CN115201298B - Hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping - Google Patents
Hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping Download PDFInfo
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Abstract
A hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping. The application belongs to the technical field of electrochemical sensors, and particularly relates to a working electrode of an electrochemical sensor based on boron/nitrogen co-doped hollow porous carbon spheres/graphene. The application aims to solve the problems of poor cycling stability, narrow linear range and high detection limit of the enzyme-free sensor for detecting xanthine and guanine at present. The product is as follows: the composite material consists of a GCE electrode and a hollow porous carbon sphere/graphene composite material based on boron/nitrogen co-doping, wherein the hollow porous carbon sphere/graphene composite material is wrapped outside the GCE electrode; the electrochemical sensor constructed with the working electrode can detect xanthine and guanine simultaneously or individually, and exhibits superior detection performance. The linear detection ranges of xanthine and guanine were 9.15X10, respectively ‑8 M~1.03×10 ‑4 M、8.22×10 ‑8 M~1.28×10 ‑4 M, detection limits are 5.03X10 respectively ‑8 M and 4.62X10 ‑8 M。
Description
Technical Field
The application belongs to the technical field of electrochemical sensors, and particularly relates to a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping.
Background
Xanthine and guanine are important basic building blocks of DNA and play a vital role in the metabolic mechanisms of the cardiovascular system, cofactors, neurotransmitter release, etc. Xanthine and guanine are generally produced by enzyme failure in biological tissue degradation in biological fluids, but from current reports, abnormal changes in purine are often associated with diseases such as cancer, lupus erythematosus, cystic fibrosis, epilepsy, liver disease, and the like. Therefore, it is necessary to construct a highly sensitive purine detection method. To date, various techniques have been employed for quantitative purine detection, including high performance liquid chromatography, capillary electrophoresis, gas chromatography, fluorescence, and the like. Electrochemical sensors/biosensors are inherently advantageous compared to the above-described testing techniques: low cost, high sensitivity, simplicity, portability and feasibility are receiving increasing attention. Nevertheless, there is still a challenge to find a novel electrode material that can improve the reliability, efficiency, simplicity and selectivity of electrochemical sensors while detecting xanthines and guanines.
The porous carbon material refers to carbon materials with different pore structures, and the pore diameter of the porous carbon material can be regulated and controlled according to the requirements of practical application (such as the size of adsorbed molecules and the like) so that the size of the porous carbon material is between nanometer micropores and micrometer macropores. The porous carbon material not only has the advantages of high chemical stability, good conductivity, low cost, environmental friendliness and the like of the carbon material, but also has the characteristics of high specific surface area, rich pore channel structure, adjustable pore diameter and the like due to the introduction of a porous structure, and the open three-dimensional gap can facilitate permeation of biomolecules and provide a convenient channel for transfer of electrons/protons. The porous carbon material has the characteristics of good thermal stability, high mechanical stability, excellent conductivity, developed pore structure, large specific surface area and the like, so that the porous carbon material has great application potential in the fields of adsorption, separation, catalysis, gas storage, energy storage, conversion and the like. Particularly in the field of energy storage and conversion, the porous carbon material can play an important role as an active substance, a conductive agent, a coating layer, a flexible substrate, a carrier and the like. As a novel carbon material, porous carbon nanospheres with hollow structures have been attracting attention because of their excellent mechanical strength, controllable internal pore volume, high specific surface area and other functional properties and unique structures. These good characteristics make it exhibit a certain application potential in various fields of gas sensors, catalysis, energy storage and the like. Particularly, the porous carbon sphere has great advantages in ion/electron transmission and biomolecule adsorption/desorption due to the unique three-dimensional structure as a sensor electrode material.
The hetero atoms are doped in the carbon material, so that the performance of the carbon material can be greatly changed, such as changing the surface structure, improving the electron transmission rate, modulating the pore channel structure, enhancing the hydrophilicity, increasing the specific surface area and the like, thereby expanding the application range of the carbon material in various fields. Wherein the non-metallic heteroatom doping can both optimize the conductivity of the carbon material and contribute additional electrocatalytic capacity during redox. The conductivity and the surface polarity of the carbon frame can be obviously improved by doping nitrogen, and the boron can generate additional active sites for grafting to the carbon surface, so that the carbon electrode has higher wettability and durability. Reduced graphene oxide contains residual oxygen and other heteroatoms, as well as good conductivity and structural defects. The reduced graphene oxide is used as a substrate to load the porous carbon spheres, so that the larger ductility and the specific surface area of the porous carbon spheres not only can improve the dispersibility of the carbon spheres and make up the defect of self-agglomeration, but also can keep stronger sensing characteristics.
Disclosure of Invention
The application aims to solve the problems of poor cycling stability, narrow linear range and high detection limit of the existing enzyme-free sensor for detecting xanthine and guanine, and provides a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping.
The application discloses a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping, which is characterized by comprising a GCE electrode and boron/nitrogen co-doping hollow porous carbon sphere/graphene wrapped outside the GCE electrode and used for simultaneously and respectively detecting xanthine and guanine.
In the hollow porous carbon sphere/graphene based on boron/nitrogen co-doping, the hollow porous carbon nanospheres coated with silicon dioxide and carbonized are subjected to acid etching to form a hollow porous structure with pores, wherein the average particle size is 174nm, and the average pore size is 6nm.
The boron/nitrogen co-doped hollow porous carbon nanosphere precursor is heated in a tube furnace at 700 ℃ for reaction for 3 hours.
The carbonized boron/nitrogen co-doped hollow porous carbon nanosphere precursor is immersed in 7% -10% hydrofluoric acid solution and stirred for 24-h.
The mass ratio of the boron/nitrogen co-doped hollow porous carbon nanospheres to the graphite oxide is 1:4-6.
The hollow porous carbon sphere/graphene co-doped with boron/nitrogen is added with 25 mL-35 mL deionized water, and then is subjected to ultrasonic treatment for 30min, and stirred for 1h.
The hollow porous carbon sphere/graphene co-doped with boron/nitrogen is subjected to hydrothermal reaction at 160 ℃ in a reaction kettle to obtain 3h.
And 4-6 mu L of the boron/nitrogen co-doped hollow porous carbon sphere/graphene is dripped on the GCE electrode by a dripping method, and the hollow porous carbon sphere/graphene is obtained by natural airing.
The application has the beneficial effects that:
compared with the traditional xanthine and guanine sensor, the hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping is constructed. The problems of poor circulation stability, narrow linear range, high detection limit and the like existing in xanthine and guanine detection in practical application are solved. The linear ranges of the xanthine and guanine electrochemical sensors prepared based on the working electrode of the electrochemical sensor based on the hollow porous carbon sphere/graphene co-doped with boron/nitrogen are 9.15 multiplied by 10 respectively -8 M ~1.03×10 -4 M、8.22×10 -8 M ~1.28×10 -4 M (M: mol/mL) with detection limits of 5.03X10 respectively -8 M and 4.62X10 -8 M has wider linear range, lower detection limit and more sensitivity to detection of xanthine and guanine. This is mainly due to the synergistic effect of boron and nitrogen hetero atoms, porous carbon nanospheres and reduced graphene oxide, namely, the transmission rate of electrons on the electrode surface is promoted, the active adsorption sites of biological micromolecules on the electrode surface are enlarged, and the electrode is prepared by the methodAnd the electrocatalytic xanthine and guanine activities are greatly improved.
Drawings
FIG. 1 is a partial enlarged view of a scanning electron microscope of a solid carbon sphere obtained by test I and subjected to carbonization treatment only without acid etching boron/nitrogen co-doping;
FIG. 2 is a scanning electron microscope image of a boron/nitrogen co-doped hollow porous carbon sphere obtained by test one;
FIG. 3 is a transmission electron microscope image of a boron/nitrogen co-doped hollow porous carbon sphere obtained by test one;
FIG. 4 is an enlarged view of a partial transmission electron microscope of the boron/nitrogen co-doped hollow porous carbon sphere obtained in test one;
FIG. 5 is a scanning electron microscope image of the boron/nitrogen co-doped hollow porous carbon spheres/graphene obtained in test one;
FIG. 6 is an X-ray powder diffraction pattern of the boron/nitrogen co-doped hollow porous carbon sphere precursor, solid carbon spheres that were only carbonized without acid etching boron/nitrogen co-doping, and boron/nitrogen co-doped hollow porous carbon spheres obtained in validation test one;
FIG. 7 is an infrared spectrum of a boron/nitrogen co-doped hollow porous carbon sphere precursor, a solid carbon sphere treated only by carbonization without acid etching boron/nitrogen co-doping, and a boron/nitrogen co-doped hollow porous carbon sphere obtained in validation test one;
FIG. 8 is a differential pulse voltammogram of the boron/nitrogen co-doped hollow porous carbon spheres/graphene obtained in the first validation test for simultaneous detection of xanthine and guanine; the concentration range from bottom to top is 10-50 mu M;
FIG. 9 is a graph of differential pulse voltammetry of a boron/nitrogen co-doped hollow porous carbon sphere/graphene to detect xanthine in a concentration range of 10-60. Mu.M when 50. Mu.M guanine is pre-existing for a proof test of electrochemical sensor performance;
FIG. 10 is a graph of differential pulse voltammetry of a boron/nitrogen co-doped hollow porous carbon sphere/graphene to detect guanine in a concentration range of 10 to 60. Mu.M when 50. Mu.M xanthine is pre-existing for a proof test of electrochemical sensor performance;
FIG. 11 is a calibration curve of response current versus concentration for a validation test of the performance of an electrochemical sensor that catalyzes xanthines and guanines at a concentration range of 10-50. Mu.M;
FIG. 12 is a differential pulse voltammogram of continuous simultaneous detection of xanthine and guanine for boron/nitrogen co-doped hollow porous carbon spheres/graphene for validation testing of an electrochemical sensor performance;
FIG. 13 is a graph of calibration of response current vs. xanthine concentration for a proof test of electrochemical sensor performance;
FIG. 14 is a graph of calibration of response current vs. guanine concentration for a proof test of electrochemical sensor performance.
Detailed Description
The first embodiment is as follows: the hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping is characterized by comprising a GCE electrode and boron/nitrogen co-doped hollow porous carbon sphere/graphene wrapped outside the GCE electrode.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the hollow porous carbon sphere co-doped with boron/nitrogen is formed by a hollow porous structure with pores, which is coated by silicon dioxide and is only carbonized but not etched by acid, wherein the hollow porous structure with pores is formed by etching the solid carbon nanospheres co-doped with boron/nitrogen, and the average particle size is 174 and nm, and the average pore size is 6 and nm. Other steps and parameters are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the boron/nitrogen co-doped hollow porous carbon sphere precursor is heated in a tube furnace at 700 ℃ for reaction 3h. Other steps and parameters are the same as in the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the carbonized boron/nitrogen co-doped solid carbon nanosphere precursor is immersed in 7% -10% hydrofluoric acid solution and stirred for 24-h. Other steps and parameters are the same as in one to three embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the mass ratio of the boron/nitrogen co-doped hollow porous carbon nanospheres to the graphite oxide is 1:4-6. Other steps and parameters are the same as in one to four embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the boron/nitrogen co-doped hollow porous carbon sphere/graphene is added with 25-35 mL of deionized water, and then is subjected to ultrasonic treatment for 30min and stirred for 1h. Other steps and parameters are the same as in one to five embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the hollow porous carbon sphere/graphene co-doped with boron/nitrogen is subjected to hydrothermal reaction for 3 hours at 160 ℃ in a reaction kettle. Other steps and parameters are the same as in one of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and 4-6 mu L of the boron/nitrogen co-doped hollow porous carbon sphere/graphene is dripped on the GCE electrode by a dripping method, and the hollow porous carbon sphere/graphene is obtained by natural airing. Other steps and parameters are the same as in one of the first to seventh embodiments.
Detailed description nine: the preparation method of the hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping in the embodiment comprises the following steps:
1. preparation of hollow porous carbon spheres based on boron/nitrogen co-doping:adding 2.4 g-3.0 g of cetyltrimethylammonium bromide solution into 95 mL-105 mL of deionized water, dropwise adding 0.1 mL-1 mL of ammonia water under intense stirring, and marking as solution A; />0.2 g-0.8 g of resorcinol and 0.05 g-0.15 g of boric acid are dissolved in the solution A and stirred for 1h, designated as solution B. />7.0-8.0 mL of tetraethyl orthosilicate and 2.3-3.3 mL of formaldehyde are added into the solution B, stirred for 24 hours at normal temperature, and then centrifuged, washed and dried to collect gray solid products. />And (3) placing the gray solid product into a tube furnace for heating, reacting for 2-4 hours at 700 ℃ at a heating rate of 4-6 ℃/min under the protection of nitrogen, and collecting the black product after cooling to normal temperature. />Immersing the black product into 7% -10% hydrofluoric acid solution, stirring for 24 hours at normal temperature, centrifuging, washing, and drying to obtain the boron/nitrogen co-doped hollow porous carbon spheres.
Step oneThe amount of ammonia water in the solution A is 0.1 mL-1 mL;
step oneThe amount of the tetraethyl orthosilicate is 7.0 mL-8.0 mL;
step oneThe formaldehyde amount is 2.3 mL-3.3 mL;
step oneWherein the heating rate is 4-6 ℃/min;
step oneThe concentration of the hydrofluoric acid solution is 7-10%.
2. Preparation of hollow porous carbon spheres and reduced graphene oxide based on boron/nitrogen co-doping: weighing the final product boron/nitrogen co-doped hollow porous carbon spheres and graphene solid according to the mass ratio of 1:4-6, putting the mixture into a three-necked round bottom flask, adding 25-35 mL of deionized water, performing ultrasonic treatment for 30min, and stirring for 1h at normal temperature. Then, the mixed solution was transferred to a 50mL stainless steel autoclave, and subjected to hydrothermal reaction at 160℃for 3 hours to obtain a black suspension. And then, centrifuging, washing and vacuum drying the mixture to obtain a black product, namely the boron/nitrogen co-doped hollow porous carbon spheres and the reduced graphene oxide.
In the second step, the mass ratio of the boron/nitrogen co-doped hollow porous carbon spheres to the graphene solid is 1:4-6;
the amount of deionized water in the second step is 25-35 mL;
3. preparation of a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping: weighing 4-6 mg of black product, grinding the black product into powder, dispersing the powder into 900-980 mu L of deionized water/20-100 mu L of naphthol (0.2-1 wt%) mixed solvent, carrying out ultrasonic treatment for 27-33 min, accurately removing 4-6 mu L of suspension liquid, dripping the suspension liquid on the surface of a GCE electrode with a smooth mirror surface, and naturally airing the GCE electrode at normal temperature for later use.
In the third step, the mass of the black product is 4 mg-6 mg;
in the third step, the mass percentage of the deionized water/naphthol mixed solvent is 0.2-1 wt%;
the suspension in the third step is 4-6 mu L;
the xanthine and guanine electrochemical sensors prepared in this embodiment can be used to detect xanthine and guanine simultaneously and separately. The linear ranges are 9.15×10 respectively -8 M ~1.03×10 -4 M、8.22×10 -8 M ~1.28×10 -4 M, detection limits are 5.03X10 respectively -8 M and 4.62X10 -8 M has wider linear range, lower detection limit and more sensitivity to detection of xanthine and guanine. The working electrode prepared by the method has the advantages of simple preparation, quick response and the like, and detects xanthine and guanineIs more sensitive. The method is mainly due to the synergistic effect of boron and nitrogen heteroatoms, the porous carbon nanospheres and the reduced graphene oxide, namely, the transmission rate of electrons on the surface of the electrode is promoted, and the active adsorption sites of biological micromolecules on the surface of the electrode are enlarged, so that the electrocatalytic xanthine and guanine activities of the biological micromolecules are greatly improved.
Detailed description ten: this embodiment differs from the ninth embodiment in that: step oneThe amount of ammonia water in the solution A is 0.1 mL-1 mL. Other steps and parameters are the same as in the ninth embodiment.
Eleventh embodiment: this embodiment differs from the ninth or tenth embodiment in that: step oneThe amount of tetraethyl orthosilicate is 7.0 mL-8.0 mL. Other steps and parameters are the same as those of the ninth or tenth embodiment.
Twelve specific embodiments: this embodiment differs from one of the embodiments nine to eleven in that: step oneThe formaldehyde content is 2.3 mL-3.3 mL. Other steps and parameters are the same as in one of the ninth to eleventh embodiments.
Thirteen specific embodiments: this embodiment differs from one of the ninth to twelfth embodiments in that: step oneThe heating rate is 4 ℃/min to 6 ℃/min. Other steps and parameters are the same as in one of the ninth to twelfth embodiments.
Fourteen specific embodiments: this embodiment differs from one of the ninth to thirteenth embodiments in that: step oneThe concentration of the hydrofluoric acid solution is 7-10%. Other steps and parameters are the same as those of one of the ninth to thirteenth embodiments.
Fifteen embodiments: this embodiment differs from one of the embodiments nine to fourteen in that: and in the second step, the mass ratio of the boron/nitrogen co-doped hollow porous carbon spheres to the graphene solid is 1:4-6. Other steps and parameters are the same as in one of the ninth to fourteenth embodiments.
Sixteen specific embodiments: this embodiment differs from one of the ninth to fifteenth embodiments in that: and in the second step, the amount of deionized water is 25-35 mL. Other steps and parameters are the same as those of one of the ninth to fifteenth embodiments.
Seventeenth embodiment: this embodiment differs from one of the ninth to sixteenth embodiments in that: and in the third step, the mass of the black product is 4 mg-6 mg. Other steps and parameters are the same as those of one of the ninth to sixteenth embodiments.
The concrete implementation mode is eighteen: this embodiment differs from one of the ninth to seventeenth embodiments in that: and in the third step, the mass percentage of the deionized water/naphthol mixed solvent is 0.2-1 wt%. Other steps and parameters are the same as those of one of the ninth to seventeenth embodiments.
Detailed description nineteenth embodiment: this embodiment differs from one of the embodiments nine to eighteenth in that: the amount of the suspension in the third step is 4-6. Mu.L. Other steps and parameters are the same as those of one of the embodiments nine to eighteen.
The effect of the present application was verified by the following experiment
Experiment one, the preparation method of the hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping of the experiment is carried out according to the following steps:
1. preparation of hollow porous carbon spheres based on boron/nitrogen co-doping:2.8g of cetyltrimethylammonium bromide solution was added to 100mL of deionized waterDropwise adding 0.5mL of ammonia water under vigorous stirring, and marking as a solution A; />0.5 g resorcinol and 0.1 g boric acid were dissolved in solution a and stirring was continued for 1h, designated solution B. />Tetraethyl orthosilicate 7.2 mL and formaldehyde 2.8 mL are added into the solution B, stirred for 24 hours at normal temperature, and then centrifuged, washed and dried to collect the gray solid product. />The gray solid product is placed in a tube furnace to be heated, reacted for 3 hours at 700 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and the black product is collected after the temperature is reduced to normal temperature. />And immersing the black product into 8% hydrofluoric acid solution, stirring for 24 hours at normal temperature, centrifuging, washing and drying to obtain the boron/nitrogen co-doped hollow porous carbon spheres.
Step oneThe amount of ammonia water in the solution A is 0.5mL;
step oneThe amount of tetraethyl orthosilicate is 7.2 mL;
step oneWherein the formaldehyde is in an amount of 2.8 mL;
step oneWherein the heating rate is 5 ℃/min;
step oneThe concentration of the hydrofluoric acid solution is 8%.
2. Preparation of hollow porous carbon spheres/graphene based on boron/nitrogen co-doping: the final product boron/nitrogen co-doped hollow porous carbon spheres and graphite oxide are mixed according to the mass ratio of 1:5 weighing and placing the mixture into a three-neck round-bottom flask, adding 30 mL deionized water, performing ultrasonic treatment for 30min, and stirring at normal temperature for 1h. Afterwards, the mixed solution was transferred to a 50mL stainless steel autoclave for hydrothermal reaction at 160 ℃ for 3h to obtain a black suspension. And then, centrifuging, washing and vacuum drying the mixture to obtain a black product, namely the boron/nitrogen co-doped hollow porous carbon spheres and the reduced graphene oxide.
In the second step, the mass ratio of the boron/nitrogen co-doped hollow porous carbon spheres to the graphene solid is 1:5, a step of;
the amount of deionized water in the second step is 30 mL;
3. preparation of a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping: weighing 5. 5 mg black products, grinding the black products into powder, dispersing the powder into 950 mu L of deionized water/50 mu L of naphthol (0.5. 0.5 wt%) mixed solvent, carrying out ultrasonic treatment for 30min, accurately removing 5 mu L of suspension liquid, dripping the suspension liquid on the surface of a GCE electrode with a smooth mirror surface, and naturally airing the GCE electrode at normal temperature for later use.
The black product in the third step has a mass of 5 mg;
in the third step, the mass percentage of the deionized water/naphthol mixed solvent is 0.5 percent wt percent;
the amount of the suspension in the third step was 5. Mu.L.
Characterization of the morphology of hollow porous carbon spheres/graphene based on boron/Nitrogen co-doping on the GCE electrode obtained in test
A scanning electron microscope image of the boron/nitrogen co-doped solid carbon spheres that were only carbonized without acid etching, as obtained in experiment one shown in fig. 1, was obtained, and it was seen that the surfaces of the nanospheres were loaded with numerous silica particles. As shown in figure 2, the scanning electron microscope image of the obtained boron/nitrogen co-doped hollow porous carbon sphere can show a novel hollow porous structure with pores, and well maintains the original spherical morphology, and the interconnected pore structures provide effective paths for biomolecule and ion transfer. A transmission electron micrograph of the resulting boron/nitrogen co-doped hollow porous carbon spheres as shown in fig. 3 demonstrates the presence of a large number of porous pores on the carbon nanospheres that provide numerous active sites to accommodate a large number of biomolecules for reaction. As shown in FIG. 4, a partial magnified scanning electron microscope image of the boron/nitrogen co-doped hollow porous carbon sphere obtained after the test shows that the light areas represent pores of different shapes and sizes, and the dark areas represent the outer edge shells and the center. Test one obtained boron/nitrogen co-doped hollow porous carbon sphere/graphene as shown in fig. 5
Scanning electron microscope images; from the figure, the porous carbon nanospheres are uniformly dispersed on the surface of graphene, so that the agglomeration effect of the carbon nanospheres is effectively solved, and the corresponding dispersibility and conductivity are improved.
From fig. 5, it can be seen that the carbon nanospheres are uniformly dispersed on the surface of graphene, and a three-dimensional hierarchical porous structure is formed as a conductive scaffold. The unique structure and the form can maintain stable electrochemical contact, and enhance the transmission of the electrode/charge between interfaces, thereby improving the electrocatalytic and sensing capabilities of the material;
secondly, analyzing the phase purity and the crystal structure of the boron/nitrogen co-doped hollow porous carbon sphere precursor obtained in the first test, the boron/nitrogen co-doped solid carbon sphere which is only carbonized and not subjected to acid etching and the boron/nitrogen co-doped hollow porous carbon sphere by utilizing X-ray powder diffraction (XRD), so as to obtain an X-ray powder diffraction pattern of three substances shown in figure 6; the boron/nitrogen co-doped hollow porous carbon sphere precursor has a distinct silica diffraction peak with a peak position substantially consistent with standard silica card (PDF # 50-1432), which can indicate that elemental silicon in tetraethyl orthosilicate has been converted to crystalline silica and encapsulated in solid nanospheres. The boron/nitrogen co-doped solid carbon spheres which are only carbonized but not acid etched have slight red shift of wide characteristic peaks and no new peaks, and the characteristic peaks are consistent with silicon dioxide (PDF # 50-1432), so that the carbonization treatment can be proved to not cause structural damage of the solid nanospheres and falling of silicon elements. The X-ray powder diffraction pattern of the hollow porous carbon spheres co-doped with boron/nitrogen shows two broad diffraction bands representing the (002) and (100) crystal planes of the carbon material, respectively, wherein the peak located at 24 ° is a typical characteristic peak of amorphous carbon, and the peak near 43 ° represents a partially ordered carbon matrix. And no characteristic peak of silica was observed, indicating that the acid etched silicon element has been completely removed from the solid carbon nanospheres. From the results of the X-ray powder diffraction, it can be concluded that hollow porous carbon spheres were successfully prepared.
(III) utilizing infrared spectroscopy (FI-IR) to characterize the formation and structure of the boron/nitrogen co-doped hollow porous carbon sphere precursor obtained in the test I, the boron/nitrogen co-doped solid carbon sphere which is only carbonized and not subjected to acid etching and the boron/nitrogen co-doped hollow porous carbon sphere, and obtaining an infrared spectrogram of three substances shown in figure 7; in the infrared spectrum of the boron/nitrogen co-doped hollow porous carbon sphere precursor,v as (C-H 2 ) The asymmetric telescopic absorption characteristic peak of (2) is positioned at 2931 cm -1 ，v s (C-H 3 ) The symmetrical telescopic vibration peak of (a) is positioned at 2884 cm -1 ，v as The asymmetric stretching vibration peaks of (Si-O) are located at 1084 and 1218 cm -1 Located at 796 cm -1 The characteristic peak at this point is attributed to tetraethyl orthosilicatev s Symmetrical stretching vibration peak of (Si-O) at 470 cm -1 The characteristic peak of (2) belongs to the O-Si-O valence band. Appear at 1487 cm -1 Characteristic peaks at the positions corresponding to CH in cetyltrimethylammonium bromide 3 -(N + ) An antisymmetric variable angle vibration band.
(IV) verifying the sensing performance of the hollow porous carbon sphere/graphene modified GCE electrode based on boron/nitrogen co-doping obtained in the test I
1. Preparation of electrochemical sensor
The three-electrode system formed by taking the hollow porous carbon sphere/graphene modified GCE electrode based on boron/nitrogen co-doping as a working electrode, taking an Ag/AgCl electrode as a reference electrode and taking a platinum wire electrode as an auxiliary electrode is an electrochemical sensor.
2. Detecting xanthine and guanine simultaneously or separately with the electrochemical sensor obtained in the first step
Conclusion: a differential pulse voltammogram of the catalytic xanthine and guanine of the electrochemical sensor shown in fig. 8 is obtained, wherein the concentration range from bottom to top of fig. 8 is 10-50 μm. In a 0.1M (ph=7.0) phosphate buffer solution, the electrocatalytic activity of the boron/nitrogen co-doped hollow porous carbon sphere/graphene for analyte was investigated using differential pulse method only when one analyte concentration was changed while the other was maintained. As can be seen from fig. 9, the response current of xanthine increases linearly with the accumulation of xanthine concentration between 10 and 60 μm, and is not affected by the presence of guanine. As can be seen from fig. 10, the response current of guanine increases linearly with the accumulation of guanine concentration between 10 and 60 μm, and is not affected by the presence of xanthine. Fig. 9 and 10 show that the boron/nitrogen co-doped hollow porous carbon sphere/graphene has excellent electrocatalytic properties, and that the two analytes do not interfere with each other, and that the detection of xanthine and guanine can be performed simultaneously or separately. As can be seen from fig. 11, the anodic peak current gradually increased with the gradual addition of equal amounts of xanthine and guanine. As can be seen from fig. 11, the response current and the concentration of added xanthine/guanine are in a linear relationship, which shows that the hollow porous carbon nanosphere electrode co-doped with boron and nitrogen has obvious response to catalytic oxidation of xanthine and guanine, and can detect the concentration. This is because the boron/nitrogen co-doped hollow porous carbon spheres/graphene promote effective contact of biomolecules with reaction sites, and simultaneously improve the conductivity of the composite material, greatly accelerate proton/electron transport, and thus present higher electrocatalytic current and lower catalytic potential. It is described that an electrochemical sensor constructed based on boron/nitrogen co-doped hollow porous carbon spheres/graphene has excellent detection performance for detecting xanthine and guanine.
(V) detection of the linear Range and detection Limit of an electrochemical sensor based on a hollow porous carbon sphere/graphene-modified GCE electrode based on boron/Nitrogen co-doping obtained in experiment one of the present application
Preparation of electrochemical sensor: the three-electrode system formed by taking the hollow porous carbon sphere/graphene modified GCE electrode based on boron/nitrogen co-doping as a working electrode, taking an Ag/AgCl electrode as a reference electrode and taking a platinum wire electrode as an auxiliary electrode is an electrochemical sensor.
The detection limit and the detection range of the electrochemical sensor are studied by differential pulse voltammetry. As can be seen from fig. 12, in the PBS buffer solution with 0.1M ph=7.0, the response current of both increases gradually with the continuous accumulation of the xanthine and guanine concentrations, and the catalytic current produces a significant response even at very low concentrations. By a response current as shown in FIG. 13vs.The calibration graph of xanthine concentration shows that the corresponding linear regression equation is: i p = 0.612 C xan + 13.5. Correlation coefficient R of the linear equation 2 =0.993, demonstrating good linearity of the curve. The electrochemical sensor has a response current range of 9.15X10 when catalyzing xanthine -8 ~ 1.03×10 -4 M, limit of detection 5.03X10 -8 M. Response current as shown in FIG. 14vs.The calibration graph of guanine concentration shows that the corresponding linear regression equation is: i p = 0.564 C gua + 6.35. Correlation coefficient R of the linear equation 2 =0.992, demonstrating good linearity of the curve. The response current range of the electrochemical sensor for catalyzing guanine is calculated to be 8.22 multiplied by 10 -8 ~ 1.28×10 -4 M, detection limit of 4.62X10 -8 M. These excellent properties are mainly due to synergistic effects and unique structural features between the components, promoting effective contact of biomolecules with reactive sites, and simultaneously improving the conductivity of the composite material, greatly accelerating proton/electron transport.
In summary, a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping is successfully prepared, and a xanthine and guanine electrochemical sensor built based on the electrode has excellent detection performance.
Claims (2)
1. A preparation method of a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping is characterized by comprising the following steps of:
step one, preparing a hollow porous carbon sphere based on boron/nitrogen co-doping: adding 2.4 g-3.0 g of cetyltrimethylammonium bromide solution into 95 mL-105 mL of deionized water, dropwise adding 0.1 mL-1 mL of ammonia water under intense stirring, and marking as solution A; dissolving 0.2 g-0.8 g of resorcinol and 0.05 g-0.15 g of boric acid in the solution A and continuously stirring for 1h, and marking as a solution B; adding 7.0-8.0 mL of tetraethyl orthosilicate and 2.3-3.3 mL of formaldehyde into the solution B, stirring for 24 hours at normal temperature, and then centrifuging, washing and drying to collect gray solid products; heating the gray solid product in a tube furnace, reacting at 700 ℃ for 2-4 hours at a heating rate of 4-6 ℃/min under the protection of nitrogen, and collecting the black product after cooling to normal temperature; immersing the black product into 7% -10% hydrofluoric acid solution, stirring for 24 hours at normal temperature, centrifuging, washing and drying to obtain boron/nitrogen co-doped hollow porous carbon spheres;
preparing a hollow porous carbon sphere and reduced graphene oxide based on boron/nitrogen co-doping: weighing a final product boron/nitrogen co-doped hollow porous carbon sphere and graphene solid according to a mass ratio of 1:4-6, putting the final product into a three-necked round bottom flask, adding 25-35 mL of deionized water, performing ultrasonic treatment for 30min, stirring at normal temperature for 1h, transferring the mixed solution into a 50mL stainless steel high-pressure reaction kettle, and performing hydrothermal reaction at 160 ℃ for 3h to obtain black suspension; then, centrifuging, washing and vacuum drying the mixture to obtain a black product, namely the hollow porous carbon spheres co-doped with boron/nitrogen and the reduced graphene oxide;
preparing a hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping: weighing 4-6 mg of black product obtained in the second step, grinding the black product into powder, dispersing the powder into a mixed solvent of 900-980 mu L of deionized water and 0.2-1 wt% of 20-100 mu L of naphthol, carrying out ultrasonic treatment for 27-33 min, accurately removing 4-6 mu L of suspension liquid, dripping the suspension liquid on the surface of a GCE electrode with a smooth mirror surface, and naturally airing the GCE electrode at normal temperature for later use.
2. The hollow porous carbon sphere/graphene electrochemical sensing electrode based on boron/nitrogen co-doping, which is prepared by the preparation method according to claim 1.
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