CN114539543A - Nano-strip manganese-doped metal organic framework material Mn @ HKUST-1, and preparation method and application thereof - Google Patents
Nano-strip manganese-doped metal organic framework material Mn @ HKUST-1, and preparation method and application thereof Download PDFInfo
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- CN114539543A CN114539543A CN202111631025.8A CN202111631025A CN114539543A CN 114539543 A CN114539543 A CN 114539543A CN 202111631025 A CN202111631025 A CN 202111631025A CN 114539543 A CN114539543 A CN 114539543A
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Abstract
The invention discloses a preparation method of a nano banded manganese doped metal organic framework material Mn @ HKUST-1, which comprises the following steps: mixing the metal organic framework material HKUST-1 and manganese salt in a solution, carrying out ultrasonic reaction for 10 min-2 h, centrifuging, washing and drying to obtain the nano strip manganese doped metal organic framework material Mn @ HKUST-1. The invention also discloses a manganese-doped metal organic framework material Mn @ HKUST-1 prepared by the method and application thereof in H detection2O2The use of (1). The nano strip manganese doped metal organic framework material Mn @ HKUST-1 is used for detecting H2O2Has high sensitivity and selectivity, and is suitable for use as H2O2A sensor. The conductive ink is prepared based on Mn @ HKUST-1, and the flexible sensing device is constructed by a screen printing technology, so that H can be dynamically realized in real time2O2High sensitivity and specificity detection.
Description
Technical Field
The invention relates to the technical field of metal organic framework materials, in particular to a nano strip manganese doped metal organic framework material Mn @ HKUST-1, and a preparation method and application thereof.
Background
In recent years, Metal Organic Frameworks (MOFs) have been widely used in various fields due to advantages of highly porous surfaces, excellent thermo-chemical stability, tunable structures, and versatility. At present, there is a concern about the application of MOFs in nanoenzyme sensors. However, MOFs such as HKUST-1 are generally polyhedral structures, and in the sensing process, reactants are not easy to approach active sites, so that the utilization rate of the catalytic active sites is low, and thus the electrocatalytic performance of the sensor is low. Therefore, in order to improve the sensitivity of sensors constructed based on MOFs, it is very important to carefully design electrodes with more exposed reactive sites and reasonable electronic structure. And the surface electronic structure has a stronger oxidation state or reduction state, which is greatly helpful to the oxidation or reduction kinetics of the electrode. Hydrogen peroxide (H)2O2) One of the active oxygens is a product of a biological metabolic reaction and is also a potential biomarker of certain physiological diseases. Therefore, a detection method with high sensitivity and good selectivity is developed based on the MOFs nano-bionic enzyme for reliably and dynamically detecting H in real time2O2And has important significance for diagnosing and researching related diseases.
Conventional H2O2The sensor comprises an enzyme sensor and a bionic enzyme sensor, wherein the enzyme sensor has the defects of poor repeatability, short service life, high cost, easy inactivation, strict operation requirement and the like, and the applicability of the sensor is limited. The bionic enzyme sensor gradually becomes electrochemical detection H due to the characteristics of low cost, high stability, simple preparation, good catalytic activity and the like2O2Is a hot point of research. At present, reported H2O2The bionic enzyme sensor still has the problems of high detection limit, low sensitivity for detecting small molecules in cells and the like. Therefore, H with high sensitivity and good selectivity is prepared2O2Sensors are important for the diagnosis and study of major diseases. Fundamentally, the surface electronic structure with a stronger oxidation state or reduction state greatly contributes to the oxidation or reduction kinetics of the electrode, respectively. In order to increase the sensitivity of the sensor, it is very important to carefully design the electrodes with a reasonable electronic structure.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nano-strip manganese-doped metal-organic framework material Mn @ HKUST-1 for detecting H2O2Has high sensitivity and selectivity, and is suitable for use as H2O2A sensor.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a nano banded manganese doped metal organic framework material Mn @ HKUST-1, which comprises the following steps:
mixing the metal organic framework material HKUST-1 and manganese salt in a solution, carrying out ultrasonic reaction for 10 min-2 h, centrifuging, washing and drying to obtain the nano strip manganese doped metal organic framework material Mn @ HKUST-1.
According to the invention, HKUST-1 is subjected to manganese doping in a mode of mixing HKUST-1 and manganese salt, so that a doped metal organic framework material Mn @ HKUST-1 with a stronger oxidation state surface electronic structure is obtained, the appearance of the Mn @ HKUST-1 doped material is changed into a nano-belt structure from a polyhedral structure, the specific surface area of the HKUST-1 material is effectively increased, the reaction active area is increased, and the electrocatalytic activity of the material is greatly improved.
Further, the manganese salt includes, but is not limited to, one or more of manganese chloride, manganese sulfate, manganese nitrate.
Further, the solution includes, but is not limited to, ethanol, methanol.
Further, the concentration of HKUST-1 in the mixed solution is 0.1-1mM, and the concentration ratio of HKUST-1 to manganese ions is 1:1-1:15, preferably 1:1-1: 10.
Further, the drying methods include, but are not limited to, freeze drying, vacuum drying, and room temperature drying.
Further, the preparation method of the metal organic framework material HKUST-1 comprises the following steps:
dissolving copper salt and trimesic acid in N, N-dimethylformamide to ensure that the concentration of the copper salt is 0.2-1.0M and the concentration ratio of copper ions to the trimesic acid is 1:1-1: 5; adding 20-80% ethanol water solution, stirring, and performing ultrasonic treatment for 3-30 min to fully dissolve the suspension until the suspension is clear; reacting the reaction solution at 60-100 ℃ for 10-40 hours, centrifugally washing the reaction product with DMF and ethanol, and drying at 25-80 ℃ for 5-72 hours to obtain the metal organic framework material HKUST-1.
Further, the copper salt is one or more of copper salts such as copper nitrate, copper acetate, copper sulfate and copper chloride; the addition amount of the ethanol water solution is 1-5 times of the volume of the solution.
The invention also provides the nano-strip manganese-doped metal organic framework material Mn @ HKUST-1 prepared by the method.
The invention also provides a flexible sensing device which is a printing electrode prepared by mixing the nano strip-shaped manganese doped metal organic framework material Mn @ HKUST-1 and carbon slurry according to the mass ratio of 1:2-1:10 and then carrying out screen printing. The size and shape of the printed electrode can be designed according to the specific requirements of the experiment.
The invention also provides the application of the flexible sensing device in electrochemical detection of H2O2The use of (1).
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, Mn @ HKUST-1 with a strong oxidation state surface electronic structure is obtained by manganese doping of HKUST-1, and the shape of the HKUST-1 is changed from a polyhedral structure to a nano-belt structure, so that the specific surface area of the material is effectively increased, the reaction active area is increased, and the electrocatalytic activity of the material is greatly improved. In addition, the manganese etching is a process which is mild, convenient and simple to operate, is suitable for large-scale production, and therefore has a great application prospect.
2. The nano strip manganese doped metal organic framework material Mn @ HKUST-1 is used for detecting H2O2Has high sensitivity and selectivity, and is suitable for use as H2O2A sensor. The conductive ink is prepared based on Mn @ HKUST-1, and the flexible sensing device is constructed by a screen printing technology, so that H can be dynamically realized in real time2O2High sensitivity and specificity.
Drawings
FIG. 1 is an SEM image of HKUST-1(A) and Mn @ HKUST-1 (B);
FIG. 2 is an XRD pattern of HKUST-1 and Mn @ HKUST-1;
FIG. 3A is a graph of HKUST-1 and Mn @ HKUST-1 vs. 1mM H2O2The CV response of (c); FIG. 3B is a current response histogram corresponding to A;
FIG. 4 shows Mn @ HKUST-1 vs. H2O2Selective testing of (2).
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
Example 1: preparation of nano-strip manganese doped Mn @ HKUST-1
1. HKUST-1 synthesized by thermal synthesis method
Respectively weighing copper nitrate trihydrate [ Cu (NO) by using an electronic balance3)2·3H2O]0.55g and 0.28g of trimesic acid (1,3, 5-benzenetricarboxylic acid); firstly, dissolving copper nitrate trihydrate in 3.75mLN, N-dimethylformamide, then adding trimesic acid into a reaction solution in which the copper nitrate is dissolved, then adding 5mL of anhydrous ethanol and 2.5mL of deionized water into the reaction solution, and fully stirring to ensure that the concentration of the copper nitrate in the reaction system is 0.2M and the concentration of the trimesic acid is 0.1M, thus obtaining a blue suspension. And placing the beaker filled with the reaction solution into an ultrasonic cleaner for 5 minutes to fully dissolve the suspension until the suspension is clear. A tetrafluoroethylene stirrer was added to the beaker, and the beaker was placed on a magnetic stirrer and stirred for 10 minutes. The reaction solution was transferred to a 12.5mL inner container of a Teflon reaction kettle, the reaction kettle was placed in an electric thermostat, and the temperature was set at 85 ℃ for 24 hours. And taking out the reacted solution, separating the waste liquid by using a centrifugal machine, washing the obtained precipitate for three times by using 8mL of DMF (dimethyl formamide), then washing the precipitate for three times by using 8mL of ethanol to obtain a dark blue precipitate, putting the obtained precipitate into a vacuum drying oven, and drying the precipitate for 12 hours at the temperature of 60 ℃ to obtain dried dark blue powder HKUST-1.
2. Mn doping is carried out on HKUST-1 to prepare Mn @ HKUST-1
Weighing 0.355g (1 mu M) of the blue powder and 2.275g (5 mu M) of manganese chloride tetrahydrate, dissolving in 12.5mL of ethanol, putting a stirrer in the solution, stirring for 10 minutes by using a magnetic stirrer, taking out the stirrer by using a pair of tweezers, placing a beaker in an ultrasonic cleaner for 1 hour by ultrasonic treatment, centrifuging the reaction solution for 10 minutes at the rotating speed of 1000rpm by using a high-speed refrigerated centrifuge, removing the upper layer waste liquid, washing by using ethanol, placing the washed material in a vacuum drying oven, adjusting the temperature to 60 ℃, and drying for 12 hours to obtain the blue powder, namely, using a vacuum drying oven to dry the blue powder at the temperature of 60 ℃ to obtain the blue powderHKUST-1 and MnCl2·4H2Mn @ HKUST-1 obtained by Mn doping O at a ratio of substance amount of 1:5 is recorded as sample Mn @ HKUST-1(1: 5).
3. Changing HKUST-1 and MnCl2·4H2O ratio the above procedure was repeated to produce samples Mn @ HKUST-1(1:1), Mn @ HKUST-1(1:3), Mn @ HKUST-1(1:7) and Mn @ HKUST-1(1:10), respectively.
Performance testing and characterization
1. Physical and chemical property characterization of HKUST-1 and Mn @ HKUST-1
(1) Through SEM test, as can be seen from FIG. 1A, HKUST-1 has a polyhedral structure, and the crystal surface is relatively complete and smooth; as can be seen from FIG. 1B, the Mn @ HKUST-1 doped with Mn is a nano-ribbon structure, and the width of the nano-ribbon is about 150 nm.
(2) XRD testing was performed on HKUST-1 and Mn @ HKUST-1, and the results are shown in FIG. 2. The XRD pattern of the material is good in peak shape and sharp in peak appearance, which shows that the crystallization state of the material is good. And the peak position of Mn @ HKUST-1 is the same as that of HKUST-1, which shows that the experimental work function of Mn2+Partial replacement is carried out on copper in HKUST-1, and Mn doping is successfully carried out on HKUST-1.
Example 2: application of nano-strip manganese doped Mn @ HKUST-1 material in biosensing field
(1) Respectively and uniformly mixing the Mn @ HKUST-1 powder and the carbon slurry in a mass ratio of 1:2-1:10, then obtaining a printing electrode by printing technologies such as screen printing and the like, and carrying out electrochemical test. (the shape and size of the printed electrodes can be designed according to specific experimental requirements)
(2) In this example, the electrode printed with the nano-strip Mn @ HKUST-1 was subjected to H-printing by Cyclic Voltammetry (CV) and chronoamperometry2O2The electrochemical performance test of (1). The printed electrodes of the control group and the experimental group were conductive ink printed electrodes (wherein the diameter of the working electrode was 1.5mm) prepared by a screen printing technique after mixing HKUST-1 and Mn @ HKUST-1 with carbon paste at a mass ratio of 1:5, respectively.
Electrodes made of two different materials were tested against 1mM H with CV by an electrochemical workstation2O2The results show that: mn @ HKUST-1 to 1mM H2O2The current response of the current is obviously higher than that of HKUST-1 to 1mM H2O2Current response (fig. 3A). A bar graph is prepared according to the current value of the reduction peak in the experiment (as shown in figure 3B), and the data shows that the Mn @ HKUST-1 material obtained after Mn doping HKUST-1 is used for H2O2The response of the material is obviously higher than that of HKUST-1, which shows that the doping of Mn obviously improves the material to H2O2The sensing performance of (2).
In addition, Mn @ HKUST-1 was tested for H by chronoamperometry2O2The specificity was evaluated. Chronoamperometry results (FIG. 4) show that 2. mu. M H was added to 0.01M PBS2O2Then, obvious response current appears, but no obvious response current appears after the same concentrations of glucose (Glu), Uric Acid (UA), ascorbic Acid (ASC), Dopamine (DA), KCl and NaCl are added, which indicates that the electrode pair H printed by the Mn @ HKUST-1 conductive ink2O2The detection has good selectivity.
In conclusion, the nano-strip manganese doped metal organic framework material Mn @ HKUST-1 prepared by the method has good electrocatalytic activity, can be prepared into a flexible sensor, and realizes H pair2O2High sensitivity and specificity detection.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A preparation method of a nano-strip manganese doped metal organic framework material Mn @ HKUST-1 is characterized by comprising the following steps:
mixing the metal organic framework material HKUST-1 and manganese salt in a solution, carrying out ultrasonic reaction for 10 min-2 h, centrifuging, washing and drying to obtain the nano strip manganese doped metal organic framework material Mn @ HKUST-1.
2. The preparation method of the nano-strip manganese doped metal organic framework material Mn @ HKUST-1 according to claim 1, wherein the manganese salt is one or more of manganese chloride, manganese sulfate and manganese nitrate.
3. The preparation method of the nano strip manganese doped metal organic framework material Mn @ HKUST-1 according to claim 1, wherein the solution comprises ethanol and methanol.
4. The preparation method of the nano-ribbon manganese-doped metal-organic framework material Mn @ HKUST-1 according to claim 1, wherein the concentration of HKUST-1 in the mixed solution is 0.1-1mM, and the concentration ratio of HKUST-1 to manganese ions is 1:1-1: 15.
5. The preparation method of the nano strip manganese doped metal organic framework material Mn @ HKUST-1 according to claim 1, wherein the drying method comprises freeze drying, vacuum drying and room temperature drying.
6. The preparation method of the nano strip manganese doped metal-organic framework material Mn @ HKUST-1 according to claim 1, wherein the preparation method of the metal-organic framework material HKUST-1 comprises the following steps:
dissolving copper salt and trimesic acid in N, N-dimethylformamide to ensure that the concentration of the copper salt is 0.2-1.0M and the concentration ratio of copper ions to the trimesic acid is 1:1-1: 5; adding 20-80% ethanol water solution, stirring, and performing ultrasonic treatment for 3-30 min to fully dissolve the suspension until the suspension is clear; reacting the reaction solution at 60-100 ℃ for 10-40 hours, centrifugally washing the reaction product with DMF and ethanol, and drying at 25-80 ℃ for 5-72 hours to obtain the metal organic framework material HKUST-1.
7. The preparation method of the nano-strip manganese doped metal-organic framework material Mn @ HKUST-1 as claimed in claim 6, wherein the copper salt is one or more of copper nitrate, copper acetate, copper sulfate and copper chloride; the addition amount of the ethanol water solution is 1-5 times of the volume of the solution.
8. The nano-strip manganese-doped metal-organic framework material Mn @ HKUST-1 prepared by the method according to any one of claims 1 to 7.
9. A flexible sensing device is characterized in that the flexible sensing device is a printing electrode which is prepared by mixing the nano-strip manganese-doped metal organic framework material Mn @ HKUST-1 of claim 8 with carbon paste according to the mass ratio of 1:2-1:10 and then carrying out screen printing.
10. Use of the flexible sensor device of claim 9 for electrochemical detection of H2O2The use of (1).
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| CN106215866A (en) * | 2016-08-31 | 2016-12-14 | 太原理工大学 | The method that bimetallic MOFs material is prepared in steam assistant metal displacement |
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| CN111135869A (en) * | 2019-12-29 | 2020-05-12 | 苏州阿德旺斯新材料有限公司 | Preparation method of titanium dioxide nanobelt @ MOF composite material |
| CN111569944A (en) * | 2020-05-20 | 2020-08-25 | 湖南垚恒环境科技有限公司 | Manganese ion doped metal organic framework material and preparation method thereof |
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Patent Citations (4)
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| CN106215866A (en) * | 2016-08-31 | 2016-12-14 | 太原理工大学 | The method that bimetallic MOFs material is prepared in steam assistant metal displacement |
| CN109293940A (en) * | 2018-11-22 | 2019-02-01 | 苏州大学 | One-dimensional HKUST-1 nanobelt and preparation method thereof |
| CN111135869A (en) * | 2019-12-29 | 2020-05-12 | 苏州阿德旺斯新材料有限公司 | Preparation method of titanium dioxide nanobelt @ MOF composite material |
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