CN111440328B - Boric acid modified metal oxide nano array-MOF composite material, and preparation method and application thereof - Google Patents
Boric acid modified metal oxide nano array-MOF composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a boric acid modified metal oxide nano array-MOF composite material, a preparation method and application thereof, and belongs to the technical field of nano composite materials. According to the method, a transition metal oxide nano array is grown on the surface of carbon cloth, an MOF material is grown in situ on the surface of the carbon cloth as a flexible substrate, and finally a boric acid group functional monomer is introduced, wherein the MOF materials of different types and different morphologies are uniformly distributed on the surface of the metal oxide nano array in a monodispersion mode. The preparation method is simple, mild in condition, adjustable in morphology, controllable in structure and uniform in component distribution, reserves the integrity of the metal oxide nano array and the MOF material porous framework structure, has good conductivity and excellent electrocatalytic performance of the metal oxide and the MOF material, and meanwhile, the surface of the composite material is modified by boric acid functional groups to serve as a flexible self-supporting electrode material and can specifically recognize cis-dihydroxy biomolecules.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a boric acid modified metal oxide nano array-MOF composite material, and a preparation method and application thereof.
Background
The transition metal oxide nano materials have good semiconductivity, electrocatalysis and redox capability, and the cost is low, so the transition metal oxide nano materials are widely concerned in the field of biosensing. But the performance of the constructed biosensors is not generally high. The main reasons are that: 1) the non-noble metal oxide belongs to semiconductor materials, has the characteristics of semiconductors, is poor in conductivity, and slow in electron transfer rate, so that the sensitivity of the sensor is low; 2) the non-noble metal oxide nano material is simply stacked, the effective reaction area is small, and the performance of the constructed biosensor is not high; 3) most of the synthesized non-noble metal enzyme-free sensing nano materials need to be fixed on electrodes such as glassy carbon and the like by using a conductive adhesive, and the use of the adhesive can bury partial active sites and reduce the catalytic activity. In recent years, researchers compound metal oxides and carbon materials, so that the problem of poor conductivity of the metal oxides can be solved, and the catalytic activity of the electrode material can be further improved by utilizing the synergistic catalytic action of the carbon materials and the metal oxide nano materials on target analytes, so that the performance of the sensor is improved. Meanwhile, in order to further improve the response signal of the biosensing, the sensing material is modified by biomolecules, so that the specific recognition capability of the sensing material is improved, and the selectivity and the sensitivity of the electrochemical biosensor are improved.
Metal-Organic Frameworks (MOFs) are porous materials with various structures and easy modification, are widely concerned due to the ultrahigh porosity and huge specific surface area, and have potential application prospects in the fields of catalysis, separation, sensors, gas adsorption and storage and the like. Although MOFs have outstanding catalytic activity, there are problems of poor conductivity and easy structural collapse,
disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a boric acid modified metal oxide nano array-MOF composite biosensor, the composite material prepared by the method has good electrical conductivity of a carbon material and excellent electrocatalytic properties of the metal oxide nano array and the MOF material, and can be used for electrochemically detecting cis-dihydroxy biomolecules by modification of phenylboronic acid functional groups.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a boric acid modified metal oxide nano array-MOF composite material comprises the following steps:
(a) preparation of metal oxide nano-arrays: firstly, growing any one or two of copper, cobalt, nickel, iron, zinc and manganese on the surface of carbon cloth by combining a hydrothermal method, a solvothermal method and an electrochemical deposition method with carbonization treatment to form a single metal or double metal oxide nano array;
(b) preparing a MOF material modified metal oxide nano array: taking the metal oxide nano array obtained in the step (a) as a substrate, adding 5-20 parts by weight of surfactant, 20-200 parts by weight of organic ligand, 100-800 parts by weight of organic solvent and 5-20 parts by weight of metal salt, and growing an MOF material in situ to obtain a metal oxide nano array-MOF composite material;
(c) preparation of the boric acid modified metal oxide nano array-MOF composite material: modifying the material obtained in the step (b) by using a surface stabilizer, then immersing the modified material into a solution containing a boric acid group functional monomer for 3-10 hours, adding the composite material into a cross-linking agent solution or cross-linking agent saturated steam, and reacting for 3-20 hours to obtain the boric acid modified metal oxide nano array-MOF composite material.
On the basis of the scheme, in the step b):
the surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, triethylamine, triethyldiamine, polyethylene pyrrolidone, polyacrylamide, polypropylene imine, alkyl sodium sulfonate, sodium fatty acid, polyoxyethylene ether, sodium carboxylate, hexadecyl trimethyl ammonium bromide, polyethylene glycol, polyethylene oxide, P123 and F127;
preferably, the organic ligand is selected from at least one of 2-aminoterephthalic acid, 2-hydroxyterephthalic acid, 2, 5-diaminoterephthalic acid, 2, 5-dihydroxyterephthalic acid, terephthalic acid, trimesic acid, 2-methylimidazole, benzimidazole, 2-nitroimidazole and 4-nitroimidazole;
preferably, the organic solvent is at least one of methanol, ethanol, water and DMF;
preferably, the metal salt is at least one of copper, cobalt, nickel, iron, zinc and manganese salts, and preferably, the metal salt is one of nitrate, acetate, sulfate and chlorate.
On the basis of the scheme, in the step c):
the surface stabilizer is at least one of imidazole-2-formaldehyde, 2-aminoimidazole, 4-imidazole formaldehyde, 1-ethyl-1H-imidazole-2-formaldehyde and 1-methyl-1H-imidazole-2-formaldehyde;
the surface stabilizer in the step (c) of the invention has two functions, namely, the surface modification of the metal oxide nano array-MOF composite material is provided with amino/aldehyde groups, and meanwhile, imidazole rings have the function of stabilizing the MOF material.
Preferably, the borate functional monomer is at least one of 2-aminobenzeneboronic acid, 3-aminobenzeneboronic acid, 4-aminobenzeneboronic acid, 3-acrylamidophenylboronic acid, 3-fluoro-4-aldophenylboronic acid, 4-fluoro-2-aldophenylboronic acid, 4-fluoro-3-aldophenylboronic acid, 4-carbamoylphenylboronic acid, 3-amino-4-fluorobenzeneboronic acid, 3-amino-5-fluorobenzeneboronic acid, 3- (2-carbonylvinyl) phenylboronic acid and 4-formylphenylboronic acid;
preferably, the cross-linking agent is at least one of formaldehyde, glyoxal and glutaraldehyde.
On the basis of the scheme, the mass ratio of the surface stabilizer to the metal oxide nano array-MOF composite material is 1-3: 1;
preferably, the concentration of the boric acid functional monomer is 3% -15%.
On the basis of the scheme, the carbonization treatment in the step a) is carried out in the atmosphere of air in a muffle furnace, the temperature is 200-500 ℃, the heating rate is 3-10 ℃/min, and the reaction time is 1.5-5 h.
On the basis of the scheme, the MOF material in-situ growth in the step b) is obtained by carrying out room-temperature standing, hydrothermal reaction or solvothermal method on the MOF material in-situ growth;
preferably, the reaction time of the room-temperature rest is 30min-36 h; the temperature of the hydrothermal reaction is 80-200 ℃, and the reaction time is 5-30 h.
On the basis of the scheme, the shape of the nano array in the step a) is at least one of a nano wire, a nano rod, a nano sheet, a nano belt and a nano flower.
The boric acid modified metal oxide nano array-MOF composite material prepared by the method is used for biosensors.
A biosensor is a three-electrode system which is formed by taking the boric acid modified metal oxide nano array-MOF composite material as a flexible self-supporting working electrode, an Ag/AgCl or saturated calomel electrode as a reference electrode and a platinum wire or a platinum sheet as a counter electrode, an electrochemical signal of the working electrode is detected through an electrochemical workstation, and cis-dihydroxy biomolecules are detected through the electrochemical signal intensity.
On the basis of the scheme, the cis-dihydroxy biomolecule is a biomolecule with a 1,2/1, 3-cis-diol structure; preferably one of a nucleotide, a glycoside, a polysaccharide, dopamine, epinephrine and glycoprotein.
The technical scheme of the invention has the advantages that:
(1) the carbon cloth three-dimensional self-supporting nano array is designed to be used as an electrode to construct an electrochemical biosensor, so that the use of an adhesive in the fixing process of an electrocatalyst is avoided, more active sites are exposed, and the three-dimensional framework material of the self-supporting material has the characteristics of light weight, large specific surface area, high mechanical strength, stable performance, processability, good conductivity and the like;
2) different synthesis methods and synthesis conditions are controlled, transition metal oxide nano arrays with different particle sizes or morphologies are obtained on the self-supporting carbon cloth, and a nano-structure material MOF material is further grown, so that a larger specific surface area of the electrocatalyst is obtained, the effective reaction area of the sensor is greatly enlarged, and more active sites are favorably exposed;
(3) the metal oxide, the MOF material and the carbon material are compounded, so that the problem of poor conductivity of the metal oxide and the MOF material can be solved, and the catalytic activity of the electrode material can be further improved by utilizing the synergistic catalytic action of the metal oxide, the MOF material and the carbon material on biomolecules, so that the performance of the sensor is improved;
(4) according to the metal oxide nano array-MOF composite material obtained by the invention, MOF particles are uniformly distributed on the surface and inside of the metal oxide nano array and have good binding force with the metal oxide nano array, so that the falling of the MOF particles in the reaction process is effectively reduced, and the cyclic use stability of the composite material in the electrochemical biosensing process is ensured.
Drawings
FIG. 1 is a boronic acid modified FeCo2O4SEM photograph of nanosheet array-MOF composite
FIG. 2 is a cyclic voltammogram of different modified electrodes in phosphate buffered saline at 50. mu.M dopamine, 0.1M, pH 7.0
FIG. 3 is a boronic acid modified FeCo2O4A cyclic voltammogram of a phosphoric acid buffer solution containing 50 mu M of dopamine is obtained by using a nanosheet array-MOF composite material modified electrode at different scanning rates, wherein the pH value of the electrode is 7.0;
FIG. 4 is a graph of oxidation peak current versus scan rate in a linear fashion;
FIG. 5 is the oxidation peak current measured in 8 replicates after elution of the modified electrode;
FIG. 6 shows boric acid modified MnCo2O4SEM photographs of the nanoflower array-MOF composite;
FIG. 7 boronic acid modified MnCo2O4Detecting differential pulse voltammograms of adrenalin with different concentrations by using a nanoflower array-MOF composite material electrode;
fig. 8 is a linear relationship between epinephrine and oxidation peak current at different concentrations.
Detailed Description
Terms used in the present invention have generally meanings as commonly understood by one of ordinary skill in the art, unless otherwise specified.
The present invention will be described in further detail with reference to the following data in conjunction with specific examples. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1:
(a)FeCo2O4preparation of nanosheet arrays
Firstly, a piece of carbon cloth (1 x 8cm) is soaked in concentrated HNO3In solution at 90 deg.CAfter 2 hours, each wash was performed with acetone, ethanol, and deionized water for 10 minutes to obtain an activated carbon cloth. 1mmol of Fe (NO)3)3·9H2O、2mmol Co(CH3COO)2·4H2O、4mmol NH4HCO3Dissolving 8mmol of urea in 50mL of mixed solution of ethylene glycol and water (1:1), stirring vigorously at room temperature for 20min to obtain uniform mixed solution, soaking activated three-dimensional carbon cloth in the mixed solution, transferring the mixture to a high-pressure reaction kettle, reacting at 200 ℃ for 8 h, cooling to room temperature after the reaction is finished, taking out and fully washing the product, drying at 60 ℃, finally, putting the obtained reaction product into a tubular furnace, annealing at 400 ℃ for 2 h at the temperature-rising rate of 5 ℃/min in the air atmosphere to obtain FeCo supported on the carbon cloth2O4A nanosheet array;
(b) CoZn-MOF material modified FeCo2O4Preparation of nanosheet arrays
The carbon cloth surface FeCo obtained in the step (a)2O4The nano sheet array is used as a substrate and is immersed into a mixed solution containing 7.5g of 2-methylimidazole, 38mL of methanol and ethanol (1:1), and ultrasonic dispersion is carried out uniformly; weighing 0.75g of cobalt nitrate hexahydrate, 0.75g of zinc nitrate hexahydrate and 1.5g of polypropylene imine, adding the mixture into a mixed solution of 38mL of methanol and ethanol (1:1), uniformly dispersing by using ultrasonic waves, adding the above solutions, mixing the two solutions for 30s, incubating at room temperature for 24h, collecting reaction products on the surface of the carbon cloth, washing the reaction products with ethanol for several times, and finally drying in vacuum at 80 ℃ to obtain FeCo modified by a CoZn-MOF material2O4A nanosheet array;
(c) boronic acid modified FeCo2O4Preparation of nanosheet array-MOF composite material
Immersing the material obtained in the step (b) in a methanol solution containing 4-imidazolecarboxaldehyde for 5 hours, then immersing the material in a solution containing 3-fluoro-4-aldehyde phenylboronic acid group functional monomer for 5 hours, then adding a 5% glyoxal crosslinking agent solution into the composite material, and reacting for 3 hours to obtain boric acid modified FeCo2O4A nanosheet array-MOF composite.
(d) Dopamine biosensor
Boronic acid modified FeCo2O4The method comprises the following steps of using a nanosheet array-MOF composite material as a flexible self-supporting working electrode, using Ag/AgCl as a reference electrode and using a platinum wire as a counter electrode to form a three-electrode system, detecting an electrochemical signal of the working electrode through an electrochemical workstation, and detecting dopamine through a CV electrochemical signal. FIG. 1 is a boronic acid modified FeCo2O4SEM photograph of a nanosheet array-MOF composite, from which it is seen that the MOF material is in FeCo2O4The surface of the nano-sheet array is uniformly and compactly arranged and grown, the polyhedron appearance is regular, and FeCo2O4The combination of the nano-sheet array and the porous and hollow structure of the MOF material is beneficial to increasing the electrochemical activity of the surface of the electrode, the electron transfer rate on the electrode is increased, and the oxidation peak current intensity of dopamine detection is facilitated; FIG. 2 is a cyclic voltammogram of different modified electrodes in phosphate buffered saline at 50. mu.M dopamine, 0.1M, pH 7.0; with FeCo, in contrast to bare carbon cloth2O4The nano-sheet array, the MOF and the boric acid functional monomer are gradually modified on the surface of the carbon cloth, and the oxidation peak current of the composite electrode is obviously improved, because the surface area of the carbon cloth electrode modified by the nano-sheet array structure and the special structure of the MOF is large, the contact area of the electrode surface reaction is increased, and the active sites of the reaction are increased; FeCo on the other hand2O4The good electrocatalysis capability of the MOF improves the conduction rate of electrons and increases the electrochemical catalytic response current; moreover, modification of boric acid functional groups can realize the specific and selective dopamine adsorption of modified electrodes, so boric acid-MOF/FeCo2O4The peak current of the nanosheet array/carbon cloth electrode is the largest. FIG. 3 is a boronic acid modified FeCo2O4A cyclic voltammogram of a phosphoric acid buffer solution containing 50 mu M of dopamine is obtained by using a nanosheet array-MOF composite material modified electrode at different scanning rates, wherein the pH value of the electrode is 7.0; FIG. 4 is a graph of oxidation peak current versus scan rate in a linear fashion; boric acid-MOF/FeCo2O4The response of the nano-sheet array/the carbon cloth to DA is increased along with the increase of the scanning speed, the peak current responding to DA is in a linear relation with the scanning speed, and the correlation coefficient is divided into0.996, so boric acid-MOF/FeCo2O4The response of the nanosheet array/carbon cloth to DA can be regarded as an absorption-controlled electrochemical reaction process; FIG. 5 is the oxidation peak current measured in 8 replicates after elution of the modified electrode; based on boric acid-MOF/FeCo under optimal experimental conditions2O4The nano-sheet array/carbon cloth modified electrode adopts a CV method to test DA solution with the same concentration. After each test, the modified electrode was washed by immersing in 0.5mol/L sulfuric acid solution and deionized water to remove residual DA and possible oxidation products on the surface of the electrode, and the measurement was repeated, which indicated that: the peak current response is 95.38% of that of the newly manufactured electrode, and the modified electrode has good detection stability.
Example 2:
(a)MnCo2O4preparation of nanoflower array
Firstly, a piece of carbon cloth (1 x 8cm) is soaked in concentrated HNO3Reacting in the solution at 90 ℃ for 2 hours, and then washing with acetone, ethanol and deionized water for 10 minutes respectively to obtain the activated carbon cloth. 2mmol of Mn (NO)3)2·3H2O，4mmol Co(NO3)2·6H2Dissolving O and 0.84 g of hexamethylene tetramine in 60mL of mixed solution of ethanol and water (5:1), vigorously stirring at room temperature for 20min to obtain uniform mixed solution, soaking the activated three-dimensional carbon cloth in the mixed solution, transferring the mixture to a high-pressure reaction kettle, reacting at 200 ℃ for 12 h, cooling to room temperature after the reaction is finished, taking out a product, fully washing, drying at 60 ℃, finally, putting the obtained reaction product into a tubular furnace, annealing at 350 ℃ for 2 h at the heating rate of 2 ℃/min in the air atmosphere to obtain MnCo supported on the carbon cloth2O4And (4) a nanoflower array.
(b) MnCo modified by CoCu-MOF material2O4Preparation of nanoflower array
MnCo on the surface of the carbon cloth obtained in the step (a)2O4The nanoflower array was the substrate, immersed in 105mL of DMF, water and ethanol containing 9.6g of 2, 5-diaminoterephthalic acid, 0.7g of cobalt nitrate hexahydrate, 0.9g of copper nitrate trihydrate and 0.8g F127(1:1:1), uniformly dispersing by using ultrasonic waves, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 160 ℃, cooling to room temperature after the reaction is finished, taking out and fully washing the product, collecting the reaction product on the surface of the carbon cloth, washing the reaction product with ethanol for several times, and finally drying the reaction product in vacuum at 80 ℃ to obtain the CoCu-MOF material modified MnCo2O4A nanoflower array;
(c) boric acid modified MnCo2O4Preparation of nanoflower array-MOF composite material
Immersing the material obtained in the step (b) in a methanol solution containing 2-aminoimidazole for 5 hours, then immersing the material in a solution containing 3-amino-4-fluorobenzeneboronic acid functional monomer for 5 hours, then adding the composite material into 10% formaldehyde crosslinking agent saturated steam (25 ℃), and reacting for 12 hours to obtain the boric acid modified MnCo2O4The nanoflower array-MOF composite material.
(d) Adrenergic biosensor
Boric acid modified MnCo2O4And then detecting an electrochemical signal of the working electrode through an electrochemical workstation, and performing a linear regression equation on epinephrine through the DPV electrochemical signal intensity to obtain a working curve. FIG. 6 shows boric acid modified MnCo2O4SEM photographs of the nanoflower array-MOF composite; FIG. 7 boronic acid modified MnCo2O4Detecting differential pulse voltammograms of adrenalin with different concentrations by using a nanoflower array-MOF composite material electrode; FIG. 8 is a linear relationship between epinephrine concentrations and oxidation peak currents, after the electrode was enriched in a buffered solution containing epinephrine for 10min, the electrode was tested using Differential Pulse Voltammetry (DPV) and found that the oxidation peak currents increased linearly with increasing concentration and the oxidation peak currents showed good linear relationship (5 μ M-80 μ M) over a range of concentrations, where δ is the standard deviation of the oxidation peak current values, according to DL 3 δ/M; m is the slope of the corresponding regression curve, giving a limit of detection of 0.048. mu.M.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a boric acid modified metal oxide nano array-MOF composite material is characterized by comprising the following steps:
(a) preparation of metal oxide nano-arrays: firstly, growing any one or two of copper, cobalt, nickel, iron, zinc and manganese on the surface of carbon cloth by combining a hydrothermal method, a solvothermal method and an electrochemical deposition method with carbonization treatment to form a single metal or double metal oxide nano array;
(b) preparing a MOF material modified metal oxide nano array: taking the metal oxide nano array obtained in the step (a) as a substrate, adding 5-20 parts by weight of surfactant, 20-200 parts by weight of organic ligand, 100-800 parts by weight of organic solvent and 5-20 parts by weight of metal salt, and growing an MOF material in situ to obtain a metal oxide nano array-MOF composite material;
(c) preparation of the boric acid modified metal oxide nano array-MOF composite material: modifying the material obtained in the step (b) by using a surface stabilizer, then immersing the modified material into a solution containing a boric acid group functional monomer for 3-10 hours, adding the composite material into a cross-linking agent solution or cross-linking agent saturated steam, and reacting for 3-20 hours to obtain the boric acid modified metal oxide nano array-MOF composite material.
2. The method of making a boronic acid modified metal oxide nanoarray-MOF composite according to claim 1, wherein in step b):
the surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, triethylamine, triethyldiamine, polyethylene pyrrolidone, polyacrylamide, polypropylene imine, alkyl sodium sulfonate, sodium fatty acid, polyoxyethylene ether, sodium carboxylate, hexadecyl trimethyl ammonium bromide, polyethylene glycol, polyethylene oxide, P123 and F127;
the organic ligand is at least one of 2-amino terephthalic acid, 2-hydroxy terephthalic acid, 2, 5-diamino terephthalic acid, 2, 5-dihydroxy terephthalic acid, trimesic acid, 2-methylimidazole, benzimidazole, 2-nitroimidazole and 4-nitroimidazole;
the organic solvent is at least one of methanol, ethanol, water and DMF;
the metal salt is at least one of copper, cobalt, nickel, iron, zinc and manganese salts.
3. The method of making a boronic acid modified metal oxide nanoarray-MOF composite according to claim 1, wherein in step c):
the surface stabilizer is at least one of imidazole-2-formaldehyde, 2-aminoimidazole, 4-imidazole formaldehyde, 1-ethyl-1H-imidazole-2-formaldehyde and 1-methyl-1H-imidazole-2-formaldehyde;
the boric acid group functional monomer is at least one of 2-aminobenzeneboronic acid, 3-aminobenzeneboronic acid, 4-aminobenzeneboronic acid, 3-acrylamidophenylboronic acid, 3-fluoro-4-aldehyde phenylboronic acid, 4-fluoro-2-aldehyde phenylboronic acid, 4-fluoro-3-aldehyde phenylboronic acid, 4-carbamoylphenylboronic acid, 3-amino-4-fluorobenzeneboronic acid, 3-amino-5-fluorobenzeneboronic acid, 3- (2-carbonylvinyl) phenylboronic acid and 4-formylphenylboronic acid;
the cross-linking agent is at least one of formaldehyde, glyoxal and glutaraldehyde.
4. The method of making a boronic acid modified metal oxide nanoarray-MOF composite of claim 1,
the mass ratio of the surface stabilizer to the metal oxide nano array-MOF composite material is 1-3: 1;
the concentration of the boric acid group functional monomer is 3% -15%.
5. The method of making a boronic acid modified metal oxide nanoarray-MOF composite of claim 1,
the carbonization treatment in the step a) is carried out in the atmosphere of air in a muffle furnace, the temperature is 200-500 ℃, the heating rate is 3-10 ℃/min, and the reaction time is 1.5-5 h.
6. The method of making a boronic acid modified metal oxide nanoarray-MOF composite according to claim 1, wherein the in-situ grown MOF material in step b) is an in-situ grown MOF material by room temperature rest, hydrothermal reaction or solvothermal method.
7. The method of making a boronic acid modified metal oxide nanoarray-MOF composite of claim 1,
the shape of the nano array in the step a) is at least one of a nano wire, a nano rod, a nano sheet, a nano belt and a nano flower.
8. The boronic acid-modified metal oxide nanoarray-MOF composite material prepared by the method of any one of claims 1 to 7, wherein the boronic acid-modified metal oxide nanoarray-MOF composite material is used in a biosensor.
9. A biosensor is characterized in that the biosensor is a three-electrode system which is formed by taking the boric acid modified metal oxide nano array-MOF composite material as a flexible self-supporting working electrode according to claim 8, taking an Ag/AgCl or saturated calomel electrode as a reference electrode and taking a platinum wire or a platinum sheet as a counter electrode, an electrochemical signal of the working electrode is detected through an electrochemical workstation, and cis-dihydroxy biomolecules are detected through the strength of the electrochemical signal.
10. The biosensor of claim 9, wherein the cis-dihydroxy biomolecule is a biomolecule of the 1,2/1, 3-cis diol structure.
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