglomerated morphologies, and the agglomerated crystals obstruct the exposure of active sites of the original multilevel structure and influence the electrochemical performance of the metal organic framework CuBDC nanosheet of the invention.
EXAMPLE 5 working electrode for electrochemical workstation
The invention may also provide an embodiment of a working electrode of an electrochemical workstation, comprising: the metal organic framework nanosheet or the nanosheet prepared in any one of the above embodiments is capable of catalytically oxidizing the corresponding substance, which is ascorbic acid.
EXAMPLE 6A sensor
This example provides a sensor for the enzyme-free electrochemical detection of ascorbic acid. The preparation method of the sensor comprises the following steps of adopting a multi-stage structure metal organic frame material CuBDC nanosheet as a sensing electrode material, modifying the sensing electrode material on a pretreated Glassy Carbon Electrode (GCE), respectively preparing a mixed solution of 0.08mol/L disodium hydrogen phosphate, 0.02mol/L sodium dihydrogen phosphate and 0.1mol/L potassium chloride, and standing to obtain an electrolyte; the working electrode is a glassy carbon electrode, the reference electrode is a silver/silver chloride electrode, the auxiliary electrode is a platinum wire, and the three electrodes are inserted into electrolyte; the detection of ascorbic acid was performed under a voltage of 0.3V vs. ag | AgCl applied to the working electrode at the electrochemical workstation.
The enzyme-free electrochemical ascorbic acid sensor composed of the multilevel-structure metal-organic framework material CuBDC nanosheets prepared by the embodiment of the invention is used for detecting ascorbic acid:
(1) the prepared conducting substrates of the multilevel-structure metal organic frame CuBDC/glassy carbon electrode and the like are used as working electrodes, silver/silver chloride is used as a reference electrode, a platinum wire is used as an auxiliary electrode, and a phosphate buffer solution with the pH value of 7.4 is inserted into the auxiliary electrode;
(2) the ascorbic acid is detected under the voltage of 0.2V-0.5V vs. Ag | AgCl by adopting a time-current testing technology.
The experimental procedure for this example is as follows:
2Cu(II)+C 6 H 8 O 6 →2Cu(I)+C 6 H 6 O 6 +2H +
2Cu(I)→2Cu(II)+2e -
the electric signal generated by the catalytic oxidation of the ascorbic acid and Cu (II) realizes the detection of the ascorbic acid by the multi-level structure metal organic framework enzyme-free electrochemical ascorbic acid sensor, and a linear fitting straight line of the ascorbic acid concentration and the electric signal is obtained based on the principle.
FIG. 3 is a response curve and a linear relationship curve of current density to ascorbic acid concentration when different concentrations of ascorbic acid were added dropwise in this example. Fig. 4 shows the influence of various test agents on the detection of the metal organic framework CuBDC nanosheet/glassy carbon electrode non-enzyme sensor in this embodiment. Fig. 5 shows the stability of the metal organic framework material CuBDC nanosheet/glassy carbon electrode enzyme-free electrochemical ascorbic acid sensor of the present embodiment.
As shown in figure 3, the ascorbic acid solution with different concentrations is dripped by adopting a time-current testing technology to obtain a time-current step-shaped curve and a concentration-current density linear relation straight line, and the result shows that the sensitivity of the sensor for electrochemically detecting the ascorbic acid in the human sweat without the enzyme reaches 0.381 mA.mM -1 ·cm -2 The linear range is 0.006-0.676 mM.
As shown in FIG. 4, 0.1mmol/L ascorbic acid, 0.05mmol/L cysteine, 0.05mmol/L sodium chloride, 0.05mmol/L potassium chloride, 0.05mmol/L lactic acid, 0.05mmol/L fructose, 0.05mmol/L glucose, 0.05mmol/L uric acid were added to the test solution, respectively, and the detection result showed that the sensor had excellent selectivity.
As shown in FIG. 5, electrochemical response test of 0.05mmol/L ascorbic acid on electrode was performed every three days under 30 days of normal temperature and pressure storage, and the test result shows that the sensor has excellent stability.
The enzyme-free electrochemical ascorbic acid sensor based on the CuBDC nanosheet of the metal organic framework material, which is prepared by the invention, has good electrochemical performance and can be practically applied and popularized.

Claims (10)

1. A metal-organic framework nanosheet, characterized by: the method comprises the following steps:
a plurality of two-dimensional CuBDC nanosheets;
the plurality of two-dimensional CuBDC nanosheets are assembled into a multi-stage structure in a long-range manner; the orientation of the plurality of two-dimensional CuBDC nanosheets is consistent, and no agglomeration exists among the plurality of two-dimensional CuBDC nanosheets;
the two-dimensional CuBDC nanosheet is triangular, the thickness of the nanosheet is 10-40nm, and the length of the tip is 50-200 nm.
2. A method of making metal organic framework nanoplates as in claim 1, wherein: the method comprises the following steps:
s1: soaking calcium carbonate paper in a copper nitrate solution to obtain hydroxyl copper nitrate-calcium carbonate paper;
s2: etching the copper hydroxyl nitrate-calcium carbonate paper by using a potassium hydroxide solution to obtain copper hydroxide-calcium carbonate paper; and
s3: and soaking the copper hydroxide-calcium carbonate paper in an organic solution of terephthalic acid, and carrying out water bath heat preservation to obtain the metal organic framework nanosheet.
3. A process for the preparation of metal organic framework nanoplatelets according to claim 2, characterized in that: wherein the content of the first and second substances,
removing the residual copper nitrate solution on the surface of the copper hydroxyl nitrate-calcium carbonate paper before soaking the copper hydroxyl nitrate-calcium carbonate paper by the potassium hydroxide solution in the step S2; and
removing the residual potassium hydroxide solution on the surface of the copper hydroxide-calcium carbonate paper before soaking the copper hydroxide-calcium carbonate paper by the organic solution of terephthalic acid in step S3.
4. A process for the preparation of metal-organic framework nanoplatelets according to claim 2 or 3, characterized in that: in the step S1, the concentration of the copper nitrate solution is 0.09 g/ml to 0.26 g/ml; the soaking time of the calcium carbonate paper by the copper nitrate solution is 12 to 48 hours.
5. A process for the preparation of metal-organic framework nanoplatelets according to claim 2 or 3, characterized in that: in the step S2, the concentration of the potassium hydroxide solution is 0.03-0.08 g/ml; the soaking time of the copper hydroxyl nitrate-calcium carbonate paper by the potassium hydroxide solution is 1 to 12 hours.
6. A process for the preparation of metal organic framework nanoplatelets according to claim 4 characterized in that: in the step S2, the concentration of the potassium hydroxide solution is 0.03-0.08 g/ml; the soaking time of the copper hydroxyl nitrate-calcium carbonate paper by the potassium hydroxide solution is 1 to 12 hours.
7. A process for the preparation of metal-organic framework nanoplatelets according to claim 2 or 3 or 6, characterized in that: in the step S3, the concentration of the terephthalic acid solution is 0.001-0.003 g/ml; soaking the copper hydroxide-calcium carbonate paper in an organic solution of terephthalic acid for 2 to 9 hours; the temperature of the water bath is 30-60 ℃.
8. Method for the preparation of metal organic framework nanoplatelets according to claim 7, characterized in that: in the step S3, the organic solvent of the organic solution of terephthalic acid is a solution of N, N-dimethylformamide.
9. A working electrode for an electrochemical workstation, comprising: nanosheet comprising a metal organic framework as defined in claim 1, or prepared by a method of preparation as defined in any one of claims 2 to 8.
10. A sensor, characterized by: a working electrode comprising the electrochemical workstation of claim 9 to detect ascorbic acid in human sweat by enzyme-free electrochemistry.
CN202210656983.9A 2022-06-10 2022-06-10 Metal organic frame nano-sheet, preparation method, working electrode and sensor Active CN115109262B (en)

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CN107238650A (en) * 2017-06-09 2017-10-10 吉林大学 A kind of two-dimentional nickel cobalt bimetallic MOFs nanometer sheets and its applied in glucose detection
CN108866561A (en) * 2018-06-27 2018-11-23 大连理工大学 A kind of preparation method and applications of electro-catalysis carbon dioxide reduction electrode

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