CN115109262B - Metal organic frame nano-sheet, preparation method, working electrode and sensor - Google Patents
Metal organic frame nano-sheet, preparation method, working electrode and sensor Download PDFInfo
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- CN115109262B CN115109262B CN202210656983.9A CN202210656983A CN115109262B CN 115109262 B CN115109262 B CN 115109262B CN 202210656983 A CN202210656983 A CN 202210656983A CN 115109262 B CN115109262 B CN 115109262B
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Abstract
The invention discloses a metal organic frame nano sheet, a preparation method, a working electrode and a sensor, and belongs to the technical field of nano materials and electrochemistry. The metal organic framework nanosheets comprise: the two-dimensional CuBDC nanometer sheets are in a multi-stage structure, the two-dimensional CuBDC nanometer sheets are Cheng Zuzhuang long, the directions of the two-dimensional CuBDC nanometer sheets are consistent, no aggregation exists among the two-dimensional CuBDC nanometer sheets, the two-dimensional CuBDC nanometer sheets are triangular, and the thickness is 10-40nm. The invention improves the defect of easy agglomeration of the two-dimensional nano-sheets, 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
Technical Field
The invention relates to the technical field of nanomaterials 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 for human body, and can treat scurvy, enhance immunity of human body, promote absorption of minerals such as calcium, phosphorus and iron, and assist metabolism of skin tissue. Too much or too little intake of ascorbic acid can lead to various diseases, the most well known of which is scurvy. Because the human body can not self-synthesize the ascorbic acid, how to monitor the concentration of the ascorbic acid in the human body is important for preventing and treating various diseases such as scurvy. The electrochemical method has the outstanding advantages of simple operation, rapid and accurate detection, low cost and easy miniaturization of instruments and devices, and the portable sensor for detecting human sweat and ascorbic acid becomes a big hot spot in the development. The ascorbic acid sensor provided in the market at present adopts biological enzyme as a sensing material, but natural enzyme is used as protein, the activity is very easy to be interfered by the outside (pH, temperature and the like), the stability is poor, the measurement is inaccurate and even the detection function is completely lost, the cost is extremely high, and the fixing step is complicated. Compared with an enzyme type ascorbic acid sensor, when the technology of the enzyme-free ascorbic acid sensor is adopted, the catalytic oxidation of the ascorbic acid can be realized on the surface of the electrode, and the detection of the human body ascorbic acid can be realized through the correlation of a current signal and the concentration of the ascorbic acid.
Among the many sensing materials, metal organic frameworks are widely used in the electrochemical sensing field due to their large specific surface area, many active sites and adjustable pore channel sizes. The surface of the metal organic framework with the two-dimensional nano sheet morphology is provided with a plurality of low coordination atoms which can be used as active sites of electrocatalytic oxidation reduction, so that the adsorption and oxidation of the object to be detected on the surface of the metal organic framework are greatly facilitated, and the sensing performance of the metal organic framework is improved. However, the nano-sheets of the metal organic frameworks prepared in the prior art are extremely easy to agglomerate, so that the defect that active sites cannot be fully utilized is caused, and the electrochemical sensor based on the metal organic frameworks has lower detection accuracy and poorer detection repeatability on ascorbic acid.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problems that the metal organic frame material is easy to agglomerate and the sensing electrode performance is insufficient, and aims to provide a multi-level structure metal organic frame CuBDC nano-sheet with simple process, low cost and excellent electrochemical performance, and a preparation method and application thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows:
in a first aspect, the invention provides a metal organic framework material nano sheet, which comprises a plurality of two-dimensional CuBDC nano sheets, wherein the lengths Cheng Zuzhuang of the plurality of two-dimensional CuBDC nano sheets are in a multi-stage structure, the orientations of the plurality of two-dimensional CuBDC nano sheets are consistent, and agglomeration among the plurality of two-dimensional CuBDC nano sheets does not exist, and the two-dimensional CuBDC nano sheets are triangular in shape and have a thickness of 10-40nm.
In a second aspect, the present invention also provides a method for preparing a metal-organic framework nanosheet, which is characterized in that: the method comprises the following steps:
s1: immersing the calcium carbonate paper in a copper nitrate solution to obtain hydroxyl copper nitrate-calcium carbonate paper;
s2: etching the hydroxy copper nitrate-calcium carbonate paper by potassium hydroxide solution to obtain copper hydroxide-calcium carbonate paper; and
s3: 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 nano-sheet.
As a preferred embodiment, the method comprises, among others,
removing residual copper nitrate solution on the surface of the hydroxy copper nitrate-calcium carbonate paper before soaking the hydroxy copper nitrate-calcium carbonate paper in the potassium hydroxide solution in the step S2; and
removing potassium hydroxide solution remained on the surface of the copper hydroxide-calcium carbonate paper before the copper hydroxide-calcium carbonate paper is soaked in the organic solution of terephthalic acid in the step S3.
Further, in the step S1, the concentration of the copper nitrate solution is 0.09-0.26g/ml; the soaking time of soaking the calcium carbonate paper by the copper nitrate solution is 12-48 hours.
Further, in the step S2, the concentration of the potassium hydroxide solution is 0.03-0.08g/ml; the soaking time of soaking the hydroxy copper nitrate-calcium carbonate paper in the potassium hydroxide solution is 1-12 hours.
Further, in the step S3, the concentration of the terephthalic acid solution is 0.001-0.003g/ml; soaking copper hydroxide-calcium carbonate paper for 2-9 hours by using an organic solution of terephthalic acid; the temperature of the water bath heat preservation is 30-60 ℃.
Further, in the step S3, the organic solvent of the organic solution of terephthalic acid is an N, N-dimethylformamide solution.
In a third aspect, the present invention provides a working electrode for an electrochemical workstation, characterized by: comprising a metal organic framework nanoplatelet as described above, or comprising nanoplatelets prepared by a method of preparation as described in any of the above.
In a fourth aspect, the present invention provides a sensor characterized by: a working electrode comprising an electrochemical workstation as described above to detect human sweat ascorbic acid by enzyme-free electrochemistry.
Compared with the prior art, the invention has the following advantages:
the metal organic frame CuBDC nano-sheet prepared by the method has uniform morphology and simple preparation conditions, the multi-stage structure assembled for a long time of the metal organic frame CuBDC nano-sheet effectively avoids agglomeration of the nano-sheet, the multi-stage structure exposes more active sites, the electrochemical performance of the metal organic frame CuBDC nano-sheet is greatly improved, the metal organic frame CuBDC nano-sheet is used as a working electrode of a sensor, the sensor has higher sensitivity, lower detection limit and better selectivity, and the preparation method is simple, easy to repeatedly implement and has good industrial value.
Drawings
FIG. 1 is an SEM image of a metal-organic framework CuBDC nanoplatelet of example 1 of the invention;
FIG. 2 is an XRD pattern of a metal organic framework CuBDC nanoplatelet of example 3 of the invention;
FIG. 3 is a graph showing the response curve and the linear relationship between current density and ascorbic acid concentration of the metal organic framework CuBDC nanosheets/glassy carbon electrode enzyme-free sensor in example 6 of the present invention when different concentrations of ascorbic acid are added dropwise;
FIG. 4 is a graph showing the effect of various reagents to be tested on detection of a metal organic framework CuBDC nanosheets/glassy carbon electrode enzyme-free sensor according to example 6 of the present invention;
fig. 5 is the stability of the metal organic framework material CuBDC nanoplatelets/glassy carbon electrode enzyme-free electrochemical ascorbic acid sensor of example 6 of the present invention.
Detailed Description
Specific embodiments of a method for preparing a multi-stage structure metal-organic framework CuBDC enzyme-free electrochemical detection ascorbic acid sensor according to the technical scheme of the present invention are described in detail below with reference to the accompanying drawings.
Example 1 Metal organic framework Material nanoplatelets
The present embodiment provides a metal organic framework material nanoplatelet comprising a plurality of two-dimensional CuBDC (bdc=1, 4-dicarboxyphenyl) nanoplatelets. The lengths Cheng Zuzhuang of the two-dimensional CuBDC nano sheets are in a multi-stage structure, the orientations of the two-dimensional CuBDC nano sheets are consistent, no aggregation exists among the two-dimensional CuBDC nano sheets, the two-dimensional CuBDC nano sheets are triangular, and the thickness is 10-40nm.
Fig. 1 is an SEM image of the CuBDC nanoplatelets of the multi-structured metal organic framework of the present embodiment. As shown in FIG. 1, the surface of the prepared multi-level structure metal organic framework material CuBDC nano-sheet is clearly observed in a Scanning Electron Microscope (SEM) to have a plurality of triangular tips vertically and orderly arranged, the thickness of a single nano-sheet is 10-40nm, and the tip length is 50-200 nm. The orientation of the two-dimensional CuBDC nano sheets is known, and the two-dimensional CuBDC nano sheets are not agglomerated, so that the defect that the two-dimensional nano sheets are easy to agglomerate is overcome.
Example 2 preparation method of Metal organic framework nanosheets
The embodiment provides a preparation method for preparing the metal organic frame nanosheets of the above embodiment, which comprises the steps of soaking calcium carbonate paper through a copper nitrate solution to obtain hydroxy copper nitrate-calcium carbonate paper; etching the copper hydroxy nitrate-calcium carbonate paper by potassium hydroxide solution to obtain copper hydroxide-calcium carbonate paper; and soaking 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 nano sheet.
In this example, the concentration of the copper nitrate solution was in the range of 0.09-0.26g/ml, and the soaking time for soaking the calcium carbonate paper by the copper nitrate solution was in the range of 12-48 hours. The concentration of the potassium hydroxide solution is in the range of 0.03-0.08g/ml, and the soaking time of soaking the hydroxy copper nitrate-calcium carbonate paper by the potassium hydroxide solution is in the range of 1-12 hours. The concentration of the terephthalic acid solution is 0.001-0.003g/ml, the soaking time of soaking copper hydroxide-calcium carbonate paper by organic solution of terephthalic acid is 2-9 hours, and the temperature of water bath heat preservation is 30-60 ℃. The organic solvent of the organic solution of terephthalic acid is an N, N-dimethylformamide solution.
In this example, the copper nitrate solution remaining on the surface of the copper hydroxycarbonate-calcium carbonate paper was removed before the copper hydroxycarbonate-calcium carbonate paper was soaked with 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 with the organic solution of terephthalic acid.
Example 3 preparation method of Multi-level Metal organic framework CuBDC nanosheets
The invention provides an embodiment of a preparation method of a multi-level structure metal organic framework CuBDC nanosheet.
The preparation method of the multi-level structure metal organic framework material CuBDC nano sheet comprises the following steps:
1) Weighing 4.8-5.7 g of copper nitrate solid, dissolving the copper nitrate solid with 40ml of ultrapure water, cutting calcium carbonate paper, soaking the calcium carbonate paper in a size of 5cm multiplied by 5cm to obtain hydroxy copper nitrate/calcium carbonate paper; the soaking time is 18-36 hours. 2) Washing the hydroxy copper nitrate/calcium carbonate paper obtained in the step 1) with ultrapure water to remove surface residues, weighing 2.18-2.88 g of potassium hydroxide solid, dissolving 40ml of ultrapure water, and soaking the hydroxy copper nitrate/calcium carbonate paper to obtain the copper hydroxide/calcium carbonate paper; 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 the terephthalic acid solid with an organic solvent, soaking the copper hydroxide/calcium carbonate paper, and preserving heat in a water bath; the organic solvent is a mixture of 20ml of ultrapure water and 20ml of N, N-dimethylformamide, and the water bath heating temperature is 50 ℃ and the heat preservation time is 3-7 hours.
Fig. 2 is an XRD pattern of the multi-structured metal-organic framework CuBDC nanoplatelets of the present embodiment. As shown in FIG. 2, the prepared multi-level structure metal organic framework material CuBDC nano-sheets have high purity and no other impurities exist.
Example 4 preparation method of Multi-level Metal organic framework CuBDC nanosheets
The embodiment provides an embodiment of a preparation method of a multi-level structure metal organic framework CuBDC nanosheet.
The preparation method of the multi-level structure metal organic framework material CuBDC nano sheet comprises the following steps:
1) Weighing 4.8g of copper nitrate solid, dissolving with 40ml of ultrapure water, cutting calcium carbonate paper, soaking with 5cm multiplied by 5cm to obtain hydroxy copper nitrate/calcium carbonate paper; the soaking time was 36 hours.
2) Washing the hydroxy copper nitrate/calcium carbonate paper obtained in the step 1) with ultrapure water to remove surface residues, weighing 2.18g of potassium hydroxide solid, dissolving 40ml of ultrapure water, and soaking the hydroxy copper nitrate/calcium carbonate paper to obtain copper hydroxide/calcium carbonate paper; is immersed for 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 the terephthalic acid solid with an organic solvent, soaking the copper hydroxide/calcium carbonate paper, and preserving heat in a water bath; the organic solvent was a mixture of 20ml of ultrapure water and 20ml of N, N-dimethylformamide, and the temperature was heated in a water bath at 50℃for 9 hours.
The multi-level structure metal organic framework material CuBDC nano-sheet obtained in the embodiment is used as a sensing electrode material to assemble an enzyme-free electrochemical detection ascorbic acid 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 CuBDC nanosheets of the multilevel structure of the embodiment presents a plurality of crystal agglomeration morphology, and the agglomeration crystals obstruct the exposure of active sites of the original multilevel structure and influence the electrochemical performance of the CuBDC nanosheets of the metal-organic frame.
Example 5 working electrode of electrochemical workstation
The present invention may also provide an embodiment of a working electrode for an electrochemical workstation comprising: the metal organic framework nanoplatelets described above or nanoplatelets prepared in any of the above embodiments are capable of catalyzing oxidation of a corresponding substance, the corresponding substance being ascorbic acid.
Example 6A sensor
The present embodiment provides a sensor for enzyme-free electrochemical detection of ascorbic acid. The preparation method of the sensor comprises the following steps of adopting a multi-level structure metal organic framework material CuBDC nano sheet as a sensing electrode material, modifying the sensing electrode material on a pretreated Glassy Carbon Electrode (GCE), respectively preparing 0.08mol/L disodium hydrogen phosphate, 0.02mol/L sodium dihydrogen phosphate and 0.1mol/L potassium chloride mixed solution, and standing the sensing electrode material to obtain 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 the electrolyte; the ascorbic acid detection was performed at an electrochemical workstation applying a voltage of 0.3v vs. ag|agcl to the working electrode.
The multi-level structure metal organic framework material CuBDC nano-sheets prepared by the embodiment of the invention form the detection of the enzyme-free electrochemical ascorbic acid sensor on the ascorbic acid:
(1) The prepared conductive substrates such as a multi-level structure metal organic framework CuBDC/glassy carbon electrode and the like are used as working electrodes, silver/silver chloride is used as a reference electrode, and a platinum wire is used as an auxiliary electrode and is inserted into phosphate buffer solution with the pH value of 7.4;
(2) The ascorbic acid is detected by a time-current test technique at a voltage of 0.2V-0.5V vs. Ag|AgCl.
The experimental procedure of 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 detection of the ascorbic acid by the multi-stage structure metal organic framework enzyme-free electrochemical ascorbic acid sensor is realized by the electric signal generated by the catalytic oxidation of the ascorbic acid and Cu (II), and the linear fitting straight line of the concentration of the ascorbic acid and the electric signal is obtained based on the principle.
FIG. 3 is a graph showing the response curve and the linear relationship between the current density and the ascorbic acid concentration when different concentrations of ascorbic acid were added dropwise in this example. Fig. 4 is a diagram showing the influence of various reagents to be tested on detection of the CuBDC nanosheets/glassy carbon electrode enzyme-free sensor of the metal organic framework in this embodiment. Fig. 5 is the stability of the metal organic framework material CuBDC nanoplatelets/glassy carbon electrode enzyme-free electrochemical ascorbic acid sensor of the present embodiment.
As shown in FIG. 3, ascorbic acid solutions with different concentrations are dripped by adopting a time-current test technology to obtain a time-current step curve and a linear relation line of concentration-current density, and the result shows that the sensitivity of the sensor for detecting human sweat by enzyme-free electrochemistry 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 results showed that the sensor had excellent selectivity.
As shown in FIG. 5, the electrochemical response test of the electrode to 0.05mmol/L ascorbic acid was performed every three days under the condition of 30 days of normal temperature and normal pressure preservation, and the detection result shows that the sensor has excellent stability.
The enzyme-free electrochemical ascorbic acid sensor based on the metal organic framework material CuBDC nano-sheet has good electrochemical performance and can be practically applied and popularized.
Claims (10)
1. A preparation method of a metal organic framework nano sheet is characterized by comprising the following steps of: the method comprises the following steps:
s1: immersing the calcium carbonate paper in a copper nitrate solution to obtain hydroxyl copper nitrate-calcium carbonate paper;
s2: etching the hydroxy copper nitrate-calcium carbonate paper by potassium hydroxide solution to obtain copper hydroxide-calcium carbonate paper; and
s3: 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 nano-sheet.
2. The method for preparing the metal-organic framework nano-sheet according to claim 1, wherein: wherein, the liquid crystal display device comprises a liquid crystal display device,
removing residual copper nitrate solution on the surface of the hydroxy copper nitrate-calcium carbonate paper before soaking the hydroxy copper nitrate-calcium carbonate paper in the potassium hydroxide solution in the step S2; and
removing potassium hydroxide solution remained on the surface of the copper hydroxide-calcium carbonate paper before the copper hydroxide-calcium carbonate paper is soaked in the organic solution of terephthalic acid in the step S3.
3. The method for preparing the metal-organic framework nano-sheet according to claim 1 or 2, wherein the method comprises the following steps: in the step S1, the concentration of the copper nitrate solution is 0.09-0.26g/mL; the soaking time of soaking the calcium carbonate paper by the copper nitrate solution is 12-48 hours.
4. A method of preparing a metal organic framework nanoplatelet according to claim 3, wherein: in the step S2, the concentration of the potassium hydroxide solution is 0.03-0.08g/mL; the soaking time of soaking the hydroxy copper nitrate-calcium carbonate paper in the potassium hydroxide solution is 1-12 hours.
5. The method for preparing the metal-organic framework nano-sheet according to claim 1, 2 or 4, wherein the method comprises the following steps: in the step S2, the concentration of the potassium hydroxide solution is 0.03-0.08g/mL; the soaking time of soaking the hydroxy copper nitrate-calcium carbonate paper in the potassium hydroxide solution is 1-12 hours.
6. The method for preparing the metal-organic framework nano-sheet according to claim 5, wherein: in the step S3, the concentration of the terephthalic acid solution is 0.001-0.003g/mL; soaking copper hydroxide-calcium carbonate paper for 2-9 hours by using an organic solution of terephthalic acid; the temperature of the water bath heat preservation is 30-60 ℃.
7. The method for preparing the metal-organic framework nano-sheet according to claim 6, wherein: in the step S3, the organic solvent of the organic solution of terephthalic acid is an N, N-dimethylformamide solution.
8. A metal organic framework nanoplatelet, characterized in that: prepared by the preparation method of any one of claims 1 to 7, comprising:
a plurality of two-dimensional CuBDC nanoplatelets;
the plurality of two-dimensional CuBDC nanoplatelets are Cheng Zuzhuang in a multi-stage structure; the orientation of the two-dimensional CuBDC nano sheets is consistent, and aggregation does not exist among the two-dimensional CuBDC nano sheets;
wherein the two-dimensional CuBDC nano-sheet is triangular, the thickness of the single nano-sheet is 10-40nm, and the tip length is 50-200 nm.
9. A working electrode for an electrochemical workstation, characterized by: comprising the metal organic framework nanoplatelets prepared by the preparation method of any one of claims 1-7.
10. A sensor, characterized in that: a working electrode comprising the electrochemical workstation of claim 9 for the detection of human sweat ascorbic acid by enzyme-free electrochemistry.
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