CN113406170B - Ni (OH) for non-enzymatic glucose detection 2 Nanosheet sensor and preparation method and application thereof - Google Patents

Ni (OH) for non-enzymatic glucose detection 2 Nanosheet sensor and preparation method and application thereof Download PDF

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CN113406170B
CN113406170B CN202110566575.XA CN202110566575A CN113406170B CN 113406170 B CN113406170 B CN 113406170B CN 202110566575 A CN202110566575 A CN 202110566575A CN 113406170 B CN113406170 B CN 113406170B
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陈燕
仲啸
何祖韵
陈海军
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South China University of Technology SCUT
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract

Hair brushBelongs to the technical field of glucose detection sensor materials, and discloses Ni (OH) for non-enzymatic glucose detection 2 A nano-sheet sensor and a preparation method and application thereof. The method comprises the following steps: dissolving nickel acetate in deionized water to obtain a deposition solution; immersing the foamed nickel substrate in nickel acetate solution, and depositing under constant current density to obtain Ni (OH) 2 Nanosheets, ni (OH) treated with an argon plasma of constant power 2 Nanosheets, resulting in the sensor. The preparation method is simple, and the electrodeposition method is utilized to synthesize Ni (OH) in one step 2 The nanosheet realizes efficient detection of glucose concentration and further improves the performance through a plasma processing technology. The invention mixes Ni (OH) 2 The nanosheet is applied to the field of glucose detection, and has the advantages of high current response, wide detection range and good selectivity.

Description

Ni (OH) for non-enzymatic glucose detection 2 Nanosheet sensor and preparation method and application thereof
Technical Field
The invention belongs to the technical field of glucose detection sensor materials, and particularly relates to Ni (OH) for non-enzymatic glucose detection 2 A nano-sheet sensor and a preparation method and application thereof.
Background
With the increasing living standard, diabetes becomes a chronic disease worldwide, and related diseases such as stroke, renal failure, heart disease and the like are brought about. Glucose is the major molecule in diabetes monitoring, and changes in its concentration have a vital role in human health. Accurate measurement of glucose is also of profound significance for future preventive medical diagnostics, food safety, environmental monitoring, pharmaceutical analysis and biotechnology.
Among the many methods for glucose measurement, optical and electrochemical analysis have been widely studied. Optical methods use a color change in the indicator to reflect the concentration of glucose. The color of the dye changes during the enzymatic reaction that converts glucose into its metabolites. (j.choi, d.kang, s.han, s.b. Kim, j.a.rogers, adv.healthcare mater.2017,6,1601355). Although color change provides an intuitive way for a patient to check for the presence of blood glucose, it is still insufficient to quantify glucose levels or to effectively measure low glucose levels. Even if quantitative measurements can be made, it is often necessary to use a cumbersome spectrophotometer, which makes colorimetric methods unsuitable for commercial use. (b. -h.hou, h.takanaga, g. Grossmann, l. -q.chen, x. -q.qu, a.m.jones, s.lande, o.schweissgut, w. Wiechert, w.b.frommer, nat.protoc.2011,6,1818). Therefore, the spectroscopic glucose detection method is more suitable for use in professional institutions such as hospitals. Electrochemical detection is considered to be an effective method for detecting glucose due to high detection efficiency and high calibration. Currently, electrochemical glucose biosensors are classified into enzymatic biosensors and non-enzymatic biosensors. The non-enzyme biosensor has the characteristics of low price, high efficiency, difficult influence from environmental change, simple preparation process and the like, and has attracted extensive attention of people. The basic components of a high performance non-enzymatic glucose biosensor are electrocatalysts with high sensitivity, long stability and good selectivity.
Defects are often observed in electrocatalysts and can alter the electronic structure, surface absorption characteristics, transport properties, etc. of the material, which can severely affect the reaction kinetics at the catalyst surface. Defect engineering has proven to be an effective method of increasing the electrocatalytic activity of transition metal oxides and hydroxides. For example, zhao et al used a bottom-up strategy to synthesize ZnAl-LDH nanosheets with varying numbers of oxygen vacancies. By increasing the density of oxygen vacancies, the formation of Zn-Vo complexes promotes CO 2 Adsorption and electron transfer processes to enhance photocatalytic CO 2 (Zhao, Y.F.; chen, G.B.; bian, T.; zhou, C.; waterhouse, G.I.N.; wu, L.Z.; tung, C.H.; smith, L.J.; O' Hare, D.; zhang, T.R. Defect-Rich Ultrathin ZnAl-layred Double Hydroxide Nanosheets for effective catalysis of CO2 to CO with Water. Adv 8978 z ft 8978 (47), 7824-7831). One-step synthesis method of Zhang et al prepares the NiFe-LDH nano-material with defects. Oxygen vacancies and cation vacancies in the material together enhance moistureThe adsorption capacity of the molecules and the binding strength of the OH intermediate formed in the OER process are enhanced, giving NiFe-LDH excellent OER reaction performance (Zhang, X.; zhao, Y.F.; zhao, Y.X.; shi, R.; waterhouse, G.I.N.; zhang, T.R.A Simple Synthetic strand heated Defect-Rich ports Monolayer NiFe-layer Double Hydroxide Nanosheets for Efficient electronic absorption Water oxidation. Adv Energy Mat 2019,9 (24)). Considering that the performance of electrochemical non-enzymatic glucose sensors depends to a large extent on the activity of the electrocatalyst, defect engineering is expected to be a promising approach to improve device sensitivity.
However, the current high-performance glucose catalyst is still in short supply, and the existing glucose catalyst synthesis method generally has high energy consumption and complex synthesis method.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide Ni (OH) for non-enzymatic glucose detection 2 A nano-sheet sensor and a preparation method and application thereof.
The invention aims to solve the problem of shortage of the current high-performance glucose catalyst and provide a green, energy-saving and simple synthetic Ni (OH) 2 A method of nanoplatelets.
Another object of the present invention is to treat the nanosheets synthesized by the above-described method with plasma. The invention can control and synthesize Ni (OH) with different oxygen defects by adjusting factors such as power, time and the like of plasma treatment 2 Nanosheets.
It is still another object of the present invention to provide the above Ni (OH) 2 Application of the nano-sheet. The Ni (OH) 2 The nanoplatelets are used to detect changes in glucose concentration in the body.
It is yet another object of the present invention to utilize the above process to observe the effect of plasma processing on the glucose sensing performance of a material.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides Ni (OH) for non-enzymatic glucose detection 2 The preparation method of the nanosheet sensor comprises the following steps:
taking the foamed nickel as a working electrode, then adopting a three-electrode system, soaking the foamed nickel in a nickel acetate solution, and carrying out electrodeposition treatment to obtain Ni (OH) load 2 Nano-sheet of foamed nickel, plasma treated to introduce defects, obtaining said Ni (OH) for non-enzymatic glucose detection 2 Nanosheet sensor (labeled as Ni (OH) 2 /NF electrode).
Further, the concentration of the nickel acetate solution is 0.05-0.2mol/L.
Preferably, the formulation of the nickel acetate solution comprises: and dissolving nickel acetate in deionized water, and uniformly mixing to obtain the nickel acetate solution.
Further, the time of the electrodeposition treatment is 100 to 500s.
Further, the current density of the electrodeposition treatment is 1 to 30mA/cm 2
Preferably, the current density of the electrodeposition treatment is 5 to 30mA/cm 2
Furthermore, in the three-electrode system, foamed nickel is used as a working electrode, ag/AgCl is used as a reference electrode, and Pt is used as a counter electrode.
Further, the plasma treatment employs argon plasma.
The power of the plasma treatment is 160-200W.
Preferably, the power of the plasma treatment is 180W.
Further, the time of the plasma treatment is 0-40min. Ni (OH) for non-enzymatic glucose assay when plasma treatment time is 0min 2 The surface of the nanosheet sensor does not introduce defects. The appearance before and after plasma treatment has no obvious change. Moreover, the present invention provides Ni (OH) load 2 The foam nickel of the nanosheet can be used for non-enzymatic glucose detection whether or not being subjected to plasma treatment, and the glucose sensing performance of the nanosheet is obviously improved after the nanosheet is subjected to plasma treatment.
Preferably, the plasma treatment time is 20-40min.
Preferably, the foamed nickel is subjected to a cleaning process before being used as a working electrode, the cleaning process comprising: the foamed nickel was ultrasonically cleaned in ethanol and water, respectively, and then rinsed with pure water.
Further preferably, the cleaning process comprises: the foamed nickel is respectively placed in ethanol and water for ultrasonic cleaning for 30min, and then is washed by pure water.
Preferably, the load Ni (OH) 2 The foamed nickel of the nanoplatelets is rinsed with deionized water to remove residual solution and dried prior to plasma treatment.
The invention provides Ni (OH) for non-enzymatic glucose detection prepared by the preparation method 2 A nanosheet sensor.
The invention provides Ni (OH) for non-enzymatic glucose detection 2 Ni (OH) on nanosheet sensor 2 The nano-sheet is nano-scale, and the diameter of the nano-sheet is less than or equal to 200nm.
The invention provides Ni (OH) for non-enzymatic glucose detection 2 Application of the nanosheet sensor in detecting the concentration of glucose in blood. The application is to judge the concentration change by electric signal conversion.
The invention provides Ni (OH) for non-enzymatic glucose detection 2 The application of the nanosheet sensor in detecting the concentration of glucose in blood comprises the following steps:
applying the Ni (OH) for non-enzymatic glucose detection 2 The method comprises the following steps of taking a nanosheet sensor as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a Pt sheet as a counter electrode, soaking the working electrode, the reference electrode and the counter electrode in electrolyte to form a three-electrode system, electrifying, then dropwise adding glucose solutions with different concentrations into the electrolyte, and respectively recording the current sizes corresponding to the glucose solutions with different concentrations; and (3) replacing the electrolyte, dripping a blood sample to be tested into the replaced electrolyte, and recording the current corresponding to the blood sample to obtain the glucose concentration in the blood sample.
The invention provides Ni (OH) for non-enzymatic glucose detection 2 Application of nanosheet sensor in detection of glucose concentration in bloodThe electrolyte is potassium hydroxide solution; the concentration of the potassium hydroxide solution is 0.05-0.2mol/L.
The invention provides Ni (OH) for non-enzymatic glucose detection 2 In the application of the nano-sheet sensor in detecting the concentration of glucose in blood, the linear sensitivity concentration range of the nano-sheet sensor is 0.001mM-0.5mM.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method provided by the invention has the advantages of low raw material price, no pollution to the environment, no need of high-energy reaction such as high temperature and high pressure and the like, and low production cost;
(2) The preparation method provided by the invention synthesizes Ni (OH) by an electrodeposition method in one step 2 The nano sheet has a simple preparation method and can be produced in batch;
(3) In the preparation method provided by the invention, the utilized flexible substrate foamed nickel with high specific surface area has more related applicable substrate selectivity, such as carbon cloth, carbon paper and the like;
(4) The preparation method provided by the invention utilizes a plasma processing technology, is simple in modification method, and can process materials in batches;
(5) The electro-deposition synthesis method used in the preparation method provided by the invention can change the morphology, yield and the like of the obtained material by changing the solution concentration, the reaction time, the substrate area and the like;
(6) The preparation method provided by the invention is simple and easy to operate, and can be used for synthesizing other related transition metal hydroxides and compounds thereof;
(7) The invention provides Ni (OH) for non-enzymatic glucose detection 2 After the nanosheet sensor is subjected to plasma treatment, the glucose sensing performance of the nanosheet sensor is obviously improved, and the nanosheet sensor can be used as a simple means for improving the performance of related materials;
(8) The invention provides Ni (OH) for non-enzymatic glucose detection 2 The nano-sheet sensor can be applied to the preparation of a blood glucose detector, and has good selectivity and stability.
Drawings
FIG. 1 shows the preparation of example 3 for non-enzymaticNi (OH) for glucose assay 2 A Scanning Electron Microscope (SEM) image of the nanosheet sensor;
FIG. 2 shows Ni (OH) for non-enzymatic glucose assay prepared in example 3 2 An X-ray energy spectrum (EDS) image of the nanosheet sensor;
FIG. 3 shows Ni (OH) for non-enzymatic glucose assay prepared in example 3 2 High Resolution Transmission Electron Microscopy (HRTEM) images of the nanosheet sensor;
FIG. 4 shows Ni (OH) for non-enzymatic glucose assay prepared in example 5 of the present invention 2 A Scanning Electron Microscope (SEM) image of the nanosheet sensor;
FIG. 5 shows Ni (OH) for non-enzymatic glucose assay prepared in example 7 of the present invention 2 A Scanning Electron Microscope (SEM) image of the nanosheet sensor;
FIG. 6 shows Ni (OH) for non-enzymatic glucose assay prepared in example 8 of the present invention 2 A Scanning Electron Microscope (SEM) image of the nanosheet sensor;
FIG. 7 shows Ni (OH) for non-enzymatic glucose assay of examples 3 and 8 2 The oxygen defect content contrast curve of the nanosheet sensor;
FIG. 8 shows Ni (OH) for non-enzymatic glucose assays of examples 3,5,7 and 8 2 A change curve of the glucose sensing current of the nanosheet sensor along with the processing time;
FIG. 9 shows Ni (OH) for non-enzymatic glucose assays of examples 3,5,7 and 8 2 The sensitivity curve of the nanosheet sensor;
FIG. 10 shows Ni (OH) for non-enzymatic glucose assay of examples 9 and 10 2 Nanosheet sensor selectivity profile.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
(1) Cleaning a foamed nickel substrate, and respectively performing ultrasonic treatment for 30min in ethanol and an aqueous solution;
(2) Washing the foamed nickel substrate in the step (1) by pure water to obtain a washed foamed nickel substrate for later use;
(3) Electrodeposition method using three-electrode system for Ni (OH) 2 And (3) nanosheets, wherein the washed foamed nickel substrate in the step (2) is used as a working electrode, ag/AgCl is used as a reference electrode, and Pt is used as a counter electrode. The foamed nickel substrate was immersed in 250mL of a 0.05mol/L nickel acetate solution at 5mA/cm 2 Is deposited for 100s at a current density of (1) to obtain Ni (OH) for non-enzymatic glucose detection 2 A nanosheet sensor.
(4) The obtained Ni (OH) for non-enzymatic glucose detection 2 The nanosheet sensor was washed with deionized water, dried, and evaluated for Ni (OH) using a three-electrode system 2 /NF electrode (the Ni (OH) for non-enzymatic glucose detection) 2 Nanosheet sensor), ni (OH) for non-enzymatic glucose detection 2 Nanosheet sensor (loaded with Ni (OH) 2 A nano-sheet foamed nickel substrate) as a working electrode, a saturated calomel electrode as a reference electrode, a Pt sheet as a counter electrode, a potassium hydroxide solution with the concentration of 0.05M as an electrolyte, and testing the current response corresponding to glucose with different concentrations to obtain the sensor with the glucose sensitivity of 7684 muA.mM -1 ·cm -2
Ni (OH) for non-enzymatic glucose assay obtained in example 1 2 The nanosheet sensor is of a nanosheet structure, the diameter of the nanosheet sensor is less than or equal to 200nm, and a scanning electron microscope image of the nanosheet sensor can be as shown in fig. 1.
Example 2
(1) Referring to the synthesis method of example 1, but with the nickel acetate solution concentration of 0.2mol/L in step (3), the deposition current density was 20mA/cm 2 Obtaining Ni (OH) for non-enzymatic glucose detection 2 A nanosheet sensor;
(2) Evaluation of Ni (OH) for non-enzymatic glucose assay using three-electrode System 2 Glucose sensing of nanosheet sensorsPerformance, test method reference example 1, but with a potassium hydroxide electrolyte concentration of 0.2M, the sensor was measured to have a glucose sensitivity of 15476. Mu.A. MM -1 ·cm -2
Example 2 obtained Ni (OH) for non-enzymatic glucose assay 2 The nanosheet sensor is of a nanosheet structure, the diameter of the nanosheet sensor is less than or equal to 200nm, and a scanning electron microscope image of the nanosheet sensor can be as shown in fig. 1.
Example 3
(1) Referring to the synthesis method of example 1, but with the nickel acetate solution concentration of 0.1mol/L in step (3), the deposition current density was 10mA/cm 2 To obtain a loaded Ni (OH) 2 Nano-sheet of foamed nickel, i.e. the Ni (OH) for non-enzymatic glucose detection 2 A nanosheet sensor;
(2) Evaluation of the Ni (OH) for non-enzymatic glucose detection Using a three-electrode System 2 The glucose sensing performance of the nanosheet sensor was tested according to example 1, except that the potassium hydroxide electrolyte concentration was 0.1M and the glucose sensitivity was 11171 μ a · mM -1 ·cm -2 As shown in fig. 9.
Wherein the obtained Ni (OH) is used for non-enzymatic glucose detection 2 The scanning electron microscope image of the nanosheet sensor is shown in FIG. 1, and the obtained material is of a nanosheet structure, and the diameter of the nanosheet structure is less than or equal to 200nm.
Wherein the obtained Ni (OH) is used for non-enzymatic glucose detection 2 An X-ray energy spectrum (EDS) imaging image of the nanosheet sensor is shown in FIG. 2, and Ni and O elements of the obtained material are uniformly distributed on the substrate.
Wherein the obtained Ni (OH) is used for non-enzymatic glucose detection 2 The image of the nanosheet sensor taken with a High Resolution Transmission Electron Microscope (HRTEM) is shown in fig. 3, and the Ni and O elements of the obtained material are uniformly distributed on the substrate.
Wherein the obtained Ni (OH) is used for non-enzymatic glucose detection 2 The defect content of the nanosheet sensor is shown in fig. 7, and it was found that the oxygen defect content was rare before the nanosheet sensor was subjected to plasma treatment.
Wherein the obtained modified glucose catalyst Ni (OH) 2 The sensing performance of (a) is shown in fig. 8.
Example 4
(1) With reference to the synthesis method of example 3, ni (OH) -supported was obtained 2 A nano-sheet of foamed nickel;
(2) Will load Ni (OH) 2 Treating the foamed nickel of the nanosheet with Ar plasma with power of 160W for 20min to obtain a modified sensor (the Ni (OH) for non-enzymatic glucose detection) 2 Nanosheet sensor) followed by glucose sensing performance testing. Test method referring to example 3, the glucose sensitivity of the modified sensor was found to be 11246 μ A. Multidot.mM -1 ·cm -2
Example 4 Ni (OH) prepared for non-enzymatic glucose assay 2 Scanning electron microscope images of nanosheet sensors before plasma treatment can be seen in fig. 1, ni (OH) for non-enzymatic glucose detection prepared in example 4 2 The shape of the nanosheet sensor after plasma treatment can be seen in FIG. 4, and the Ni (OH) for non-enzymatic glucose detection is found 2 The nanosheet sensor retains the nanosheet structure after plasma treatment.
Example 5
(1) Referring to the synthesis method of example 3, ni (OH) supported was obtained 2 A nano-sheet of foamed nickel;
(2) Ni (OH) to be used for non-enzymatic glucose detection 2 The nanosheet sensor is treated by Ar plasma with power of 180W for 20min to obtain a modified sensor (the Ni (OH) for non-enzymatic glucose detection) 2 Nanosheet sensor) followed by glucose sensing performance testing. Test methods refer to example 3.
Example 5 Ni (OH) for non-enzymatic glucose assay 2 Scanning electron microscope images of nanosheet sensors before plasma treatment can be seen in FIG. 1, which shows Ni (OH) for non-enzymatic glucose detection prepared in example 5 2 The shape of the nanosheet sensor after plasma treatment is shown in FIG. 4, and the Ni (OH) for non-enzymatic glucose detection is found 2 The nanosheet sensor still maintains nanosheet junction after plasma treatmentAnd (5) forming.
The sensitivity of the resulting modified sensor is shown in FIG. 8, and the glucose sensitivity is 11340. Mu.A. Multidot.mM -1 ·cm -2
Example 6
(1) With reference to the synthesis method of example 3, ni (OH) -supported was obtained 2 A nano-sheet of foamed nickel;
(2) Will load Ni (OH) 2 The foamed nickel of the nano-sheet is treated by Ar plasma with the power of 200W for 20min to obtain the modified sensor (the Ni (OH) for non-enzymatic glucose detection) 2 Nanosheet sensor) followed by glucose sensing performance testing. Test method referring to example 3, the glucose sensitivity of the resulting modified sensor was 11450. Mu.A.mM -1 ·cm -2
Example 6 Ni (OH) prepared for non-enzymatic glucose assay 2 Scanning electron microscope images of nanosheet sensors before plasma treatment can be seen in FIG. 1, which shows Ni (OH) for non-enzymatic glucose detection prepared in example 6 2 The shape of the nanosheet sensor after plasma treatment can be seen in FIG. 4, and the Ni (OH) for non-enzymatic glucose detection is found 2 The nanosheet sensor retains the nanosheet structure after plasma treatment.
Example 7
(1) With reference to the synthesis method of example 3, ni (OH) -supported was obtained 2 A nano-sheet of foamed nickel;
(2) Will load Ni (OH) 2 The foamed nickel of the nano-sheet is treated for 30min by Ar plasma with the power of 180W to obtain the modified sensor (the Ni (OH) for non-enzymatic glucose detection) 2 Nanosheet sensor) followed by glucose sensing performance testing. Test methods refer to example 3.
Example 7 Ni (OH) for non-enzymatic glucose assay 2 Scanning electron microscope images of nanosheet sensors before plasma treatment can be seen in FIG. 1, which shows Ni (OH) for non-enzymatic glucose detection prepared in example 7 2 The appearance of the nanosheet sensor after plasma treatment is shown in FIG. 5, and it is found thatThe Ni (OH) for non-enzymatic glucose detection 2 The nanosheet sensor retains the nanosheet structure after plasma treatment.
Wherein the sensing performance of the resulting modified sensor is shown in fig. 8.
The sensitivity of the resulting modified sensor is shown in FIG. 9, and the resulting glucose sensitivity is 11993. Mu.A. Multidot.mM -1 ·cm -2
Example 8
(1) With reference to the synthesis method of example 3, ni (OH) -supported was obtained 2 A nickel foam of nanosheets;
(2) Will load Ni (OH) 2 The foamed nickel of the nano-sheet is treated for 40min by Ar plasma with power of 180W to obtain the modified sensor (the Ni (OH) for non-enzymatic glucose detection) 2 Nanosheet sensor) followed by glucose sensing performance testing. Test methods refer to example 3.
Example 8 Ni (OH) prepared for non-enzymatic glucose assay 2 Scanning electron microscope images of nanosheet sensors before plasma treatment can be seen in fig. 1, which shows Ni (OH) for non-enzymatic glucose detection prepared in example 8 2 The shape of the nanosheet sensor after plasma treatment can be seen in FIG. 6, and the Ni (OH) for non-enzymatic glucose detection is found 2 The nanosheet sensor retains the nanosheet structure after plasma treatment.
Ni (OH) for non-enzymatic glucose assay prepared in example 3 and example 8 2 The oxygen defect content of the nanosheet sensor is compared with the curve, and as can be seen from fig. 7: example 8 Ni (OH) prepared for non-enzymatic glucose assay 2 The nanosheet sensor has more oxygen defects after plasma treatment.
The sensing performance of the modified sensor obtained in this example is shown in fig. 8. Prsistine in FIG. 8 represents Ni (OH) for non-enzymatic glucose assay prepared in example 3 2 A nanosheet sensor, ar-20min represents the modified sensor prepared in example 5, ar-30min represents the modified sensor prepared in example 7, and Ar-40min represents the sensor prepared in example 8The modified sensor of (1). From fig. 8, it can be found that: compared with a sensor without plasma treatment, the sensor after plasma treatment has better sensing performance, and the glucose sensing performance of the sensor after plasma treatment is obviously improved.
The sensitivity of the sensor obtained in this example after modification is shown in FIG. 9, and the obtained glucose sensitivity is 13940. Mu.A. Multidot.mM -1 ·cm -2 . Prsistine in FIG. 9 represents Ni (OH) for non-enzymatic glucose assay prepared in example 3 2 A nanosheet sensor, ar-20min represents the modified sensor prepared in example 5, ar-30min represents the modified sensor prepared in example 7, and Ar-40min represents the modified sensor prepared in example 8.
Example 9
(1) With reference to the synthesis method of example 3, ni (OH) -supported was obtained 2 Nanoflake nickel foam (Ni (OH) for non-enzymatic glucose detection) 2 Nanosheet sensors);
(2) Will load Ni (OH) 2 The preparation method comprises the steps of taking foamed nickel of a nanosheet as a working electrode, taking a saturated calomel electrode as a reference electrode and taking a Pt sheet as a counter electrode, soaking the working electrode, the reference electrode and the counter electrode in electrolyte (potassium hydroxide solution is selected) to form a three-electrode system, electrifying, adding 1mmol/L glucose, 0.1mol/L sodium chloride, 0.1mol/L uric acid, 0.1mol/L ascorbic acid and 0.1mol/L sucrose respectively into 0.1mol/L electrolyte under the condition of applying 0.6V bias by taking 60s as an interval, and finally adding 1mmol/L glucose. Thereby performing selectivity test of the material.
Wherein the obtained Ni (OH) is used for non-enzymatic glucose detection 2 The selectivity test of the nanosheet sensor is shown in fig. 10. Ni (OH) in FIG. 10 2 Represent Ni (OH) for non-enzymatic glucose assay prepared in example 9 2 A nanosheet sensor, ar-40min in FIG. 10, represents the modified sensor prepared in example 10.
Example 10
(1) With reference to the synthesis of example 8, a modified sensor (for non-use as described above) was obtainedEnzyme glucose detection Ni (OH) 2 Nanosheet sensors);
(2) Taking the modified sensor as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a Pt sheet as a counter electrode, soaking the working electrode, the reference electrode and the counter electrode in electrolyte (potassium hydroxide solution is selected) to form a three-electrode system, electrifying, respectively adding 1mmol/L glucose, 0.1mol/L sodium chloride, 0.1mol/L uric acid, 0.1mol/L ascorbic acid and 0.1mol/L sucrose into 0.1mol/L electrolyte under the condition of applying 0.6V bias, and finally adding 1mmol/L glucose. Thereby, the selectivity test of the material is carried out.
Wherein the selectivity test of the resulting modified sensor is shown in figure 10. Ni (OH) in FIG. 10 2 Represent Ni (OH) for non-enzymatic glucose assay prepared in example 9 2 A nanosheet sensor, ar-40min in FIG. 10, represents the modified sensor prepared in example 10.
As can be seen from FIG. 10, ni (OH) for non-enzymatic glucose assay prepared in example 9 2 The nanosheet sensor and the modified sensor prepared in example 10 have good selectivity for glucose, but the modified sensor prepared in example 10 (the sensor after plasma treatment) has better selectivity for glucose.
The above examples are only preferred embodiments of the present invention, which are intended to illustrate the present invention, but not to limit the present invention, and those skilled in the art should be able to make changes, substitutions, modifications, etc. without departing from the spirit of the present invention.

Claims (5)

1. Ni (OH) for non-enzymatic glucose detection 2 The preparation method of the nanosheet sensor is characterized by comprising the following steps of:
taking the foamed nickel as a working electrode, then adopting a three-electrode system, soaking the foamed nickel in a nickel acetate solution, and carrying out electrodeposition treatment to obtain Ni (OH) load 2 Performing plasma treatment on the nano-sheet foamed nickel to obtain the Ni (OH) for non-enzymatic glucose detection 2 A nanosheet sensor;
the concentration of the nickel acetate solution is 0.01-0.2mol/L; the time of the electrodeposition treatment is 100-500s; the current density of the electrodeposition treatment is 1-30mA/cm 2 (ii) a In the three-electrode system, foamed nickel is used as a working electrode, ag/AgCl is used as a reference electrode, and Pt is used as a counter electrode; argon plasma is adopted in the plasma treatment; the power of the plasma treatment is 160W-200W, and the time of the plasma treatment is 0-40min.
2. Ni (OH) for non-enzymatic glucose assay prepared by the method of claim 1 2 A nanosheet sensor.
3. The Ni (OH) of claim 2 for non-enzymatic glucose testing 2 Application of the nanosheet sensor in detecting the concentration of glucose in blood.
4. Ni (OH) for non-enzymatic glucose detection according to claim 3 2 The application of the nanosheet sensor in detecting the concentration of glucose in blood is characterized by comprising the following steps:
applying the Ni (OH) for non-enzymatic glucose detection 2 The method comprises the following steps of taking a nanosheet sensor as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a Pt sheet as a counter electrode, soaking the working electrode, the reference electrode and the counter electrode in electrolyte to form a three-electrode system, electrifying, then dropwise adding glucose solutions with different concentrations into the electrolyte, and respectively recording the current sizes corresponding to the glucose solutions with different concentrations; and (3) replacing the electrolyte, dripping a blood sample to be tested into the replaced electrolyte, and recording the current corresponding to the blood sample to obtain the glucose concentration in the blood sample.
5. Ni (OH) for non-enzymatic glucose detection according to claim 4 2 The application of the nanosheet sensor in detecting the concentration of glucose in blood is characterized in that the electrolyte is a potassium hydroxide solution; of the potassium hydroxide solutionThe concentration is 0.05M-0.2M.
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