CN113252617B - Glucose sensor with h-BN/Au-Pt net-shaped nano structure with photoelectric co-catalysis characteristic, preparation and application - Google Patents

Glucose sensor with h-BN/Au-Pt net-shaped nano structure with photoelectric co-catalysis characteristic, preparation and application Download PDF

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CN113252617B
CN113252617B CN202110442174.3A CN202110442174A CN113252617B CN 113252617 B CN113252617 B CN 113252617B CN 202110442174 A CN202110442174 A CN 202110442174A CN 113252617 B CN113252617 B CN 113252617B
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崔清强
田悦
陈明
徐林林
焦安欣
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Shandong University
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Abstract

The invention provides a glucose sensor with a photoelectric co-catalysis characteristic h-BN/Au-Pt reticular nano structure, and preparation and application thereof. The preparation method comprises the following steps: mixing the h-BN dispersion, ethanol and K2PtCl4The water solution is fully mixed and uniformly dispersed, and the h-BN/Pt nano composite material is obtained through laser irradiation, centrifugation and drying; dispersing the h-BN/Pt nano composite material in deionized water, and slowly dripping HAuCl4Fully reacting the water solution, and then centrifuging and drying to obtain the h-BN/Au-Pt nano composite material; dispersing the h-BN/Au-Pt nano composite material in a solvent to obtain h-BN/Au-Pt dispersion liquid; and dropping the h-BN/Au-Pt dispersion liquid on a conductive substrate, drying and annealing to obtain the catalyst. The preparation method is simple, green, efficient and low in cost; the prepared h-BN/Au-Pt reticular nano material is small in size, the obtained sensor is low in detection lower limit of glucose, and excellent in sensitivity, selectivity and stability of glucose low-concentration detection.

Description

Glucose sensor with h-BN/Au-Pt net-shaped nano structure with photoelectric co-catalysis characteristic, preparation and application
Technical Field
The invention relates to a glucose sensor with a photoelectric co-catalysis characteristic h-BN/Au-Pt reticular nano structure, and preparation and application thereof, and belongs to the field of preparation and application of novel nano materials.
Background
In 1747, the german chemist maglaff first separated glucose as the most widely distributed monosaccharide in nature, glucose is an indispensable nutrient for metabolism in organisms, and the heat released by the oxidation reaction of the glucose is an important source of energy required by human life activities. Meanwhile, chemical components in human blood are important parameters for evaluating the health degree of human bodies, and the blood sugar level is also an important index for measuring the metabolic capability of human bodies and the clinical diagnosis of diabetes. There is an urgent need for a diabetic to quickly and accurately detect the blood glucose level in the body.
Since the first enzyme electrode emerged in 1962, many researchers have been working on glucose sensors that are rapid, sensitive, low cost, and reusable. Some metal electrodes can still generate electrochemical oxidation on sugar under the condition of no enzyme, and with the continuous emergence of new materials, the development of enzyme-free sensors is close to practical application, and the process is further accelerated in the nanometer age. Song uses SiO2The highly ordered mesoporous platinum material is prepared by the template, and the open three-dimensional pore structure of the mesoporous platinum material is very goodThe electronic transmission speed is improved to a great extent, and the activity hidden by the platinum electrode is excavated out, so that the anti-poisoning capability of the mesoporous platinum is enhanced; the glucose biosensor can be applied to an enzyme-free glucose biosensor, can directly detect glucose and has high sensitivity. However, the preparation process is complex, a chemical reagent HF solution is used in the process, and certain potential safety hazards exist. Chinese patent document CN111505078A discloses an enzyme-free glucose sensor electrode of a Ni/Au composite nanowire array and a preparation method thereof. Conducting treatment on the anodic aluminum oxide template; performing Au deposition in the anodic aluminum oxide conductive template, and then performing Ni deposition; removing the anodic aluminum oxide conductive template deposited with the Au and the Ni to obtain a Ni/Au composite nanowire array; and adhering one end of the Ni/Au composite nanowire array to the modified electrode, and performing potential sweeping until the cyclic voltammogram is stable to obtain the enzyme-free glucose sensor electrode. The non-enzymatic glucose sensor electrode adopts an electrodeposition method to construct noble metal elements and non-noble metal elements with different electronegativities into a double-layer nanowire structure, so that the electrode current is obviously improved; but the lower detection limit is higher, the detection of the low-concentration glucose cannot be effectively realized, and the method disclosed by the invention is long in time consumption and higher in cost. For another example, chinese patent document CN104777203A discloses a preparation method of a Pt-Ni alloy nanotube array electrode and an application thereof in an enzyme-free glucose sensor. Spraying gold on one surface of a porous template, wherein the porous template comprises an AAO template and a PC template which are fixed on the surface of an electrode through conductive silver adhesive, and sealing the periphery of the template by using insulating rubber; and (2) preparing Ni nanowires in a porous template through electrodeposition, removing the template to obtain a Ni nanowire array electrode, and preparing the Pt-Ni alloy nanotube array electrode by adopting a current displacement method, wherein the precursor solution is chloroplatinic acid or potassium chloroplatinate. The linear response range of the prepared non-enzyme sensor to glucose is 1-9Mm, and the detection sensitivity is 57.87 mu AmM-1(ii) a However, the lower limit of detection is high, and the detection of low-concentration glucose cannot be effectively realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a glucose sensor with a photoelectrocatalysis characteristic h-BN/Au-Pt net-shaped nano structure, and preparation and application thereof. The preparation method is simple, green, efficient and low in cost; the prepared h-BN/Au-Pt reticular nano material is small in size, the obtained sensor is low in detection lower limit of glucose, and excellent sensitivity, selectivity and stability are shown for low-concentration detection of glucose.
The technical scheme of the invention is as follows:
a glucose sensor with a photoelectrocatalysis h-BN/Au-Pt net-shaped nano structure is composed of a conductive substrate and an h-BN/Au-Pt net-shaped nano material loaded on the conductive substrate.
Preferably, according to the present invention, the conductive substrate is an FTO substrate.
According to the invention, the h-BN/Au-Pt net-shaped nano material is preferably an Au-Pt alloy nano net-shaped structure loaded on the h-BN nano flaky material.
Preferably, according to the invention, the loading of the h-BN/AuPt reticular nanomaterial on a 1X 1cm conductive substrate is 0.025 mg.
The preparation method of the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectrocatalysis characteristic comprises the following steps:
(1) mixing the h-BN dispersion, ethanol and K2PtCl4The water solution is fully mixed and uniformly dispersed, and the h-BN/Pt nano composite material is obtained through laser irradiation, centrifugation and drying;
(2) dispersing the h-BN/Pt nano composite material in deionized water, and slowly dripping HAuCl4Fully reacting the water solution, and then centrifuging and drying to obtain the h-BN/Au-Pt nano composite material;
(3) dispersing the h-BN/Au-Pt nano composite material in a solvent to obtain h-BN/Au-Pt dispersion liquid; and (3) dropping the h-BN/Au-Pt dispersion liquid on a conductive substrate, drying and annealing to obtain the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectric co-catalysis characteristic.
Preferably, in step (1), the h-BN dispersion is a colloidal solution obtained by sufficiently dispersing the h-BN powder in deionized water; the volume ratio of the mass of the h-BN powder to the deionized water is 0.1-1g/L, and preferably 0.5 g/L.
According to a preferred embodiment of the invention, in step (1), the h-BN dispersion, ethanol and K2PtCl4The volume ratio of the aqueous solution is 7-9: 1-3: 1, preferably 8:2: 1.
Preferably, according to the invention, in step (1), K2PtCl4The concentration of the aqueous solution is 0.01 to 0.03mol/L, preferably 0.015 mol/L.
Preferably, in step (1), the laser irradiation wavelength is 375nm, the pulse width is 10ns, the frequency is 10HZ, and the power is 370 mW; the laser irradiation time is 50 to 90 minutes, preferably 60 minutes.
Preferably according to the invention, the centrifugation speed in step (1) is 4000-; the time is 5 to 15 minutes, preferably 10 minutes.
Preferably, according to the invention, HAuCl is used in step (2)4The concentration of the aqueous solution is 0.1 to 0.5mmol/L, preferably 0.25 mmol/L.
Preferably, according to the invention, in step (2), the mass to volume ratio of the h-BN/Pt nanocomposite to the deionized water is 0.002-0.008g/mL, preferably 0.005 g/mL.
Preferably according to the invention, in step (2), the h-BN/Pt nanocomposite and HAuCl4The mass ratio of (A) to (B) is 20 to 120:1, preferably 35 to 45:1, and more preferably 40: 1.
Preferably, according to the invention, in step (2), HAuCl4The dropping rate of the aqueous solution is 0.01mL/min to 0.03mL/min, preferably 0.02 mL/min.
According to the present invention, preferably, in the step (2), the reaction temperature is 15-25 ℃, preferably 20 ℃; the reaction time is 5 to 15 minutes, preferably 10 minutes.
Preferably according to the invention, in step (2), the centrifugation speed is 3000-5000rpm, preferably 4000 rpm.
According to the present invention, in step (3), the solvent is a mixed solution of deionized water and ethanol, and a volume ratio of the deionized water to the ethanol is 4-6: 1, preferably 5: 1.
preferably, according to the invention, in step (3), the ratio of the mass of the h-BN/Au-Pt nanocomposite to the volume of the solvent is between 0.5 and 1mg/mL, preferably 0.83 mg/mL.
According to the present invention, in the step (3), the drying temperature is 40-60 ℃, preferably 50 ℃; the time is 10 to 30 minutes, preferably 20 minutes.
Preferably, in step (3), the annealing atmosphere is an inert atmosphere, the annealing temperature is 150-250 ℃, and the annealing time is 1-3 hours. Preferably, the annealing atmosphere is argon, the annealing temperature is 200 ℃, and the annealing time is 2 hours.
The glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectrocatalysis characteristic is applied to the detection of glucose.
The invention has the following technical characteristics and beneficial effects:
1. the invention puts two-dimensional h-BN nano-sheet carrier in ethanol and K2PtCl4The load growth of Pt on a two-dimensional h-BN nanosheet carrier is realized through laser irradiation in the aqueous solution, and the Pt nanoclusters grow and are embedded into the 2D h-BN nanosheets. In the nucleation process of Pt, photon energy corresponding to 375nm can be effectively absorbed by the h-BN nano-sheets, so that a large number of electron-hole pairs are generated; ethanol in the solution is used as a hole consuming agent to inhibit the recombination of photo-generated electron-hole pairs; at the same time, photoproduction electrons are used as an effective reducing agent to reduce Pt2+Ions and promote nucleation thereof; thereby effectively realizing the loading of the Pt nanoclusters on the 2D h-BN nanosheets. The invention utilizes the laser-induced photochemical method to effectively load metal on the nano sheet material, and the preparation method is simple, controllable, green, environment-friendly, efficient and low in cost.
2. The invention dissolves h-BN/Pt composite material in deionized water, takes HAuCl4The aqueous solution is slowly dropped into the h-BN/Pt solution. The h-BN/Pt nano composite material can be used as a precursor, the h-BN/Pt nano carrier is further modified by overgrowth of a Pt/Au hybrid structure, and spontaneous electric replacement reaction occurs on the surface of the h-BN loaded and grown Pt particles to form the BN/Pt-Au composite material. Finally, randomly bonding nanoclusters on the h-BN nanosheets; with a P in the center of the clusterAnd t core, finally forming a core-shell structure consisting of the Pt core and the Au-Pt alloy shell.
3. In the h-BN/Au-Pt nano composite material, Pt is used as a core, and Au-Pt alloy is used as a nanocluster of a shell and loaded on an h-BN nano sheet. The h-BN/Au-Pt nano composite material is loaded on a conductive substrate, and the discovery that after annealing, the appearance of the h-BN/Au-Pt nano composite material is obviously changed, Au-Pt nano particles are mutually communicated after annealing, a communicated net-shaped structure is formed on a two-dimensional plane h-BN nano sheet, sharp corners appear at the particle connecting positions, Pt nano cores disappear, and a nano net with an Au-Pt alloy structure is formed on an h-BN carrier.
4. The glucose sensor prepared by the invention is more beneficial to realizing the detection of low-concentration glucose because the h-BN/Au-Pt reticular nano material has larger specific surface area; the glucose sensor can fully exert the synergistic effect of platinum and gold, and Au-Pt has electronic coupling of a mesh-shaped electronic transmission channel embedded in a two-dimensional material, so that low-concentration glucose detection can be better carried out. The glucose sensor prepared by the invention has the detection limit of 0.406nM for glucose molecules, low detection lower limit, excellent sensitivity, selectivity and stability for low-concentration detection of glucose, and important application value in biomedicine.
Drawings
FIG. 1 is a high magnification TEM image of the original h-BN powder in step (1) of example 1;
FIG. 2 is a TEM spectrum of the h-BN/Pt nanocomposite prepared in step (1) of example 1;
FIG. 3 is a high-power TEM image spectrum of the h-BN/Au-Pt nanocomposite prepared in step (2) of example 1;
FIG. 4 is an EDS energy spectrum of the h-BN/Au-Pt nano mesh material in the glucose sensor prepared in the step (3) of example 1;
FIG. 5 is a TEM spectrum of the h-BN/Au-Pt nano mesh material in the glucose sensor prepared in step (3) of example 1;
FIG. 6 is an elemental analysis spectrum of the h-BN/Au-Pt nano network material in the glucose sensor prepared in the step (3) of example 1;
FIG. 7 is a DPV curve of a glucose sensor obtained by the method of example 1 in test example 1 at different glucose concentrations;
FIG. 8 is a graph showing the current response of the glucose sensor obtained in example 1 under different light excitation and dark conditions in test example 2 at different concentrations of glucose;
FIG. 9 is a calibration curve of the glucose sensor of FIG. 8 under dark conditions and under different wavelengths of light;
FIG. 10 is a linear regression equation corresponding to the calibration curve of FIG. 9;
FIG. 11(a) is a graph showing the current response of the glucose sensor obtained in example 1 under the excitation of near infrared light at 808nm in different concentrations in test example 2; (b) is the linear regression equation corresponding to FIG. 11 (a);
FIG. 12 is an i-t curve obtained by irradiating a glucose sensor obtained by the method of example 1 in a blank solution (i.e., a 0.1mol/L phosphate buffer solution containing no glucose) with 808nm near-infrared laser in test example 2.
FIG. 13 is a UV-VISIBLE absorption spectrum of the h-BN/Au-Pt nano mesh material in the glucose sensor obtained in Experimental example 3, the comparative example and example 1.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available.
Pure h-BN nanosheet and HAuCl4Commercially available from Shanghai Aladdin chemical Co., Ltd.
K2PtCl4Glucose and other chemical reagents are available from Mecanne Biotech, Inc., Shanghai.
Example 1
A preparation method of a glucose sensor with a photoelectric co-catalysis characteristic h-BN/Au-Pt reticular nano structure comprises the following steps:
(1) 0.05g of pure h-BN powder is slowly dispersed in 100mL of deionized water under the room temperature environment, and ultrasonic dispersion is carried out for 10 minutes to form a uniformly dispersed colloidal solution. Subsequently, 4mL of the h-BN colloidal solution were taken out, and 1mL of ethanol and 500. mu.L of 0.015mol/L of K2PtCl4And mixing and fully stirring the aqueous solution, and performing ultrasonic dispersion for 10 seconds to obtain a mixed solution. The mixed solution was irradiated with laser having a wavelength of 375nm, a pulse width of 10ns, a frequency of 10Hz, and a laser power of 370mW for 60 minutes. After the irradiation is finished, centrifuging for 10 minutes at 4500rpm, and drying the precipitate to obtain the h-BN/Pt nano composite material.
(2) And (2) dispersing 0.02g of the h-BN/Pt nano composite material obtained in the step (1) in 4mL of deionized water to be used as a carrier for Au growth. Standing the mixed solution for 10 minutes, uniformly dispersing, and taking HAuCl4An aqueous solution (6mL, 0.25mmol/L) was slowly added dropwise to the mixture using a syringe pump at a rate of 0.02 mL/min. Fully reacting for 10 minutes at 20 ℃, centrifuging at 4000rpm, and drying to obtain the h-BN/Au-Pt nano composite material. The element analysis test shows that the Au/Pt molar ratio in the h-BN/Au-Pt nano composite material is 5/9.
(3) And (3) taking 0.05mg of the h-BN/Au-Pt nano composite material prepared in the step (2), dispersing the h-BN/Au-Pt nano composite material into a mixed solution prepared from 50 mu L of deionized water and 10 mu L of ethanol, and ultrasonically oscillating for 10 seconds. 30 μ L of the sample suspension was dropped onto a 1 ﹡ 1cm FTO substrate and dried at 50 deg.C for 20 minutes. And annealing the obtained electrode material on the FTO substrate for 2 hours at the annealing temperature of 200 ℃ in an argon environment to obtain the glucose sensor with the photoelectric co-catalysis characteristic h-BN/Au-Pt reticular nano structure.
The high magnification TEM pattern of the original h-BN powder in step (1) of this example is shown in FIG. 1. As the figure shows, the two-dimensional h-BN support with a large surface area, mostly is an oval sheet of several hundred nanometers.
The TEM spectrum of the h-BN/Pt nanocomposite prepared in step (1) of this example is shown in FIG. 2. Two-dimensional h-BN nano-carrier is placed in K2PtCl4The Pt supported growth is realized by laser irradiation of 375nm in aqueous solution and ethanol for 60 minutes. As shown in fig. 2The nano structure is characterized by TEM, a large number of Pt nanoclusters can be seen to be uniformly decorated on the surface of the h-BN nanosheets, and the structural details of the edges clearly reveal that the Pt nanoclusters are indeed grown and embedded in the 2D h-BN nanosheets. In fact, during nucleation of Pt, photon energy corresponding to 375nm can be efficiently absorbed by h-BN nanosheets, thereby generating a large number of electron-hole pairs. Ethanol in the solution acts as a hole consuming agent, inhibiting the recombination of photo-generated electron-hole pairs. Meanwhile, photoproduction electrons are used as an effective reducing agent to reduce Pt2+Ions and promote nucleation thereof. The h-BN/Pt nano composite material can be used as a precursor, and the h-BN/Pt nano carrier is further modified by growing a Pt/Au hybrid structure.
The high-power TEM image of the h-BN/Au-Pt nanocomposite prepared in step (2) of this example is shown in FIG. 3, from which the morphology and structural features of h-BN/Au-Pt can be seen. The low-magnification TEM image in fig. 3(a) shows that the nanoclusters on the two-dimensional h-BN nanosheets are randomly bonded with an average transverse diameter of about 10 nm. In fig. 3(b), a dark contrast light image is shown, and it is evident that there is a Pt core of about 2-3nm at the center of the cluster, eventually forming a core-shell structure of Pt core and Au — Pt alloy shell.
In the glucose sensor prepared in step (3) of this example, the EDS spectrum of the h-BN/Au-Pt nano mesh material is shown in fig. 4, where the molar content of Pt is 5.5%, the molar content of Au is 3.1%, and the atomic ratio of Pt to Au is 9: 5.
In the glucose sensor prepared in step (3) of this example, a TEM image of the h-BN/Au-Pt nano-network material is shown in FIG. 5. Interestingly, the morphology of the h-BN/Au-Pt nanocomposite changed significantly after 2 hours of annealing at 200 degrees Celsius, as shown in FIG. 5 (a). The Pt/Au nano particles are mutually communicated after being annealed, and a communicated net structure is formed on the two-dimensional plane h-BN nano sheet. As shown in the figure, sharp corners appear at the particle connection positions, the Pt nano cores disappear, and a nano net with an Au-Pt alloy structure is formed on the h-BN carrier.
In the glucose sensor prepared in the step (3) of the embodiment, an intuitive element analysis map of the h-BN/Au-Pt nano mesh material is shown in FIG. 6, and obviously Au and Pt are distributed in the Pt/Au nano mesh quite uniformly, which shows the bimetallic properties of the Au and the Pt.
Example 2
A method for preparing a glucose sensor with a h-BN/Au-Pt reticular nano structure with photoelectric co-catalysis characteristics, as described in example 1, except that the laser irradiation time in the step (1) is 1.5 hours; the other steps and conditions were identical to those of example 1.
Examples 3 to 6
A method for preparing a glucose sensor with a h-BN/Au-Pt reticular nano structure with photoelectric co-catalysis characteristics comprises the following steps of (1), respectively adding 2mL, 4mL, 8mL and 10mL of 0.25mmol/L chloroauric acid aqueous solution in the step (2); the other steps and conditions were identical to those of example 1.
Example 7
A method for preparing a glucose sensor with h-BN/Au-Pt reticular nano-structure with photoelectrocatalysis characteristics, as described in example 1, except that the annealing time in the step (3) is 1 hour; the other steps and conditions were identical to those of example 1.
Comparative example 1
A method for preparing a glucose sensor, as described in example 1, except that the annealing is not performed in step (3), and the specific preparation steps are as follows: and (3) taking 0.05mg of the h-BN/Au-Pt nano composite material prepared in the step (2), dispersing the h-BN/Au-Pt nano composite material into a mixed solution prepared from 50 mu L of deionized water and 10 mu L of ethanol, and ultrasonically oscillating for 10 seconds. Dropping 30 mu L of sample suspension on an FTO substrate of 1 ﹡ 1cm, and drying for 20 minutes at 50 ℃ to obtain a glucose sensor; the other steps and conditions were identical to those of example 1.
Comparative examples 2 to 4
A method for manufacturing a glucose sensor, as described in example 1, except that the annealing temperatures in the step (3) are 100 ℃, 300 ℃ and 400 ℃, respectively; the other steps and conditions were identical to those of example 1.
Test example 1
In consideration of the fact that the glucose sensor with the h-BN/Au-Pt net-shaped nano structure obtained by the method has excellent electro-oxidation activity and photosensitivity, the surface plasma assisted h-BN/Au-Pt nano electrode is researched and used for glucose oxidation.
The glucose sensor obtained by the method of the embodiment 1 of the invention is a working electrode, a saturated calomel electrode and a platinum sheet are respectively used as a reference electrode and a contrast electrode, artificial tears containing glucose with different concentrations are added into 0.1mol/L phosphate buffer solution to be used as electrolyte solution, the final concentrations of the glucose in the electrolyte solution are respectively 0, 0.01, 0.05, 0.1, 0.5 and 1mmol/L, and the differential pulse voltammetry is adopted to detect the relevant response corresponding to the concentration of the glucose.
FIG. 7 is a DPV curve (voltage on the abscissa and current on the ordinate) of a glucose sensor obtained by the method of example 1 at different glucose concentrations; as shown in FIG. 7, the current intensity with the oxidation peak value of 0.31V increases with the increase of the glucose concentration (0-1 mM), which indicates that the glucose sensor obtained by the method of the invention has sensitive detection on the oxidation of glucose at different concentrations, is suitable for glucose sensing, and benefits from the synergistic effect of Au, Pt and h-BN and the effective electronic channel formed by the bimetallic nano-network.
Test example 2
(1) By adopting a standard three-electrode system of an electrochemical workstation, a glucose sensor obtained by the method in the embodiment 1 of the invention is used as a working electrode, a saturated calomel electrode and a platinum sheet are respectively used as a reference electrode and a comparison electrode, 0.1mol/L phosphate buffer solution is used as a basic electrolyte solution, and artificial tears containing glucose are respectively added at intervals of fixed time.
Meanwhile, light with different wavelengths is used for excitation (532, 635, 808, 980nm and Xenon lamp (Xenon lamp)), the bias voltage is adjusted to 0.31V, and the corresponding current response changes along with the change of the glucose concentration as shown in FIG. 8 (the abscissa is time and the ordinate is current).
The concentration in fig. 8 is the concentration of glucose in the system after adding glucose-containing artificial tears to the electrolyte. As can be seen from fig. 8, compared with the dark condition, the current under the photo-excitation is significantly increased because a large number of thermal electrons and thermal holes are generated by the surface of the metal Au under the excitation, glucose is used as a sacrificial agent of the thermal holes, and the thermal holes are effectively consumed while being oxidized, and the thermal electrons are rapidly introduced into an external circuit through an electron transport channel specific to the mesh structure under the action of the bias voltage, so that the current intensity is increased, and thus the effective improvement of the sensitivity of the glucose sensing under the photo-assistance is achieved.
(2) The measurements under the above excitation conditions all show a good linear relationship, as shown in FIG. 9, with the corresponding calibration curve plotted (glucose concentration (mmol/L) on the abscissa and current on the ordinate), whose sensitivity is highly correlated with the LSPR properties of the h-BN/Au-Pt nano-network structure, and the generalized structure is shown in FIG. 10. Comparing corresponding R2It was found that h-BN/Au-Pt sensors excited by light in the near infrared (808nm and 980nm) range are more favorable for improving the accuracy of glucose sensors. In the range of 0.1-1 mmol/L, the sensitivities of 808nm excitation and 980nm excitation are 113.15 and 81.03 mu AmM respectively-1The sensitivity is respectively 26.93 and 24.92 mu AmM in the range of 1-17 mmol/L-1。
(3) By adopting a standard three-electrode system of an electrochemical workstation, a glucose sensor obtained by the method in the embodiment 1 of the invention is used as a working electrode, a saturated calomel electrode and a platinum sheet are respectively used as a reference electrode and a comparison electrode, 0.1mol/L phosphate buffer solution is used as a basic electrolyte solution, and artificial tears containing glucose are respectively added at intervals of fixed time. Meanwhile, 808nm near infrared light is used for excitation, the bias voltage is adjusted to 0.31V, and the corresponding current response is shown in FIG. 11.
The concentration in fig. 11(a) is the concentration of glucose in the system after adding artificial tears containing glucose to the electrolyte. FIG. 11(a) shows the current response (time on the abscissa and current on the ordinate) in the range of 0.03 to 100. mu.M of glucose concentration in the electrolyte. Then, a linear relationship of the response current with the change in glucose was plotted as in FIG. 11 (b). Under the condition of lower glucose level (0.03-2.99 mu M), the linear regression equation under the irradiation of 808nm is that I (mu A) is 2.41+ lgC (mu M), R20.9043, in the range of 2.99 to 100 μ M,its linear regression equation is I (μ a) ═ 1.23+9.09lg (μ M), R20.9862. Therefore, the detection sensitivity of glucose is 1.44. mu.A (lg. mu.M) at 0.03 to 2.99. mu.M in a low concentration range-19.09. mu.A (lg. mu.M) at 2.99 to 100. mu.M-1.
(4) In addition, according to the formula LOD of 3 σ/s, where σ is the standard deviation of blank signals (the number of acquisitions n is 5, as shown in fig. 12), and s is the sensitivity of the sensor, the detection limit of the sensor under the excitation of 808nM near infrared light is calculated to be 4.06nM, which indicates that the sensor has high sensitivity to glucose, has the capability of detecting trace glucose, and can be used for actual biological detection.
Test example 3
The h-BN/Au-Pt nano mesh material in the glucose sensors prepared in example 1 and the comparative example were subjected to an ultraviolet-visible light absorption test, and the test results are shown in FIG. 13.
As can be seen from the figure, the absorption of the h-BN/Au-Pt nano composite material to light is changed after annealing, so that the absorption range is expanded to a near infrared band, and the light response of near infrared light excitation is realized. Due to the wider visible and near-infrared strong absorption characteristics (400-1000nm), effective excitation can be realized by adopting lasers with the wavelengths of 532, 635, 808 and 980nm, and the corresponding current is remarkably improved. Compared with the annealing at 200 ℃ in the embodiment 1 of the invention, the materials at other annealing temperatures have visible light absorption bands, which is not beneficial to the near infrared light excitation to improve the sensitivity of the sensor.

Claims (10)

1. A glucose sensor with a photoelectrocatalysis h-BN/Au-Pt net-shaped nano structure is characterized in that the glucose sensor consists of a conductive substrate and an h-BN/Au-Pt net-shaped nano material loaded on the conductive substrate; the h-BN/Au-Pt net-shaped nano material is an Au-Pt material with a net-shaped structure loaded on a two-dimensional plane h-BN nano sheet;
the preparation method of the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectrocatalysis characteristic comprises the following steps:
(1) mixing the h-BN dispersion, ethanol and K2PtCl4The water solution is fully mixed and dispersed evenly, and the h-BN/Pt nano composite material is obtained through laser irradiation, centrifugation and drying;
the h-BN dispersion liquid is a colloidal solution formed by fully dispersing h-BN powder into deionized water; the volume ratio of the mass of the h-BN powder to the deionized water is 0.1-1 g/L; h-BN dispersion, ethanol and K2PtCl4The volume ratio of the aqueous solution is 7-9: 1-3: 1; k2PtCl4The concentration of the aqueous solution is 0.01-0.03 mol/L; the laser irradiation wavelength is 375nm, the pulse width is 10ns, the frequency is 10HZ, and the power is 370 mW; the laser irradiation time is 50-90 minutes;
(2) dispersing the h-BN/Pt nano composite material in deionized water, and slowly dripping HAuCl4Fully reacting the water solution, and then centrifuging and drying to obtain the h-BN/Au-Pt nano composite material;
HAuCl4the concentration of the aqueous solution is 0.1-0.5 mmol/L; the mass ratio of the h-BN/Pt nano composite material to the deionized water is 0.002-0.008 g/mL; h-BN/Pt nanocomposite and HAuCl4The mass ratio of (A) to (B) is 20-120: 1; the reaction temperature is 15-25 ℃; the reaction time is 5-15 minutes;
(3) dispersing the h-BN/Au-Pt nano composite material in a solvent to obtain h-BN/Au-Pt dispersion liquid; dropping the h-BN/Au-Pt dispersion liquid on a conductive substrate, drying and annealing to obtain the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectric co-catalysis characteristic;
the solvent is a mixed solution of deionized water and ethanol, and the volume ratio of the deionized water to the ethanol is (4-6): 1; the mass of the h-BN/Au-Pt nano composite material is 0.5-1mg/mL to the volume of the solvent; the drying temperature is 40-60 ℃ and the drying time is 10-30 minutes; the annealing atmosphere is inert atmosphere, the annealing temperature is 150-250 ℃, and the annealing time is 1-3 hours.
2. The glucose sensor with the h-BN/Au-Pt reticular nanostructure with the photoelectrocatalytic property as in claim 1, is characterized by comprising one or more of the following conditions:
i. the conductive substrate is an FTO substrate;
ii. The h-BN/Au-Pt net-shaped nano material is formed by loading an Au-Pt alloy nano net-shaped structure on an h-BN nano flaky material;
iii, the loading amount of the h-BN/AuPt net-shaped nanometer material on a 1 x 1cm conductive substrate is 0.025 mg.
3. The method for preparing the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectrocatalysis characteristic as in any one of the claims 1-2, comprising the steps of:
(1) mixing the h-BN dispersion, ethanol and K2PtCl4The water solution is fully mixed and uniformly dispersed, and the h-BN/Pt nano composite material is obtained through laser irradiation, centrifugation and drying;
the h-BN dispersion liquid is a colloidal solution formed by fully dispersing h-BN powder into deionized water; the volume ratio of the mass of the h-BN powder to the deionized water is 0.1-1 g/L; h-BN dispersion, ethanol and K2PtCl4The volume ratio of the aqueous solution is 7-9: 1-3: 1; k2PtCl4The concentration of the aqueous solution is 0.01-0.03 mol/L; the laser irradiation wavelength is 375nm, the pulse width is 10ns, the frequency is 10HZ, and the power is 370 mW; the laser irradiation time is 50-90 minutes;
(2) dispersing the h-BN/Pt nano composite material in deionized water, and slowly dripping HAuCl4Fully reacting the water solution, and then centrifuging and drying to obtain the h-BN/Au-Pt nano composite material;
HAuCl4the concentration of the aqueous solution is 0.1-0.5 mmol/L; the mass ratio of the h-BN/Pt nano composite material to the deionized water is 0.002-0.008 g/mL; h-BN/Pt nanocomposite and HAuCl4The mass ratio of (A) to (B) is 20-120: 1; the reaction temperature is 15-25 ℃; the reaction time is 5-15 minutes;
(3) dispersing the h-BN/Au-Pt nano composite material in a solvent to obtain h-BN/Au-Pt dispersion liquid; dropping the h-BN/Au-Pt dispersion liquid on a conductive substrate, drying and annealing to obtain the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectric co-catalysis characteristic;
the solvent is a mixed solution of deionized water and ethanol, and the volume ratio of the deionized water to the ethanol is 4-6: 1; the mass of the h-BN/Au-Pt nano composite material is 0.5-1mg/mL to the volume of the solvent; the drying temperature is 40-60 ℃, and the drying time is 10-30 minutes; the annealing atmosphere is inert atmosphere, the annealing temperature is 150-250 ℃, and the annealing time is 1-3 hours.
4. The method for preparing the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectrocatalysis characteristic in claim 3, wherein in the step (1), one or more of the following conditions are included:
i. the volume ratio of the mass of the h-BN powder to the deionized water is 0.5 g/L;
ii. h-BN dispersion, ethanol and K2PtCl4The volume ratio of the aqueous solution is 8:2: 1;
iii、K2PtCl4the concentration of the aqueous solution is 0.015 mol/L;
iv, the centrifugal rotating speed is 4000-; the time is 5-15 minutes.
5. The method for preparing the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectrocatalysis characteristic in claim 3, wherein in the step (1), the laser irradiation time is 60 minutes.
6. The method for preparing the glucose sensor with the h-BN/Au-Pt reticular nano-structure with the photoelectrocatalysis characteristic in claim 3, wherein in the step (2), one or more of the following conditions are included:
i. HAuCl in step (2)4The concentration of the aqueous solution is 0.25 mmol/L;
ii. The mass ratio of the h-BN/Pt nano composite material to the deionized water is 0.005 g/mL;
iii, h-BN/Pt nanocomposite and HAuCl4The mass ratio of (A) to (B) is 35-45: 1.
7. The method for preparing the glucose sensor with the h-BN/Au-Pt reticular nano-structure with the photoelectrocatalysis characteristic in claim 3, wherein in the step (2), one or more of the following conditions are included:
i、HAuCl4the dropping speed of the aqueous solution is 0.01mL/min to 0.03 mL/min;
ii. The reaction temperature is 20 ℃; the reaction time was 10 minutes;
iii, the centrifugal speed is 3000-.
8. The method for preparing the glucose sensor with the h-BN/Au-Pt reticular nano-structure with the photoelectrocatalysis characteristic in claim 3, wherein in the step (3), one or more of the following conditions are included:
i. the volume ratio of the deionized water to the ethanol is 5: 1;
ii. The mass of the h-BN/Au-Pt nano composite material is 0.83mg/mL to the volume of the solvent;
iii, the drying temperature is 50 ℃; the time period required was 20 minutes.
9. The method for preparing the glucose sensor with the h-BN/Au-Pt reticular nano structure with the photoelectrocatalysis characteristic in claim 3, wherein in the step (3), the annealing atmosphere is argon, the annealing temperature is 200 ℃, and the annealing time is 2 hours.
10. The use of the glucose sensor with h-BN/Au-Pt reticular nano-structure with photoelectrocatalysis characteristics as in any one of claims 1-2, in the detection of glucose.
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