CN114539543B - Nano-ribbon manganese-doped metal organic framework material Mn @ HKUST-1, and preparation method and application thereof - Google Patents
Nano-ribbon manganese-doped metal organic framework material Mn @ HKUST-1, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano-strip 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-belt-shaped 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 detection 2 O 2 The use of (1). The nano-strip manganese doped metal organic framework material Mn @ HKUST-1 of the invention is used for detecting H 2 O 2 Has high sensitivity and selectivity, and is suitable for use as H 2 O 2 A sensor. The flexible sensing device prepared by conductive ink based on Mn @ HKUST-1 and constructed by a screen printing technology can dynamically realize H in real time 2 O 2 High 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 structures. And the surface electronic structure has a stronger oxidation state or reduction state, which greatly helps the oxidation or reduction kinetics of the electrode. Hydrogen peroxide (H) 2 O 2 ) One of the active oxygens is a product of a biological metabolic reaction and is also a potential biomarker for 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 time 2 O 2 And has important significance for diagnosing and researching related diseases.
Conventional H 2 O 2 The 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 the sensor due to the characteristics of low cost, high stability, simple preparation, good catalytic activity and the likeFor electrochemical detection of H 2 O 2 Is a hot point of research. At present, reported H 2 O 2 The 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 prepared 2 O 2 Sensors 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 H 2 O 2 Has high sensitivity and selectivity, and is suitable for use as H 2 O 2 A sensor.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a nano-strip 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-belt-shaped manganese doped metal organic framework material Mn @ HKUST-1.
According to the invention, HKUST-1 is subjected to manganese doping by mixing HKUST-1 with manganese salt, so that a doped metal organic framework material Mn @ HKUST-1 with a stronger oxidation state surface electronic structure is obtained, the shape of the Mn @ HKUST-1 doped material is changed from a polyhedral structure to a nano-belt 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, preferably 1:1-1.
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 a nano-belt 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-belt-shaped manganese doped metal organic framework material Mn @ HKUST-1 with carbon slurry according to the mass ratio of 1:2-1 to 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 H 2 O 2 The 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 electro-catalytic 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 of the invention is used for detecting H 2 O 2 Has high sensitivity and selectivity, and is suitable for use as H 2 O 2 A sensor. The flexible sensing device prepared by preparing conductive ink based on Mn @ HKUST-1 and constructed by a screen printing technology can dynamically realize H in real time 2 O 2 High sensitivity and specificity detection.
Drawings
FIG. 1 is an SEM picture 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 H 2 O 2 The CV response of (c); FIG. 3B is a histogram of the current response corresponding to A;
FIG. 4 shows the pair of Mn @ HKUST-1 and H 2 O 2 Selective 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. Synthesis of HKUST-1 by thermal synthesis
Respectively weighing copper nitrate trihydrate [ Cu (NO) by using an electronic balance 3 ) 2 ·3H 2 O]0.55g and 0.28g of trimesic acid (1,3,5-benzenetricarboxylic acid); dissolving copper nitrate trihydrate in 3.75mLN and N-dimethylformamide, adding trimesic acid into a reaction solution in which the copper nitrate is dissolved, adding 5mL of absolute ethyl alcohol 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, thereby 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 stir bar 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 of HKUST-1 is carried out 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 tweezers, placing a beaker in an ultrasonic cleaner for ultrasonic treatment for 1 hour, centrifuging the reaction solution for 10 minutes at the rotating speed of 1000rpm by using a high-speed refrigerated centrifuge, removing the upper 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 HKUST-1 and MnCl 2 ·4H 2 Mn @ HKUST-1 obtained by Mn doping O in a proportion of 1:5 is recorded as sample Mn @ HKUST-1 (1:5).
3. Changes of HKUST-1 and MnCl 2 ·4H 2 Repeating the above operation after the proportion of O to obtain samples Mn @HKUST-1 (1:1), mn @ HKUST-1 (1:3), mn @ HKUST-1 (1:7) and Mn @ HKUST-1 (1.
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, mn doped with Mn @ HKUST-1 is a nano-belt structure, and the width of the nano-belt is about 150 nm.
(2) XRD tests were 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 the experiment effect of Mn 2+ 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) The Mn @ HKUST-1 powder and the carbon slurry are respectively and uniformly mixed according to the mass ratio of 1:2-1. (the shape and size of the printed electrodes can be designed according to specific experimental requirements)
(2) In this example, the electrode printed with nanoribbon Mn @ HKUST-1 was subjected to H-voltammetry (CV) and chronoamperometry (CCV) 2 O 2 The electrochemical performance test of (2). Wherein the printed electrodes of the control group and the experimental group are conductive ink printed electrodes (wherein the diameter of the working electrode is 1.5 mm) 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 workstation 2 O 2 The results show that: mn @ HKUST-1 vs. 1mM H 2 O 2 The current response of the voltage is obviously higher than that of HKUST-1 to 1mM H 2 O 2 Current response (fig. 3A). A bar graph is prepared from the current values of the reduction peaks in the experiment (see FIG. 3B), and the data show that the peak value is obtained when HKUST-1 is appliedMn @ HKUST-1 material pair H obtained after Mn doping 2 O 2 The response of the material is obviously higher than that of HKUST-1, which shows that the doping of Mn obviously improves the material to H 2 O 2 The sensing performance of (2).
In addition, test H was performed on Mn @ HKUST-1 by chronoamperometry 2 O 2 The specificity was evaluated. Chronoamperometry test results (FIG. 4) show that 2. Mu. M H was added to 0.01M PBS 2 O 2 Obvious response current appears after the conductive ink, but no obvious response current appears after the conductive ink is added with glucose (Glu), uric Acid (UA), ascorbic Acid (ASC), dopamine (DA), KCl and NaCl at the same concentration, and the electrode pair H printed by Mn @ HKUST-1 conductive ink is explained 2 O 2 The 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 + ion-mediated coupling 2 O 2 High 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 a 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 banded manganese doped metal organic framework material Mn @ HKUST-1.
2. The preparation method of the nanobelt-shaped 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 nanobelt-shaped 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.
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-belt 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 nanobelt-shaped manganese-doped metal-organic framework material Mn @ HKUST-1 according to 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-ribbon 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-belt-shaped manganese doped metal organic framework material Mn @ HKUST-1 of claim 8 with carbon slurry according to the mass ratio of 1:2-1 to 10 and then carrying out screen printing.
10. Use of the flexible sensor device of claim 9 for electrochemical detection of H 2 O 2 The use of (1).
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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 |
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