CN111999360A - Graphene-based non-enzymatic glucose sensor and preparation method and application thereof - Google Patents
Graphene-based non-enzymatic glucose sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sensors, and particularly relates to a graphene-based non-enzymatic glucose sensor and a preparation method and application thereof. The invention provides a graphene-based non-enzymatic glucose sensor which comprises a copper substrate, a graphene film growing on the surface of the copper substrate, a two-dimensional layered structure compound scattered on the surface of the graphene film and a copper nanoparticle outer layer. In the invention, the graphene is a two-dimensional nano material, has the characteristics of high specific surface area, excellent conductivity and excellent biocompatibility, and is beneficial to improving the sensitivity of the sensor; the two-dimensional layered structure compound has larger specific surface area, good conductivity, stability and mechanical property; the copper nanoparticles have large surface-to-volume ratio and electronic performance, can cooperate with a two-dimensional layered structure compound to modify a sensor substrate-electrode combination, and help biological recognition to increase target binding, amplify signals and thus improve the sensitivity and stability of the sensor and expand the detection range.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a graphene-based non-enzymatic glucose sensor and a preparation method and application thereof.
Background
The sensor is a detection device which can sense the measured information and convert the sensed information into electric signals or other information in required forms according to a certain rule to output, so as to meet the requirements of information transmission, processing, storage, display, record, control and the like. In a blood glucose detecting device, a glucose sensor plays an important role in accurately measuring a blood glucose concentration.
The existing mature glucose sensor is generally manufactured by depositing a nano-modification material on the surface of a glassy carbon electrode or an FTO (fluorine-doped tin oxide) glass slide and fixing glucose oxidase. The sensor based on the glucose oxidase has the performances of extremely high selectivity and the like, but simultaneously has the obvious defects of poor reproducibility of enzyme immobilization, high cost, easy inactivation and the like, for example, the sensor can not well immobilize the biological enzyme, and the catalytic activity of the enzyme is kept for a long time, so that the sensitivity and the stability of the sensor are poor (Lijunhua, Kuang Dynasty, Von swim orchid, Liumeng, Deng Huayang. the glucose biosensor is prepared based on a titanium dioxide/carbon nano tube/chitosan nano composite film [ J ]. the report of inorganic chemistry 2011,27(11):2172 2178.). In view of the fact that enzyme as a protein can block electron transfer between enzyme and electrode and affect sensitivity of sensor, there are also technical personnel studying non-enzymatic glucose sensors, but the obtained non-enzymatic glucose sensor cannot guarantee stability and a large detection range (Liangyu, Qing, Yangyingjun, Zhuhong, Jiaming macro. preparation of nano carbon/nano gold glucose biosensor and its influence mechanism [ J ] chemical reagent, 2019,41(11): 1139-.
At present, reports of non-enzymatic glucose sensors with high sensitivity, high stability and a large detection range are not seen for a long time.
Disclosure of Invention
In view of this, the present invention aims to provide a graphene-based non-enzymatic glucose sensor and a preparation method thereof, and the graphene-based non-enzymatic glucose sensor provided by the present invention has characteristics of large detection range, high sensitivity and high stability, does not contain an enzyme, and avoids the influence of the enzyme on the detection sensitivity.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a graphene-based non-enzymatic glucose sensor which comprises a copper substrate, a graphene film growing on the surface of the copper substrate, a two-dimensional layered structure compound scattered on the surface of the graphene film and a copper nanoparticle outer layer;
the chemical composition of the two-dimensional layered structure compound is Mn+1XnTyWherein N is 1,2 or 3, M is a transition metal element, T is a-O, -OH or-F functional group, and X is C or N.
Preferably, in the graphene-based non-enzymatic glucose sensor, the loading amount of the two-dimensional layered structure compound is 0.1-1.0 mg/g, and the loading amount of the copper nanoparticles is 0.1-0.5 mg/g.
Preferably, the two-dimensional layered structure compound includes Ti3C2Ty、Ti2CTy、Ta4C3Ty、(Ti0.5Nb0.5)2CTyAnd (V)0.5Cr0.5)3C2TyOne or more of (a).
The invention also provides a preparation method of the graphene-based non-enzymatic glucose sensor in the technical scheme, which comprises the following steps:
carrying out chemical vapor deposition on one side of the copper substrate by using a carbon source precursor gas under the condition of a shielding gas-reducing gas mixed gas to obtain a graphene-copper plate;
coating a two-dimensional layered structure compound on the graphene surface of the graphene-copper plate to obtain a two-dimensional layered structure compound-graphene-copper plate;
and performing electrochemical deposition of nano-copper on the surface of the two-dimensional layered structure compound-graphene-copper plate by using a copper sulfate solution to obtain the graphene-based non-enzymatic glucose sensor.
Preferably, the shielding gas in the shielding gas-reducing gas mixed gas is argon and/or helium, and the reducing gas is hydrogen; the volume fraction of the reducing gas in the protective gas-reducing gas mixed gas is 10-30%.
Preferably, the carbon source precursor gas is acetylene, methane or ethylene.
Preferably, the chemical vapor deposition conditions include: the background pressure is 80-100 Pa, the flow of the protective gas-reducing gas mixture is 80-100 sccm, the flow of the carbon source precursor gas is 4-10 sccm, the ambient temperature is 950-1050 ℃, and the time is 10-20 min.
Preferably, the coating amount of the two-dimensional layered structure compound is 0.03-0.08 mg/cm2。
Preferably, the concentration of the copper sulfate solution is 0.01-0.04 mol/L; the electrochemical deposition adopts constant potential deposition; the conditions of potentiostatic deposition include: the voltage is 0.2-0.6V and the time is 2-10 min.
The invention also provides an application of the graphene-based non-enzymatic glucose sensor in the technical scheme or the graphene-based non-enzymatic glucose sensor prepared by the preparation method in the technical scheme in the preparation of a blood glucose detection device.
The invention provides a graphene-based non-enzymatic glucose sensor which comprises a copper substrate, a graphene film growing on the surface of the copper substrate, a two-dimensional layered structure compound scattered on the surface of the graphene film and a copper nanoparticle outer layer; the chemical composition of the two-dimensional layered structure compound is Mn+1XnTyWherein N is 1,2 or 3, M is a transition metal element, T is a-O, -OH or-F functional group, and X is C or N. According to the invention, the copper substrate is directly adopted as the substrate, so that the reduction of the conductivity of the graphene caused by graphene transfer can be avoided; the graphene is a two-dimensional nano material, has the characteristics of high specific surface area, excellent conductivity and excellent biocompatibility, is favorable for providing an integral and continuous membrane with thick atoms as a sensor electrode, and is favorable for improving the sensitivity of the sensor; the two-dimensional layered structure compound is a novel two-dimensional transition metal carbide or nitride material with a 2D structure similar to graphene, and has a unique 2D layered structure, a large specific surface area, good conductivity, stability and mechanical properties; the copper nanoparticles have good biocompatibilityThe sensor substrate-electrode combination composed of the copper substrate and the graphene film can be cooperatively modified with a two-dimensional layered structure compound to help biological recognition, so that target combination is increased, signals are amplified, the sensitivity and stability of the sensor are effectively improved, and the detection range is enlarged.
Experimental results show that the sensitivity of the graphene-based non-enzymatic glucose sensor exceeds 100 muA.mM-1·cm-2The detection limit can reach below 10 mu mol/L, and the linear detection capability is good in the range of the glucose concentration of 0.01-3.0 mmol/L.
Detailed Description
The invention provides a graphene-based non-enzymatic glucose sensor which comprises a copper substrate, a graphene film growing on the surface of the copper substrate, a two-dimensional layered structure compound scattered on the surface of the graphene film and a copper nanoparticle outer layer;
the chemical composition of the two-dimensional layered structure compound is Mn+1XnTyWherein N is 1,2 or 3, M is a transition metal element, T is a-O, -OH or-F functional group, and X is C or N.
The copper substrate of the present invention is not particularly limited, and a copper substrate known to those skilled in the art may be used. In the invention, the thickness of the copper substrate is preferably 20-40 μm, more preferably 20-30 μm, and most preferably 25 μm.
In the present invention, the thickness of the graphene thin film is preferably a single-layer graphene thickness.
In the present invention, the chemical composition of the two-dimensional layered structure compound is Mn+1XnTyWherein N is 1,2 or 3, M is a transition metal element, T is a-O, -OH or-F functional group, and X is C or N. In the present invention, M is preferably one or more of Ti, V, Nb, Ta, Cr and Mo, and more preferably a combination of Ti, Ta, Ti and Nb or a combination of V and Cr. In the present invention, the two-dimensional layered structure compound preferably includes Ti3C2Ty、Ti2CTy、Ta4C3Ty、(Ti0.5Nb0.5)2CTyAnd (V)0.5Cr0.5)3C2TyOne or more of (a).
In the present invention, the two-dimensional layered structure compound is preferably commercially available or autonomously prepared. In the invention, the method for autonomously preparing the two-dimensional layered structure compound is preferably obtained by etching a precursor of the two-dimensional layered structure compound; the chemical composition of the precursor of the two-dimensional layered structure compound is Mn+1AXnWherein N is an integer of 1 to 3, M is one or more of transition metal elements, A is a third main group and/or a fourth main group element, and X is C or N. In the present invention, M is preferably one or more of Ti, V, Nb, Ta, Cr and Mo, more preferably a combination of Ti, Ta, Ti and Nb or a combination of V and Cr; a is preferably Al and/or Zn, more preferably Al; x is preferably C; n is 1,2 or 3. In the present invention, the two-dimensional layered structure compound precursor preferably includes Ti2AlC、Ta4AlC3、(Ti0.5Nb0.5)2AlC and (V)0.5Cr0.5)3AlC2One or more of (a). The etching method is not particularly limited, and a method for etching a two-dimensional layered structure compound precursor, which is well known to those skilled in the art, may be used. In the graphene-based non-enzymatic glucose sensor, the loading amount of the two-dimensional layered structure compound is preferably 0.1-1.0 mg/g, and more preferably 0.31-0.6 mg/g.
In the present invention, the particle size of the copper nanoparticles is preferably 100 to 400nm, and more preferably 150 to 350 nm. In the graphene-based non-enzymatic glucose sensor, the loading amount of the copper nanoparticles is preferably 0.1-0.5 mg/g, and more preferably 0.1-0.3 mg/g.
The invention also provides a preparation method of the graphene-based non-enzymatic glucose sensor in the technical scheme, which comprises the following steps:
carrying out chemical vapor deposition on one side of the copper substrate by using a carbon source precursor gas under the condition of a shielding gas-reducing gas mixed gas to obtain a graphene-copper plate;
coating a two-dimensional layered structure compound on the graphene surface of the graphene-copper plate to obtain a two-dimensional layered structure compound-graphene-copper plate;
and performing electrochemical deposition of nano-copper on the surface of the two-dimensional layered structure compound-graphene-copper plate by using a copper sulfate solution to obtain the graphene-based non-enzymatic glucose sensor.
In the present invention, the components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the method, under the condition of a protective gas-reducing gas mixed gas, chemical vapor deposition is carried out on one surface of a copper substrate by using a carbon source precursor gas, so that the graphene-copper plate is obtained.
In the present invention, the copper substrate is preferably subjected to a pretreatment before being subjected to chemical vapor deposition. In the present invention, the pretreatment preferably includes first cleaning, polishing, second cleaning, and drying, which are performed in this order.
In the present invention, the first cleaning preferably includes acetone washing, absolute ethyl alcohol washing, deionized water washing, hydrochloric acid soaking, and deionized water washing, which are sequentially performed. In the present invention, the acetone washing is preferably performed under ultrasonic conditions; the power of the ultrasound is preferably 30W; the time for washing with acetone is preferably 2-5 min, and more preferably 2-4 min. In the present invention, the anhydrous ethanol washing is preferably performed under ultrasonic conditions; the power of the ultrasound is preferably 30W; the time for washing with the absolute ethyl alcohol is preferably 2-5 min, and more preferably 2-4 min. In the invention, the mass concentration of hydrochloric acid in the hydrochloric acid soaking is preferably 10%, and the hydrochloric acid soaking time is preferably 2-5 min, and more preferably 2.5-4 min. The deionized water washing is not particularly limited in the invention, and the residual washing liquid in the previous washing step can be removed.
In the present invention, the polishing is preferably electrochemical polishing. In the present invention, the method of electrochemical polishing preferably comprises: and (3) connecting a copper substrate to be polished with a power cathode by adopting a direct-current power supply, connecting a clean pure copper plate with a power anode, and performing electrochemical polishing in polishing solution. In the present invention, the composition of the polishing solution preferably includes deionized water, absolute ethyl alcohol, orthophosphoric acid, isopropyl alcohol and urea; the volume ratio of the deionized water to the absolute ethyl alcohol to the orthophosphoric acid to the isopropanol is preferably 10: 5: 5: 1, the ratio of the volume of isopropanol to the mass of urea is preferably 1 mL: (1-2) g. In the present invention, the conditions of the electrochemical polishing include: the voltage is preferably 5-8V, more preferably 6-7V, and most preferably 7V; the current is preferably 1-3A, more preferably 1-2A, and most preferably 1A; the time is preferably 50 to 80 seconds, and more preferably 60 to 80 seconds.
In the present invention, the second cleaning preferably includes acetone washing, absolute ethyl alcohol washing, and deionized water washing, which are sequentially performed. In the present invention, the acetone washing is preferably performed under ultrasonic conditions; the power of the ultrasound is preferably 30W; the time for washing with acetone is preferably 2-5 min, and more preferably 2-4 min. In the present invention, the anhydrous ethanol washing is preferably performed under ultrasonic conditions; the power of the ultrasound is preferably 30W; the time for washing with the absolute ethyl alcohol is preferably 2-5 min, and more preferably 2-4 min. The deionized water washing is not particularly limited in the invention, and the residual washing liquid in the previous washing step can be removed.
In the present invention, the drying is preferably blow drying, more preferably nitrogen blow drying.
In the invention, the shielding gas in the shielding gas-reducing gas mixed gas is argon and/or helium, and the reducing gas is hydrogen. In the invention, the volume fraction of the reducing gas in the shielding gas-reducing gas mixed gas is preferably 10-30%, and more preferably 10-20%.
In the present invention, the carbon source precursor gas is preferably acetylene, methane, or ethylene.
In the present invention, the chemical vapor deposition conditions include: the background pressure intensity is preferably 80-100 Pa, and more preferably 85-95 Pa; the flow rate of the protective gas-reducing gas mixture is preferably 80-100 sccm, and more preferably 85-100 sccm; the flow rate of the carbon source precursor gas is preferably 4-10 sccm, more preferably 5-8 sccm, and most preferably 5 sccm; the environment temperature is preferably 950-1050 ℃, more preferably 975-1025 ℃ and most preferably 1000 ℃; the time is preferably 10 to 20min, more preferably 12 to 18min, and most preferably 15 min.
Before the chemical vapor deposition, the invention preferably cleans the cavity of the chemical vapor deposition reaction chamber. In the invention, the method for cleaning the cavity is preferably to vacuumize until the pressure in the chemical vapor deposition reaction chamber reaches 1-10 Pa, and then introduce the protective gas-reducing gas mixture to 3 multiplied by 104～6×104Pa; repeating the steps of vacuumizing and ventilating for 3-5 times. In the invention, preferably, after the cavity is cleaned, the cavity of the chemical vapor deposition reaction chamber is subjected to heat preservation at the environmental temperature, and then chemical vapor deposition is carried out; the heat preservation time is preferably 25-40 min, more preferably 30-40 min, and most preferably 30 min.
After the chemical vapor deposition, preferably after stopping introducing the carbon source precursor gas, continuously introducing a protective gas-reducing gas mixed gas until the graphene-copper plate reaches the room temperature; the flow rate of the protective gas-reducing gas mixture is preferably 60-80 sccm, and more preferably 60-70 sccm.
After the introduction of the shielding gas-reducing gas is stopped, the present invention preferably performs oxygen plasma treatment or UV treatment on the sample on which the graphene is deposited. In the present invention, the oxygen plasma treatment is preferably performed at a power of 60W for a time of 40 s. In the present invention, the power of the UV treatment is preferably 60W, and the time is preferably 10 min.
After the graphene-copper plate is obtained, coating a two-dimensional layered structure compound on the graphene surface of the graphene-copper plate to obtain the two-dimensional layered structure compound-graphene-copper plate.
In the present invention, the two-dimensional layered structure compound is identical to the two-dimensional layered structure compound of the above technical scheme, and is not described herein again. In the invention, in the graphene-based non-enzymatic glucose sensor, the coating amount of the two-dimensional layered structure compound is preferably 0.03-0.08 mg/cm2More preferably 0.05 to 0.07mg/cm2. In the present invention, the two-dimensional layered structure compound is preferably provided in the form of a two-dimensional layered structure compound dispersion; a dispersion solvent for the two-dimensional layered structure compound dispersion liquidPreferably water; the concentration of the two-dimensional layered structure compound dispersion liquid is preferably 10 mg/mL; the coating amount of the two-dimensional layered structure compound dispersion liquid is preferably 5-30 mu L/cm2More preferably 10 to 25. mu.L/cm2More preferably 15 to 22. mu.L/cm2。
In the present invention, the coating method of the two-dimensional layered structure compound is preferably spin coating or spray coating or dipping. In the invention, when the coating is spin coating, the rotation speed in the spin coating is preferably 500-1000 rpm, and more preferably 700-1000 rpm; the time is preferably 30 to 60 s/time, and more preferably 40 to 60 s/time; the number of spin-coating is preferably one or more. In the invention, when the coating is spraying, the size of the spray nozzle in the spraying is preferably 0.2-0.6 mm, more preferably 0.4-0.6 mm, and most preferably 0.5 mm; the working pressure is preferably 50 to 100psi, more preferably 60 to 90psi, even more preferably 70 to 85psi, and most preferably 80 psi. When the coating method of the two-dimensional layered structure compound is immersion, the graphene-copper plate is preferably directly immersed into the dispersion liquid of the two-dimensional layered structure compound; the immersion time is preferably 3-5 min, and more preferably 3.5-4.5 min.
After coating the two-dimensional layered structure compound, the present invention preferably further comprises drying the sample coated with the two-dimensional layered structure compound. In the invention, the drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the time is preferably 3 to 6min, more preferably 4 to 5min, and most preferably 5 min.
After the two-dimensional layered structure compound-graphene-copper plate is obtained, nano copper is electrochemically deposited on the two-dimensional layered structure compound surface of the two-dimensional layered structure compound-graphene-copper plate by using a copper sulfate solution, and the graphene-based non-enzymatic glucose sensor is obtained.
In the invention, the concentration of the copper sulfate solution is preferably 0.01-0.04 mol/L, more preferably 0.015-0.03 mol/L, and most preferably 0.02 mol/L. In the present invention, the electrochemical deposition is preferably potentiostatic deposition. In the present invention, the conditions of potentiostatic deposition include: the deposition voltage is preferably 0.2-0.6V, and more preferably 0.4-0.5V; the time is preferably 2 to 10min, and more preferably 3 to 6 min. In the graphene-based non-enzymatic glucose sensor, the loading amount of the copper nanoparticles is preferably 0.1-0.5 mg/g.
The invention also provides an application of the graphene-based non-enzymatic glucose sensor in the technical scheme or the graphene-based non-enzymatic glucose sensor prepared by the preparation method in the technical scheme in the preparation of a blood glucose detection device.
In the invention, the application specifically comprises: electrochemical determination is adopted; the device for electrochemical determination is an electrochemical workstation; the electrochemical assay employs a three-electrode system: the platinum electrode is a counter electrode, the Ag/AgCl electrode is a reference electrode, and the graphene-based non-enzymatic glucose sensor is a working electrode; the electrochemical determination is preferably to perform electrochemical measurements such as CV and DPV in potassium ferricyanide solution or PBS and study the measurement results under different glucose concentrations; the glucose concentration content was tested.
In the present invention, the detection mechanism of the graphene-based non-enzymatic glucose sensor is as follows: depending on the redox of Cu nanoparticles, specifically, Cu is oxidized into CuO in solution and further oxidized into Cu (III), glucose is catalyzed and oxidized into glucose lactone by Cu (III), Cu (III) is reduced into Cu (II), and finally the glucose lactone is hydrolyzed into gluconic acid; when the graphene-based non-enzymatic glucose sensor provided by the invention is used for carrying out electrochemical characterization on the glucose content, the current changes due to the catalytic oxidation of glucose, so that the glucose content can be characterized and analyzed.
In order to further illustrate the present invention, the following examples are provided to describe the graphene-based non-enzymatic glucose sensor and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents used in the examples are all commercially available, of which the two-dimensional layered structure compound Ti3C2TxPurchased from Jilin province, science & technology Limited, from the precursor Ti2And etching the AlC to obtain the product.
Example 1
Sequentially and respectively cleaning a copper substrate of 2cm multiplied by 2cm in acetone, ethanol and deionized water for 3min under the condition of ultrasonic 30W power to remove surface impurities and organic matters; soaking the material in hydrochloric acid with the mass concentration of 10% for 2min, performing electrochemical polishing for 80s under the conditions that the voltage is 7V and the current is 1A (the polishing solution comprises deionized water, absolute ethyl alcohol, orthophosphoric acid, isopropanol and urea, wherein the volume ratio of the deionized water, the absolute ethyl alcohol, the orthophosphoric acid and the isopropanol is 10: 5: 5: 1, and the mass ratio of the isopropanol to the urea is preferably 1 mL: 1.8g), sequentially performing ultrasonic treatment in acetone and ethanol for 2min, finally soaking the material in deionized water for multiple times for rinsing, and drying the rinsed material by using nitrogen;
placing the pretreated copper substrate on a quartz boat, placing the quartz boat in a high-temperature reaction furnace, starting a mechanical pump to pump the copper substrate to a low pressure of below 10Pa, introducing a protective gas-reducing gas mixture of 60sccm (the volume ratio of hydrogen to argon in the protective gas-reducing gas mixture is 1: 9), and raising the pressure of the furnace to 5 x 104After Pa, vacuumizing to below 10Pa again, and washing for many times to exhaust air in the cavity; after the air pressure of the cavity of the high-temperature reaction furnace is stabilized to be 100Pa, starting heating to 1050 ℃, keeping the gas flow rate unchanged for 30min, and realizing the high-temperature annealing pretreatment process of the copper substrate; then introducing 100sccm of a protective gas-reducing gas mixed gas (the volume ratio of hydrogen to argon in the protective gas-reducing gas mixed gas is 1: 9), keeping the flow rate of acetylene gas at 5sccm for 20min, and forming graphene on a copper plate by using chemical vapor deposition; turning off acetylene gas, introducing argon gas with the flow rate of 40sccm, turning off heating, cooling the sample to room temperature, taking out the sample, and performing oxygen plasma treatment for 40s under the condition of 60W to obtain a graphene-copper plate;
preparing Ti with the concentration of 10mg/mL by using deionized water3C2Tx dispersion (T is-O, -OH or-F), and ultrasonic treating at room temperature for 1h to extractHigh dispersibility, then adding the obtained Ti3C2The Tx dispersion liquid is spin-coated on a graphene-copper plate, and is spin-coated for 20s at the rotating speed of 500rpm and then is spin-coated for 5s at the rotating speed of 1000rpm during spin-coating; ti3C2After the Tx dispersion liquid is coated in a spinning mode, placing the obtained sample on a heating plate, and drying for 5min at the temperature of 100 ℃ to obtain a two-dimensional layered structure compound-graphene-copper plate;
preparing a copper sulfate solution with the concentration of 0.02mol/L by using deionized water and copper sulfate pentahydrate powder, and performing electrochemical deposition on the two-dimensional layered structure compound surface of the two-dimensional layered structure compound-graphene-copper plate for 3min under the condition of 0.5V voltage to obtain the graphene-based non-enzymatic glucose sensor.
Test example 1
The detection capability of the graphene-based non-enzymatic glucose sensor obtained in example 1 was tested for glucose using an electrochemical workstation equipped with three electrodes as a working electrode, a platinum wire as a counter electrode, and Ag/AgCl as a reference electrode.
Electrochemical characterization was performed by alternating current impedance spectroscopy (AC) Cyclic Voltammetry (CV) and chronoamperometry (DPV) in phosphate buffered saline PBS (0.1mol/L, pH 7);
wherein the test voltage of the CV method is-0.6-1.0V, and the scanning speed is 100 mV/s;
due to the large active surface areas of the graphene and the nano modified material, the redox behavior of the electrode can show a larger area, and the current density is increased; and continuously adding a glucose standard solution into the solution, researching and monitoring the timing response of the oxidation current of the sensing electrode to the glucose concentration by a timing current method, and analyzing the detection result. 5 sensing electrodes are manufactured by the same method, the sensing electrodes are respectively tested, and the reproducibility of the sensor is obtained through analysis according to the detection result.
Through detection, the graphene-based non-enzymatic glucose sensor provided by the invention has excellent detection capability on glucose, and the sensitivity exceeds 100 muA.mM-1·cm-2The detection limit can reach below 10 mu mol/L, and the linear detection capability is good in the range of the glucose concentration of 0.01-3.0 mmol/L.
Example 2
Sequentially and respectively cleaning a copper substrate of 2cm multiplied by 1.5cm in acetone, ethanol and deionized water for 3min under the condition of ultrasonic 30W power to remove surface impurities and organic matters; soaking the material in hydrochloric acid with the mass concentration of 10% for 2min, performing electrochemical polishing for 80s under the conditions that the voltage is 7V and the current is 1A (the polishing solution comprises deionized water, absolute ethyl alcohol, orthophosphoric acid, isopropanol and urea, wherein the volume ratio of the deionized water, the absolute ethyl alcohol, the orthophosphoric acid and the isopropanol is 10: 5: 5: 1, and the mass ratio of the isopropanol to the urea is preferably 1 mL: 1.8g), sequentially performing ultrasonic treatment in acetone and ethanol for 2min, finally soaking the material in deionized water for multiple times for rinsing, and drying the rinsed material by using nitrogen;
placing the pretreated copper substrate on a quartz boat, placing the quartz boat in a high-temperature reaction furnace, starting a mechanical pump to pump the copper substrate to a low pressure of below 10Pa, introducing a protective gas-reducing gas mixture of 60sccm (the volume ratio of hydrogen to argon in the protective gas-reducing gas mixture is 1: 9), and raising the pressure of the furnace to 5 x 104After Pa, vacuumizing to below 10Pa again, and washing for many times to exhaust air in the cavity; after the air pressure of the cavity of the high-temperature reaction furnace is stabilized to be 100Pa, starting heating to 1050 ℃, keeping the gas flow rate unchanged for 30min, and realizing the high-temperature annealing pretreatment process of the copper substrate; then introducing 100sccm of a protective gas-reducing gas mixed gas (the volume ratio of hydrogen to argon in the protective gas-reducing gas mixed gas is 1: 9), keeping the flow rate of acetylene gas at 5sccm for 20min, and forming graphene on a copper plate by using chemical vapor deposition; turning off acetylene gas, introducing argon gas with the flow rate of 40sccm, turning off heating, cooling the sample to room temperature, taking out the sample, and performing UV treatment for 10min under the condition of 60W to obtain a graphene-copper plate;
preparing Ti with the concentration of 5mg/mL by using deionized water3C2Tx dispersion (T is-O, -OH or-F), performing ultrasonic treatment for 1h at room temperature to improve the dispersibility, and then immersing the obtained graphene-copper plate into Ti3C2Tx dispersion for 4min, and impregnating Ti3C2Placing a sample of the Tx dispersion solution on a heating plate, and drying for 5min at 100 ℃ to obtain a two-dimensional layered structure compound-graphene-copper plate;
preparing a copper sulfate solution with the concentration of 0.02mol/L by using deionized water and copper sulfate pentahydrate powder, and performing electrochemical deposition on the two-dimensional layered structure compound surface of the two-dimensional layered structure compound-graphene-copper plate for 6min under the condition of 0.4V voltage to obtain the graphene-based non-enzymatic glucose sensor.
Through tests, the detection sensitivity and the lower detection limit of the graphene-based non-enzymatic glucose sensor obtained in the embodiment to glucose are close to those of the test example 1.
Comparative example 1
The document "Lijunhua, Kuang Dynasty, Von swim blue, Liu Meng Qin, Deng Huayang" is based on titanium dioxide/carbon nano tube/chitosan nano composite film to prepare glucose biosensor [ J ]. inorganic chemistry report, 2011,27(11): 2172-.
The electrocatalytic oxidation performance of the sensor on glucose is examined by Cyclic Voltammetry (CV) and Chronoamperometry (CA), the sensor has linear response in the range of 0.5-20.0 mmol/L on glucose, and the sensitivity is 53.62 muA.mM-1·cm-2The detection limit was 0.2 mmol/L.
Comparative example 2
Literature "luomingrong, wang liang, zhang yao static, zhao shuang" enzyme-free glucose sensor based on polydopamine/copper microparticle self-assembled multilayer film [ J]2016,44(06):882-n) (ii) a The sensitivity of the sensor can be regulated and controlled by controlling the number of the assembled layers of the multilayer film.
The electrocatalytic oxidation performance of the modified electrode on glucose is researched by adopting a cyclic voltammetry method and a current-time curve method. For four layers GCE/(PDA/Cu)4The linear range of the detected glucose is 0.5-9.0 mmol/L, and the detection limit is 5.8 mu mol/L.
As can be seen from comparison between the test example 1 and the comparative examples 1-2, the graphene-based non-enzymatic glucose sensor provided by the invention has the advantages of lower detection linearity, low detection limit and high detection sensitivity of glucose concentration, and can detect the content of low-concentration glucose with higher sensitivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A graphene-based non-enzymatic glucose sensor comprises a copper substrate, a graphene film growing on the surface of the copper substrate, a two-dimensional layered structure compound scattered on the surface of the graphene film and a copper nanoparticle outer layer;
the chemical composition of the two-dimensional layered structure compound is Mn+1XnTyWherein N is 1,2 or 3, M is a transition metal element, T is a-O, -OH or-F functional group, and X is C or N.
2. The graphene-based non-enzymatic glucose sensor according to claim 1, wherein the loading amount of the two-dimensional layered structure compound in the graphene-based non-enzymatic glucose sensor is 0.1-1.0 mg/g, and the loading amount of the copper nanoparticles is 0.1-0.5 mg/g.
3. The non-enzymatic glucose sensor of claims 1 or 2 wherein the two-dimensional layered structure compound comprises Ti3C2Ty、Ti2CTy、Ta4C3Ty、(Ti0.5Nb0.5)2CTyAnd (V)0.5Cr0.5)3C2TyOne or more of (a).
4. A method of making the graphene-based non-enzymatic glucose sensor of any one of claims 1-3, comprising the steps of:
carrying out chemical vapor deposition on one side of the copper substrate by using a carbon source precursor gas under the condition of a shielding gas-reducing gas mixed gas to obtain a graphene-copper plate;
coating a two-dimensional layered structure compound on the graphene surface of the graphene-copper plate to obtain a two-dimensional layered structure compound-graphene-copper plate;
and performing electrochemical deposition of nano-copper on the surface of the two-dimensional layered structure compound-graphene-copper plate by using a copper sulfate solution to obtain the graphene-based non-enzymatic glucose sensor.
5. The preparation method according to claim 4, wherein the shielding gas in the shielding gas-reducing gas mixed gas is argon and/or helium, and the reducing gas is hydrogen; the volume fraction of the reducing gas in the protective gas-reducing gas mixed gas is 10-30%.
6. The production method according to claim 4, wherein the carbon source precursor gas is acetylene, methane, or ethylene.
7. The production method according to claim 4, wherein the conditions of the chemical vapor deposition include: the background pressure is 80-100 Pa, the flow of the protective gas-reducing gas mixture is 80-100 sccm, the flow of the carbon source precursor gas is 4-10 sccm, the ambient temperature is 950-1050 ℃, and the time is 10-20 min.
8. The method according to claim 4, wherein the two-dimensional layered structure compound is applied in an amount of 0.03 to 0.08mg/cm2。
9. The method according to claim 4, wherein the concentration of the copper sulfate solution is 0.01 to 0.04 mol/L; the electrochemical deposition adopts constant potential deposition; the conditions of potentiostatic deposition include: the voltage is 0.2-0.6V and the time is 2-10 min.
10. Use of the graphene-based non-enzymatic glucose sensor according to any one of claims 1 to 3 or the graphene-based non-enzymatic glucose sensor prepared by the preparation method according to any one of claims 4 to 9 in preparation of a blood glucose detection device.
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