CN114199957A - High-conductivity MOFs (metal-organic frameworks) base material with ultralow detection limit on chloramphenicol, and preparation method and application thereof - Google Patents
High-conductivity MOFs (metal-organic frameworks) base material with ultralow detection limit on chloramphenicol, and preparation method and application thereof Download PDFInfo
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention belongs to the technical field of electrochemical rapid detection, and particularly discloses a high-conductivity MOFs base material with ultralow detection limit on chloramphenicol, and a preparation method and application thereof. According to the invention, the metal salt with efficient catalytic activity on chloramphenicol is loaded in the high-conductivity MOF material, so that the composite high-conductivity MOFs base material is constructed. The high conductivity of the MOF and the synergistic effect of the high-efficiency catalytic activity of the metal salt enable the high-conductivity MOFs-based material to show excellent performance in an electrochemical quick detection technology, realize a super detection limit one order of magnitude lower than that of the prior art, and have excellent detection repeatability and stability in the air in an electrochemical environment. The brand-new high-conductivity MOFs-based material prepared by the invention is expected to become a potential application material in the rapid detection technology of chloramphenicol.
Description
Technical Field
The invention belongs to the technical field of electrochemical rapid detection, and particularly relates to a high-conductivity MOFs base material with ultralow detection limit on chloramphenicol, and a preparation method and application thereof.
Background
With the increasing desire of people for high-quality life, food safety has become a key focus of academic and industrial circles. Chloramphenicol, as an antibiotic for sterilization, is often added in water and feed. Once the content of chloramphenicol entering human body through food chain exceeds standard, various diseases can be caused, and the health of human beings is threatened. In order to prevent abuse accidents, chloramphenicol detection is an essential link in environmental and food monitoring. The existing detection method is based on the chromatographic detection of national standard GB/T22338-. Although the national standard method has high precision, the method needs to depend on large instruments such as high performance liquid chromatography, mass spectrometry and the like, and each detection needs to be provided with a standard sample, so that the time is long. Therefore, the development of a novel chloramphenicol detection technique is imperative.
Electrochemical detection based on Metal Organic Frameworks (MOFs) is an emerging rapid detection technology. MOFs are three-dimensional porous structure materials formed by self-assembling metal ions or metal clusters and organic ligands. The catalyst can be fixed on the nodes or wrapped in the cavities, so that the catalyst is better in dispersion and is not easy to agglomerate. The porous structure has larger specific surface area, which is beneficial to the full permeation of electrolyte and improves the transmission of electrons between the catalyst and the electrolyte. ZIF-67C @ rGO, Fe/ZIF-8, IRMOF-8, UiO-66-NH2ZnCo-MOFs (Microchim. acta 2019,186,623; Ecotox. environ. Saf.2020,204, 111066; Talanta 2017,167, 39; Sens Actuators B chem.2017,242, 1201; J.Electrochem. Soc.,2020,167,116513) are MOFs-based catalysts used in recent years for electrochemical detection of chloramphenicol. Therefore, electrochemical detection based on MOFs is one of feasible chloramphenicol rapid detection technologies.
However, the maximum disadvantage of the rapid chloramphenicol detection technique is that the detection limit is too high (several tens of nM and several hundreds of nM in the national standard method). The key reason is that the conductivity of these MOFs is too low (10)-10S/cm). The research shows thatMost organic ligands of MOFs contain-COO-linkages, and since the electronegativity of the carboxyl oxygen is large, electrons need higher voltage to pass through these linkages, eventually resulting in less overlap of the oxygen atom with the d orbital of the metal. At present, two methods for improving the conductivity of the MOFs-based catalyst are available: first, it is compounded with other highly conductive materials such as graphene, PEDOT, etc. (mater. chem. phys.2021,270, 124831); secondly, the MOFs are calcined to porous carbon (Food chem.2021,364, 130368). These methods either require the introduction of other materials or the modification of the MOFs structure, and do not fully exploit the properties of the original MOFs.
In summary, the existing technologies for rapid detection of chloramphenicol based on MOFs still have the following points to be improved: (1) the conductivity of MOFs materials is to be improved; (2) the detection limit of chloramphenicol needs to be further reduced; (3) more transition metal materials capable of efficiently catalyzing and reducing chloramphenicol need to be excavated.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
The second purpose of the invention is to provide the high-conductivity MOFs-based material which has ultralow detection limit on chloramphenicol and is prepared by the method.
The third purpose of the invention is to provide the application of the high-conductivity MOFs-based material in a chloramphenicol quick detection technology.
The primary object of the present invention is achieved by the following scheme:
a preparation method of a high-conductivity MOFs base material with ultralow detection limit on chloramphenicol comprises the following steps:
(1) nickel chloride hexahydrate (NiCl)2·6H2O) and 2,3,6,7,10, 11-hexaamino triphenyl hexahydrochloride (HATP & 6HCl) are respectively dissolved in distilled water to form nickel chloride hexahydrate (NiCl) with the mass concentration of 0.2-20mg/mL2·6H2O) solution and organic ligand 2,3,6,7,10, 11-hexaamino triphenyl hexahydrochloride (HATP & 6HCl) solution with the mass concentration of 1-30mg/mL, the two solutions are mixed by magnetic stirring under the condition of water bath, and then the solution is slowly dripped with the organic ligand 2,3,6,7,10, 11-hexaamino triphenyl hexahydrochloride (HATP & 6HCl) solution with the molar concentration of 14mol/LContinuously stirring and mixing the strong ammonia water; centrifuging, collecting solid, washing and drying to obtain the high-conductivity MOF material Ni3(HITP)2；
(2) Taking 5-50mg of Ni obtained in the step (1)3(HITP)2Placing the mixture into an organic solvent for ultrasonic reaction, and slowly dripping a metal salt aqueous solution with the mass concentration of 0.01-2.0mol/L, wherein the dosage is 0.05-10.0 mL; stirring and reacting at room temperature, collecting a water phase after the reaction is finished, filtering and drying to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
Preferably, the nickel chloride hexahydrate (NiCl) in step (1)2·6H2O) solution of 1.32mg/mL, and the organic ligand 2,3,6,7,10, 11-hexaamino triphenyl hexahydrochloride (HATP & 6HCl) solution of 2.0 mg/mL.
Preferably, the dosage of the concentrated ammonia water in the step (1) is 0.1-1.0 mL.
Preferably, the washing in step (1) refers to washing twice with distilled water and ethanol in sequence; the drying refers to vacuum drying at 30-120 ℃ for 0.5-20 h.
Preferably, the temperature of the water bath in step (1) is 65 ℃.
Preferably, the organic solvent in step (2) is Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), CH2Cl2、CHCl3、CCl4At least one of n-hexane, cyclohexane and toluene, and the dosage is 5-20 mL;
preferably, the ultrasonic power in the step (2) is 40W, and the ultrasonic time is 10-120 min.
Preferably, the aqueous metal salt solution in the step (2) is MnCl2、Mn(NO3)2、PtCl2、PtCl4、PdCl2、Pd(OAc)2、NiCl2、Ni(NO3)2、AgNO3、Cu2(OAc)4·6H2O and Fe (NO)3)2One kind of (1).
Preferably, the reaction time of stirring at room temperature in the step (2) is 0.5-16 h.
Preferably, the drying in step (2) means vacuum drying at 30-120 ℃ for 0.5-20 h.
The second object of the present invention is achieved by the following means:
the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol, which is prepared by the preparation method.
The third object of the present invention is achieved by the following means:
the application of a high-conductivity MOFs base material with ultralow detection limit on chloramphenicol in a chloramphenicol quick detection technology.
Compared with the prior art, the invention has the following advantages and beneficial effects: the invention provides a preparation method of a high-conductivity MOFs (metal-organic frameworks) based material with ultralow detection limit on chloramphenicol, wherein the loading mechanism of metal salts in the high-conductivity MOF is as follows: first, the metal salt is adsorbed in the MOF cavity or framework; secondly, the metal ions replace the original metal ions in the MOF and are positioned on the nodes at the connection positions of the organic ligands; thirdly, the two above-mentioned modes coexist. In reported studies, the MOFs are generally selected from low-conductivity MOFs containing-COO-bridge, and metal salts are rarely supported in the MOFs to form composite materials. Although these materials can also realize rapid detection of chloramphenicol, various defects exist, such as low conductivity, which is not favorable for fully exerting catalytic reduction effect of metal ions on chloramphenicol, resulting in that no current signal can be detected at low concentration, and the detection limit cannot be further reduced. In the invention, the inventor provides an innovative material design idea through experimental research and an improved synthesis method, and belongs to the development and application of new materials. The inventor proposes that the high-conductivity MOF material is prepared by using an organic ligand containing-NH-QiaoI, and is compounded with metal ions with high-efficiency catalytic reduction capacity on chloramphenicol, so that the ultralow detection limit in the rapid detection technology is realized, the method can prepare the high-conductivity material, and the complex subsequent treatments of compounding, calcining and the like in order to improve the conductivity of the material in the prior art are avoided. The basic physicochemical property condition of the high-conductivity MOFs-based material can be confirmed through the characterization of infrared spectroscopy (FTIR), an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM) and an X-ray photoelectron spectrometer (XPS). And finally, evaluating the application prospect of the high-conductivity MOFs-based material in the chloramphenicol quick detection technology through an electrochemical test under a three-electrode system.
According to the invention, the metal salt with efficient catalytic activity on chloramphenicol is loaded in the high-conductivity MOF material, so that the composite high-conductivity MOFs base material is constructed. The high conductivity of the MOF and the synergistic effect of the high-efficiency catalytic activity of the metal salt enable the high-conductivity MOFs-based material to show excellent performance in an electrochemical quick detection technology, realize a super detection limit one order of magnitude lower than that of the prior art, and have excellent detection repeatability and stability in the air in an electrochemical environment. The brand-new high-conductivity MOFs-based material prepared by the invention is expected to become a potential application material in the rapid detection technology of chloramphenicol.
Drawings
FIG. 1 is an infrared spectrum of a highly conductive MOFs-based material before and after loading of a metal salt in example 1;
FIG. 2 is an XRD pattern of the highly conductive MOFs based material before and after loading of the metal salt in example 5;
FIG. 3 is a scanning electron microscope photograph of highly conductive MOFs based materials before and after loading of metal salts in example 2;
FIG. 4 is mapping of elements of the highly conductive MOFs-based material before and after loading of the metal salt in example 4;
FIG. 5 is an XPS plot of highly conductive MOFs based materials before and after loading with metal salts as in example 5;
FIG. 6 is a transmission electron microscope photograph, a high resolution transmission electron microscope photograph, and a selected area diffraction pattern of the highly conductive MOFs-based material before and after the metal salt loading in example 6;
FIG. 7 is a graph of the electrochemical performance test of the high conductivity MOFs-based material before and after the bare metal salt catalyst and the metal salt loading in example 7;
FIG. 8 is a kinetic test chart of the highly conductive MOFs-based material after being loaded with the metal salt in example 5;
FIG. 9 is a detection limit test chart of the highly conductive MOFs-based material after being loaded with the metal salt in example 5;
FIG. 10 is a detection limit test chart of the highly conductive MOFs-based material after loading with metal salt in example 3;
FIG. 11 is a repeatability test chart of the highly conductive MOFs-based material after loading with metal salt in example 5;
fig. 12 is a stability test chart of the highly conductive MOFs-based material after loading with metal salt in example 5.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The reagents used in the examples are commercially available without specific reference.
Example 1
6.6mg of NiCl2·6H2Dissolving O in 5mL of distilled water, dissolving 10mg of HATP & 6HCl in 5mL of distilled water, mixing the two solutions under stirring in a water bath at 65 ℃, slowly dropwise adding 0.3mL of concentrated ammonia water, continuously reacting for 2 hours under stirring in the water bath at 65 ℃, washing twice with distilled water and ethanol in sequence after the reaction is finished, and drying for 12 hours in vacuum at 80 ℃ to obtain the high-conductivity MOF material Ni3(HITP)2. 5mg of dried Ni3(HITP)2Placing the mixture in 5mL of DMF, performing ultrasonic treatment for 10min under 40W, and slowly dropwise adding 0.05mL of 0.01mol/L MnCl2And (3) stirring the aqueous solution at room temperature for reaction for 0.5h, collecting the aqueous phase after the reaction is finished, filtering, and carrying out vacuum drying at 30 ℃ for 0.5h to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
As shown in fig. 1, which is an infrared spectrum of the highly conductive MOFs-based material before and after loading of the metal salt in this example, the slight shift of each characteristic peak in the graph demonstrates the successful loading of the metal salt into the highly conductive MOF.
Example 2
1.0mg of NiCl2·6H2Dissolving O in 5mL of distilled water, dissolving 5mg of HATP & 6HCl in 5mL of distilled water, mixing the two solutions while stirring in a water bath at 65 ℃, and slowly addingDropwise adding 0.1mL of concentrated ammonia water, continuously reacting for 2 hours under the stirring of water bath at 65 ℃, washing twice with distilled water and ethanol in sequence after the reaction is finished, and vacuum drying for 0.5 hour at 30 ℃ to obtain the high-conductivity MOF material Ni3(HITP)2. 50mg of dried Ni3(HITP)2Placing in 20mL DMSO, performing ultrasonic treatment at 40W for 120min, and slowly adding 10.0mL of 2.0mol/L NiCl dropwise2And (3) stirring the aqueous solution at room temperature for reacting for 16h, collecting the aqueous phase after the reaction is finished, filtering, and carrying out vacuum drying at 120 ℃ for 20h to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
As shown in fig. 3, which is a scanning electron microscope image of the highly conductive MOFs-based material before and after loading the metal salt in this embodiment, it is shown that the morphology of the material before and after loading is not changed much, which proves that the macroscopic morphology of the MOF is not damaged by the loading treatment, and the morphology of the material before and after loading is spherical particles.
Example 3
100mg of NiCl2·6H2Dissolving O in 5mL of distilled water, dissolving 150mg of HATP & 6HCl in 5mL of distilled water, mixing the two solutions under stirring in a water bath at 65 ℃, slowly dropwise adding 1.0mL of concentrated ammonia water, continuously reacting for 2 hours under stirring in the water bath at 65 ℃, washing twice with distilled water and ethanol in sequence after the reaction is finished, and drying in vacuum at 120 ℃ for 20 hours to obtain the high-conductivity MOF material Ni3(HITP)2. 10mg of dried Ni3(HITP)2Is placed in 8mL CH2Cl2In 40W ultrasonic treatment for 20min, slowly adding 1.0mL of 0.05mol/L PtCl2And (3) stirring the aqueous solution at room temperature for 2 hours, collecting the aqueous phase after the reaction is finished, filtering, and carrying out vacuum drying at 50 ℃ for 2 hours to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
As shown in fig. 10, which is a detection limit test chart of the high-conductivity MOFs-based material after loading the metal salt in this embodiment, it can be seen that the high-conductivity MOFs-based material before and after loading the metal salt shows a lower detection limit (20nM) for chloramphenicol.
Example 4
50mg of NiCl2·6H2Dissolving O in 5mL of distilled water, dissolving 50mg of HATP & 6HCl in 5mL of distilled water, stirring in a water bath at 65 DEG CMixing the two solutions, slowly dropwise adding 0.5mL of concentrated ammonia water, continuously reacting for 2 hours in a water bath at 65 ℃ under stirring, washing twice with distilled water and ethanol in sequence after the reaction is finished, and drying for 10 hours in vacuum at 60 ℃ to obtain the high-conductivity MOF material Ni3(HITP)2. 15mg of dried Ni3(HITP)2Placed in 16mL of CHCl3In 40W, ultrasonic treatment is carried out for 30min, and 2.0mL of 0.1mol/L PtCl is slowly dripped4And (3) stirring the aqueous solution at room temperature for reacting for 4 hours, collecting the aqueous phase after the reaction is finished, filtering, and carrying out vacuum drying at 60 ℃ for 6 hours to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
Fig. 4 shows mapping of each element of the high-conductivity MOFs-based material before and after loading the metal salt in this embodiment, and it can be seen from the figure that each element is uniformly distributed.
Example 5
55mg of NiCl2·6H2Dissolving O in 5mL of distilled water, dissolving 55mg of HATP & 6HCl in 5mL of distilled water, mixing the two solutions under stirring in a water bath at 65 ℃, slowly dropwise adding 0.6mL of concentrated ammonia water, continuously reacting for 2 hours under stirring in the water bath at 65 ℃, washing twice with distilled water and ethanol in sequence after the reaction is finished, and drying for 11 hours in vacuum at 70 ℃ to obtain the high-conductivity MOF material Ni3(HITP)2. 19mg of dried Ni3(HITP)2Placing in 13mL of normal hexane, performing ultrasonic treatment at 40W for 50min, and slowly dropwise adding 4.0mL of 0.2mol/L PdCl2And (3) stirring the aqueous solution at room temperature for reacting for 6 hours, collecting the aqueous phase after the reaction is finished, filtering, and drying in vacuum at 70 ℃ for 8 hours to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
As shown in fig. 2, which is the XRD pattern of the high conductive MOFs-based material before and after loading the metal salt in this example, it can be seen from the XRD pattern that the (200) peak of the original MOF is shifted to a small angle, which proves that the Ni of the original MOF is replaced by the metal ion with larger diameter, and the (011) peak of the metal salt appears after loading, which proves that the metal salt is adsorbed on the MOF.
As shown in fig. 5, an XPS chart of the high-conductivity MOFs-based material before and after the metal salt loading in this example is shown, and the peak of the metal salt after the loading is clearly visible.
As shown in fig. 8, which is a dynamic test chart of the highly conductive MOFs-based material after loading with the metal salt in this embodiment, as the sweep rate increases, the current gradually increases, wherein the slope of the oxidation peak current is larger than that of the reduction peak current, which proves that the oxidation process has faster kinetics.
As shown in fig. 9, which is a detection limit test chart of the high-conductivity MOFs-based material after loading with the metal salt in this embodiment, it can be seen from the test chart that the high-conductivity MOFs-based material before and after loading with the metal salt exhibits an ultra-low detection limit (0.2nM) for chloramphenicol, which is one order of magnitude lower than the reported detection limit (2.8-184nM) for the MOFs-based material. It can also be seen that the linear range of the highly conductive MOFs-based material before and after the metal salt loading is 0.0002-20 uM.
As shown in fig. 11, which is a repeatability test chart of the high-conductivity MOFs-based material loaded with the metal salt in this embodiment, it can be seen from the chart that current curves circulating ten times can be well overlapped, and a peak current value remains unchanged, which proves that the high-conductivity MOFs-based material loaded with the metal salt has excellent detection repeatability.
As shown in fig. 12, which is a stability test chart of the high-conductivity MOFs-based material after loading with the metal salt in this embodiment, it can be seen from the stability test chart that the current of the material is kept near a certain value under a certain voltage, and the material still shows repeatable detection performance after being placed in the air for one month.
Example 6
65mg of NiCl2·6H2Dissolving O in 5mL of distilled water, dissolving 65mg of HATP & 6HCl in 5mL of distilled water, mixing the two solutions under stirring in a water bath at 65 ℃, slowly dropwise adding 0.7mL of concentrated ammonia water, continuously reacting for 2 hours under stirring in the water bath at 65 ℃, washing twice with distilled water and ethanol in sequence after the reaction is finished, and drying for 12 hours in vacuum at 80 ℃ to obtain the high-conductivity MOF material Ni3(HITP)2. 23mg of dried Ni3(HITP)2Placing in 15mL cyclohexane, performing ultrasonic treatment at 40W for 60min, and slowly dropwise adding 6.0mL of 0.4mol/L Cu2(OAc)4·H2O aqueous solution, stirring and reacting for 12h at room temperature, and reactingAnd (3) collecting the water phase after finishing, filtering, and drying in vacuum at 80 ℃ for 12h to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
Fig. 6 shows a transmission electron microscope image, a high-resolution transmission electron microscope image, and a selected area diffraction pattern of the high-conductivity MOFs-based material before and after loading of the metal salt in this embodiment, in which the morphology of spherical particles and lattice fringes of the material can be clearly seen, and the material is polycrystalline as can be seen from the selected diffraction pattern.
Example 7
80mg of NiCl2·6H2Dissolving O in 5mL of distilled water, dissolving 80mg of HATP & 6HCl in 5mL of distilled water, mixing the two solutions under stirring in a water bath at 65 ℃, slowly dropwise adding 0.9mL of concentrated ammonia water, continuously reacting for 2 hours under stirring in the water bath at 65 ℃, washing twice with distilled water and ethanol in sequence after the reaction is finished, and drying in vacuum at 100 ℃ for 14 hours to obtain the high-conductivity MOF material Ni3(HITP)2. 40mg of dried Ni3(HITP)2Placing in 18mL toluene, performing ultrasonic treatment at 40W for 100min, and slowly dropwise adding 8.0mL of 0.8mol/L AgNO3And (3) stirring the aqueous solution at room temperature for reacting for 14h, collecting the aqueous phase after the reaction is finished, filtering, and carrying out vacuum drying at 100 ℃ for 14h to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
As shown in fig. 7, which is a test chart of electrochemical properties of the high-conductivity MOFs-based material before and after loading the metal salt and the bare metal salt catalyst in this embodiment, it can be seen from the test chart that the original high-conductivity MOF has no catalytic effect on chloramphenicol, and the high-conductivity MOFs-based material after loading the metal salt exhibits excellent catalytic performance, but the bare metal salt has smaller resistance and larger current.
In conclusion, the invention firstly provides a design idea of a novel electrocatalyst for electrochemical detection of chloramphenicol, and a series of brand-new high-conductivity MOFs-based materials are prepared through the idea, so that an ultralow detection limit is realized. Firstly, the conductive performance of the high-conductivity MOFs is utilized, so that complex post-treatment steps such as compounding and calcining are avoided. And secondly, more metal salts with high-efficiency catalytic activity on chloramphenicol are screened, so that the design limitation of materials for electrochemical detection of chloramphenicol is broken through. And finally, by optimizing reaction parameters, the high-conductivity MOFs base material with ultra-low detection limit and excellent repeatability stability can be obtained. Experiments prove that the high-conductivity MOFs base material prepared by the idea has certain potential application value in the chloramphenicol quick detection technology.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-conductivity MOFs base material with ultralow detection limit on chloramphenicol is characterized by comprising the following steps:
(1) mixing NiCl2·6H2O and HATP & 6HCl are respectively dissolved in distilled water to form NiCl with the mass concentration of 0.2-20mg/mL2·6H2Mixing the O solution and the HATP & 6HCl solution of the organic ligand with the mass concentration of 1-30mg/mL under the condition of water bath by magnetic stirring, slowly dropwise adding strong ammonia water with the molar concentration of 14mol/L, and continuously stirring and mixing; centrifuging, collecting solid, washing and drying to obtain the high-conductivity MOF material Ni3(HITP)2；
(2) Taking 5-50mg of Ni obtained in the step (1)3(HITP)2Placing the mixture into an organic solvent for ultrasonic reaction, and slowly dripping a metal salt aqueous solution with the mass concentration of 0.01-2.0mol/L, wherein the dosage is 0.05-10.0 mL; stirring and reacting at room temperature, collecting a water phase after the reaction is finished, filtering and drying to obtain the high-conductivity MOFs base material with ultralow detection limit on chloramphenicol.
2. The method for preparing high-conductivity MOFs-based material with ultralow detection limit on chloramphenicol according to claim 1, wherein said NiCl in step (1) is2·6H2The mass concentration of the O solution is 1.32mg/mL, and the mass concentration of the organic ligand HATP & 6HCl solution is 2.0 mg/mL.
3. The method for preparing the high-conductivity MOFs-based material with ultralow detection limit on chloramphenicol according to claim 1, wherein the dosage of the concentrated ammonia water in the step (1) is 0.1-1.0 mL.
4. The method for preparing a highly conductive MOFs-based material having an ultra-low detection limit for chloramphenicol as claimed in claim 1, wherein the washing in step (1) is twice by sequentially washing with distilled water and ethanol; the drying refers to vacuum drying at 30-120 ℃ for 0.5-20 h.
5. The method for preparing high-conductivity MOFs-based material with ultralow detection limit on chloramphenicol according to claim 1, wherein the organic solvent in step (2) is DMF, DMSO, CH2Cl2、CHCl3、CCl4At least one of n-hexane, cyclohexane and toluene, and the dosage is 5-20 mL.
6. The method for preparing high-conductivity MOFs-based material with ultralow detection limit on chloramphenicol according to claim 1, wherein the ultrasonic power in step (2) is 40W, and the ultrasonic time is 10-120 min.
7. The method for preparing a highly conductive MOFs-based material having ultra-low detection limit for chloramphenicol according to claim 1, wherein said aqueous solution of metal salt in step (2) is MnCl2、Mn(NO3)2、PtCl2、PtCl4、PdCl2、Pd(OAc)2、NiCl2、Ni(NO3)2、AgNO3、Cu2(OAc)4·6H2O and Fe (NO)3)2One of the solutions.
8. The method for preparing a highly conductive MOFs-based material having ultra-low detection limit for chloramphenicol as claimed in claim 1, wherein the drying in step (2) is vacuum drying at 30-120 ℃ for 0.5-20 h.
9. A high-conductivity MOFs-based material having an ultra-low detection limit for chloramphenicol, prepared by the preparation method according to any one of claims 1 to 8.
10. An application of a high-conductivity MOFs base material with ultralow detection limit on chloramphenicol in a chloramphenicol quick detection technology.
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