CN111286967B - Heteroatom-doped/carbon nanofiber/carbon fiber biosensor and application thereof - Google Patents

Heteroatom-doped/carbon nanofiber/carbon fiber biosensor and application thereof Download PDF

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CN111286967B
CN111286967B CN202010165267.1A CN202010165267A CN111286967B CN 111286967 B CN111286967 B CN 111286967B CN 202010165267 A CN202010165267 A CN 202010165267A CN 111286967 B CN111286967 B CN 111286967B
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孟龙月
刘锐
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Yanbian University
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Abstract

The invention discloses a heteroatom doped/carbon nanofiber/carbon fiber biosensor and application thereof in the aspect of biological small molecule detection; forming a standard three-electrode system by using heteroatom doped/carbon nanofiber/carbon fiber as a working electrode, Ag/AgCl as a reference electrode and Pt as a counter electrode to prepare a heteroatom doped/carbon nanofiber/carbon fiber biosensor; the prepared sensor has high sensitivity and strong interference resistance, can simultaneously detect dopamine, ascorbic acid and uric acid, and does not generate serious interference on the detection of the dopamine due to high-concentration ascorbic acid and uric acid.

Description

Heteroatom-doped/carbon nanofiber/carbon fiber biosensor and application thereof
Technical Field
The invention belongs to the technical field of biological signal molecule detection, and particularly relates to a heteroatom-doped/carbon nanofiber/carbon fiber biosensor and application thereof.
Background
Carbon Fiber (CF) is a new high-strength and high-modulus fiber material with a carbon content of more than 95%, has the characteristics of high specific strength, ultra-high temperature resistance, fatigue resistance and the like, and is often used as a reinforcement of thermosetting or thermoplastic resin composite materials. At present, the CF reinforced resin matrix composite material has very wide application in the advanced fields of aerospace, military, national defense and the like or the civil fields of automobiles, electronic devices, high-end sports goods and the like due to the excellent performance of the CF reinforced resin matrix composite material. Among them, the CF reinforced thermoplastic composite material has been a research hotspot in recent years due to the advantages of recycling, rapid forming and good impact resistance.
The biosensor is a high and new technology developed by the interpenetration of various subjects such as biology, chemistry, physics, medicine, electronic technology and the like. The method has the characteristics of good selectivity, high sensitivity, high analysis speed, low cost, capability of carrying out online continuous monitoring in a complex system, and particularly high automation, miniaturization and integration, so that the method is rapidly developed in recent decades. The biosensor makes up the defects of the traditional detection and analysis by the characteristics of the biosensor, so that people can analyze and detect own target objects more quickly and sensitively. Therefore, biosensors have attracted much attention in the field of detection of neurotransmitters and active biomolecule ions. However, there are still many problems to be improved in the currently used biosensors, such as (1) stability: the immobilized biological material on the surface of the sensor is easy to inactivate and has poor reproducibility; (2) and (3) selectivity: the sensor surface biological material is improved to improve the affinity of the sensor surface biological material to target molecules, so that the selectivity of the biosensor is improved; (3) the economic efficiency is as follows: the biosensor has high preparation cost and poor recycling property.
Disclosure of Invention
The invention aims to solve the problems of poor stability, low selectivity and high preparation cost of the existing biosensor, and provides a heteroatom-doped/carbon nanofiber/carbon fiber biosensor which has the advantages of good stability, strong selectivity and low cost, can realize simultaneous detection of dopamine, ascorbic acid and uric acid, and does not generate serious interference on dopamine detection by high-concentration ascorbic acid and uric acid, and application thereof.
A nitrogen-doped/carbon nanofiber/carbon fiber is prepared by the following steps:
1) putting carbon fibers as a substrate material into a muffle furnace to be calcined for 0.5 to 2 hours at the temperature of 450 ℃; taking out, sequentially leaching with acetone, ethanol and deionized water for 3-5 times, drying, and soaking in catalyst for 2-24 hr; taking out, rapidly dispersing uniformly, and drying;
2) spreading the dried carbon fiber on a corundum boat; putting the corundum boat into a uniform temperature area of a tube furnace, and introducing inert gas at the flow rate of 10-500 cc/min; increasing the temperature to 400-950 ℃ within 1.5-5H, and introducing H at a flow rate of 10-300 cc/min2Maintaining for a period of time;introducing methane, acetylene or ethylene at the rate of 10-500 cc/min for 5 min-5 h, and cooling to room temperature to obtain carbon nanofiber/carbon fiber;
2) weighing carbon nanofiber/carbon fiber and urea in a mass ratio of 1-5:1-80, placing in a uniform temperature zone of a tubular furnace, and introducing N at a rate of 10-500 cc/min2Heating to 1100 deg.C, and maintaining the temperature for 2 h; cooling to room temperature to obtain nitrogen-doped/carbon nanofiber/carbon fiber;
3) putting nitrogen-doped/carbon nanofiber/carbon fiber into a quartz boat, putting the quartz boat into a plasma instrument, and adding N2In order to break the vacuum state after the protective gas is used for plasma treatment, O is introduced2Ar, adjusting O2Treating for 30 s with the Ar flow ratio of 1:5-20 and the power of 80W to obtain nitrogen-doped/carbon nanofiber/carbon fiber treated by plasma;
the catalyst in the step 1) is a nickel catalyst;
the nickel catalyst is obtained by adding a surfactant, ethanol, hydrochloric acid, deionized water and tetraethoxysilane into metal nickel and uniformly stirring; the surfactant is P123 or F127 (the molar mass ratio is 1: 0.022: 45.53: 0.085: 19.91: 2.13);
the time for introducing methane, acetylene or ethylene in the step 2) is 5-50 min;
the speed of acetylene introduction is 30cc/min, and the time is 30 min;
the temperature as described in step 2) was raised to 500 ℃.
A nitrogen-doped/carbon nanofiber/carbon fiber biosensor is characterized in that: the method comprises a standard three-electrode system, wherein a working electrode is the nitrogen-doped/carbon nanofiber/carbon fiber according to claim 1, a reference electrode is Ag/AgCl, and a counter electrode is Pt.
The nitrogen-doped/carbon nanofiber/carbon fiber is applied to the detection of small biological molecules;
the application is characterized in that: the biological micromolecules are dopamine, ascorbic acid and/or uric acid.
The invention provides an application of heteroatom doped/carbon nanofiber/carbon fiber in the aspect of biomolecule detection; forming a standard three-electrode system by using heteroatom doped/carbon nanofiber/carbon fiber as a working electrode, Ag/AgCl as a reference electrode and Pt as a counter electrode to prepare a heteroatom doped/carbon nanofiber/carbon fiber biosensor; the prepared sensor has high sensitivity and strong anti-interference, and can realize the simultaneous detection of various substances. The invention has the advantages that: 1) the carbon fiber as a substrate material has strong mechanical stability, electrical conductivity and biocompatibility; 2) the prepared heteroatom doped/carbon nanofiber/carbon fiber further changes the surface structure of the electrode, increases catalytic active sites, improves hydrophilicity, and adsorbs and effectively identifies small biological molecules; 3) more catalytic reaction sites are provided; 4) the prepared heteroatom doped/porous carbon/carbon fiber electrode has good electrochemical performance, and can be applied to the fields of detection of biological micromolecules, monitoring of clinical detection of tumor markers, environmental heavy metal ions and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a carbon fiber;
FIG. 2 is a scanning electron micrograph of carbon nanofibers/carbon fibers prepared in example 1;
FIG. 3 is a scanning electron micrograph of nitrogen-doped/carbon nanofibers/carbon fibers prepared in example 1;
FIG. 4 is a DPV graph of dopamine detection using different catalyst preparation electrodes; 1) CFs, carbon fiber; 2) Fe-CNFs/CFs, iron catalysis-carbon nanofibers/carbon fibers; 3) Co-CNFs/CFs, cobalt catalysis-carbon nanofibers/carbon fibers; 4) Ni-CNFs/CFs, nickel catalysis-carbon nanofibers/carbon fibers;
FIG. 5 is a scanning electron microscope image of carbon nanofibers/carbon fibers prepared at different growth temperatures; (a)400 ℃; (b)500 ℃; (c)600 ℃; (d)700 ℃; (e)800 ℃; (f)900 ℃;
FIG. 6 is a DPV diagram for detecting dopamine by preparing carbon nanofiber/carbon fiber electrodes at different growth temperatures; 1)400 ℃; 2)500 ℃; 3)600 ℃; 4)700 ℃; 5)800 ℃; 6)900 ℃;
FIG. 7 is a scanning electron microscope image of carbon nanofibers/carbon fibers prepared at different growth times; (a)5 min; (b)10 min; (c)30 min; (d)50 min;
FIG. 8 is a DPV diagram for detecting dopamine by preparing carbon nanofiber/carbon fiber electrodes at different growth times; 1)5 min; 2)10 min; 3)30 min; 4)50 min;
FIG. 9 scanning electron micrographs of carbon nanofibers/carbon fibers prepared at different acetylene flow rates; (a)10 cc/min; (b)30 cc/min; (c)50 cc/min;
FIG. 10 is a DPV graph of dopamine detection by carbon nanofiber/carbon fiber electrodes prepared at different acetylene flow rates; 1)10 cc/min; 2)30 cc/min; 3)50 cc/min;
FIG. 11 is a DPV graph of dopamine detection using different heteroatom-doped electrodes; 1) CFs, carbon fiber; 2) CNFs/CFs, carbon nanofibers/carbon fibers; 3) N/S-CNFs/CFs, nitrogen-sulfur double-doped/carbon nanofiber/carbon fiber; 4) S-CNFs/CFs, sulfur-doped/carbon nanofibers/carbon fibers; 5) N-CNFs/CFs, nitrogen doped/carbon nanofiber/carbon fiber;
FIG. 12 is a CV diagram for dopamine detection in different pH buffered solutions;
FIG. 13 is a graph showing an Ep-pH relationship and an Ip-pH relationship;
FIG. 14 is a CV diagram of dopamine (0.1M) at different sweeping speeds and an Ip-v relationship curve;
FIG. 15 is a DPV graph and Ip-c curves for different concentrations of dopamine;
fig. 16 simultaneously measures CV and DPV plots of dopamine, ascorbic acid and uric acid.
Detailed Description
Example 1 preparation of nitrogen-doped/carbon nanofiber/carbon fiber
A preparation method of nitrogen-doped/carbon nanofiber/carbon fiber comprises the following specific steps:
1) 3000 carbon fibers are taken as a substrate material, and the substrate material is put into a muffle furnace to be calcined for 0.5 to 2 hours at the temperature of 450 ℃; taking out, sequentially leaching with acetone, ethanol and deionized water for 3-5 times, naturally drying, and soaking in nickel catalyst for 2-24 h; taking out, quickly dispersing, uniformly spreading and airing;
2) the treated carbon fiber is tiled on a corundum boat, so that gas can simultaneously pass through the upper side and the lower side of the carbon fiber, and the carbon nanofiber can be ensured to grow uniformly on the surface of the carbon fiber; putting the corundum boat into the uniform temperature zone of the tube furnaceIntroducing N at a flow rate of 10-500 cc/min2(ii) a Heating to 500 deg.C within 1.5-5H, and introducing H at flow rate of 10-300 cc/min2Maintaining for a period of time; introducing acetylene at the rate of 30cc/min for 0.5h, cooling, and cooling to room temperature to obtain carbon nanofiber/carbon fiber;
3) weighing carbon nanofiber/carbon fiber and urea in a mass ratio of 1:1, placing the carbon nanofiber/carbon fiber and urea in a uniform temperature zone of a tubular furnace, and introducing N at a rate of 10-500 cc/min2Heating to 1100 deg.C, and maintaining the temperature for 2 h; cooling to room temperature to obtain nitrogen-doped/carbon nanofiber/carbon fiber;
4) putting nitrogen-doped/carbon nanofiber/carbon fiber into a quartz boat, putting the quartz boat into a plasma instrument, and introducing N2、O2Ar, adjusting O2Treating for 30 s with the Ar flow ratio of 1:5-1:20 and the power of 80W to obtain nitrogen-doped/carbon nanofiber/carbon fiber treated by plasma;
the nickel catalyst in the step 1) is prepared by the following method: adding a surfactant P123 or F127, ethanol, hydrochloric acid, deionized water and tetraethoxysilane into the metal nickel, and uniformly stirring to obtain the catalyst.
Through comparison of scanning electron micrographs of carbon fibers (fig. 1), carbon nanofibers/carbon fibers (fig. 2) and nitrogen-doped carbon nanofibers/carbon fibers (fig. 3), it is found that the surface of pure carbon fibers is smooth and has longitudinal ravines, the specific surface area and pore structure of carbon fibers growing carbon nanofibers are significantly increased, a basis is provided for adsorption of reactants and rapid transmission of electrons, and the nitrogen-doped carbon nanofibers/carbon fibers further change the surface structure of an electrode, so that catalytic active sites and the specific surface area are increased.
Example 2 preparation of a Sulfur-doped/carbon nanofiber/carbon fiber
A preparation method of sulfur-doped/carbon nanofiber/carbon fiber comprises the following specific steps:
1) 3000 carbon fibers are taken as a substrate material, and the substrate material is put into a muffle furnace to be calcined for 0.5 to 2 hours at the temperature of 450 ℃; taking out, sequentially leaching with acetone, ethanol and deionized water for 3-5 times, naturally drying, and soaking in iron catalyst for 2-24 hr; taking out and rapidly dispersingUniformly spreading and airing, namely spreading the treated carbon fibers on a corundum boat, so that gas can simultaneously pass through the upper side and the lower side of the carbon fibers, and ensuring that the carbon nanofibers uniformly grow on the surfaces of the carbon fibers; putting the corundum boat into a uniform temperature zone of a tube furnace, and introducing N at the flow rate of 10-500 cc/min2(ii) a Within the time of 1.5-5H, the temperature is raised to 400-950 ℃, H is introduced at the flow rate of 10-300 cc/min2Maintaining for a period of time; introducing ethylene at a rate of 10-500 cc/min for 0.5-5 h, cooling, and cooling to room temperature to obtain carbon nanofiber/carbon fiber;
2) weighing carbon nanofiber/carbon fiber and sulfur in a mass ratio of 1:16, placing the carbon nanofiber/carbon fiber and sulfur in a uniform temperature zone of a tubular furnace, and introducing N at a rate of 10-500 cc/min2Heating to 800 ℃, and keeping the temperature for 1 h; cooling to room temperature to obtain sulfur-doped/carbon nanofiber/carbon fiber;
3) putting the sulfur-doped/carbon nanofiber/carbon fiber into a quartz boat, putting the quartz boat into a plasma instrument, and introducing N2、O2Ar, adjusting O2Treating for 30 s with the Ar flow ratio of 1:5-1:20 and the power of 80W to obtain nitrogen-doped/carbon nanofiber/carbon fiber treated by plasma;
the iron catalyst in the step 1) is prepared by the following method: adding a surfactant P123 or F127, ethanol, hydrochloric acid, deionized water and tetraethoxysilane into the iron metal, and uniformly stirring to obtain the catalyst.
Example 3 preparation of boron-doped/carbon nanofiber/carbon fiber
A preparation method of boron-doped/carbon nanofiber/carbon fiber comprises the following specific steps:
1) 3000 carbon fibers are taken as a substrate material, and the substrate material is put into a muffle furnace to be calcined for 0.5 to 2 hours at the temperature of 450 ℃; taking out, sequentially leaching with acetone, ethanol and deionized water for 3-5 times, naturally drying, and soaking in nickel-cobalt catalyst for 2-24 h; taking out, quickly dispersing, uniformly spreading and airing, spreading the treated carbon fibers on a corundum boat, and allowing gas to pass through the upper side and the lower side of the carbon fibers simultaneously so as to ensure that the carbon nanofibers uniformly grow on the surfaces of the carbon fibers; putting the corundum boat into a uniform temperature zone of a tube furnace, and introducing the corundum boat at a flow rate of 10-500 cc/minN2(ii) a Within the time of 1.5-5H, the temperature is raised to 400-950 ℃, H is introduced at the flow rate of 10-300 cc/min2Maintaining for a period of time; introducing methane at a rate of 10-500 cc/min for 0.5-5 h, cooling, and cooling to room temperature to obtain carbon nanofiber/carbon fiber;
2) weighing carbon nanofiber/carbon fiber and boric acid in a mass ratio of 3:10, placing the carbon nanofiber/carbon fiber and boric acid in a uniform temperature zone of a tube furnace, and introducing N at a rate of 10-500 cc/min2Heating to 400 ℃, and keeping the temperature for 6 hours; cooling to room temperature to obtain boron-doped/carbon nanofiber/carbon fiber;
3) putting the sulfur-doped/carbon nanofiber/carbon fiber into a quartz boat, putting the quartz boat into a plasma instrument, and introducing N2、O2Ar, adjusting O2Treating for 30 s with the Ar flow ratio of 1:5-1:20 and the power of 80W to obtain nitrogen-doped/carbon nanofiber/carbon fiber treated by plasma;
the nickel-cobalt catalyst in the step 1) is prepared by the following method: adding surfactant P123 or F127, ethanol, hydrochloric acid, deionized water and tetraethoxysilane into the bimetallic nickel-cobalt mixture according to the mass proportion, and uniformly stirring to obtain the catalyst.
Example 4 preparation of Nitrogen-Sulfur double doping/carbon nanofiber/carbon fiber
A preparation method of nitrogen-sulfur double-doped/carbon nanofiber/carbon fiber comprises the following specific steps:
1) 3000 carbon fibers are taken as a substrate material, and the substrate material is put into a muffle furnace to be calcined for 0.5 to 2 hours at the temperature of 450 ℃; taking out, sequentially leaching with acetone, ethanol and deionized water for 3-5 times, naturally drying, and soaking in iron catalyst (or nickel catalyst) for 2-24 hr; taking out, quickly dispersing, uniformly spreading and airing, spreading the treated carbon fibers on a corundum boat, and allowing gas to pass through the upper side and the lower side of the carbon fibers simultaneously so as to ensure that the carbon nanofibers uniformly grow on the surfaces of the carbon fibers; putting the corundum boat into a uniform temperature zone of a tube furnace, and introducing N at the flow rate of 10-500 cc/min2(ii) a Within the time of 1.5-5H, the temperature is raised to 400-950 ℃, H is introduced at the flow rate of 10-300 cc/min2Maintaining for a period of time; introducing acetylene at a rate of 10-500 cc/min for 0.5-5 h, and coolingCooling to room temperature to obtain carbon nanofiber/carbon fiber;
2) weighing a mixture of carbon nanofiber/carbon fiber, urea and sulfur in a mass ratio of 1:8, placing the mixture in a uniform temperature zone of a tubular furnace, and introducing N at a rate of 10-500 cc/min2Heating to 1000 ℃, and keeping the temperature for 2 hours; cooling to room temperature to obtain nitrogen-sulfur double-doped/carbon nanofiber/carbon fiber;
3) putting the sulfur-doped/carbon nanofiber/carbon fiber into a quartz boat, putting the quartz boat into a plasma instrument, and introducing N2、O2Ar, adjusting O2Treating for 30 s with the Ar flow ratio of 1:5-1:20 and the power of 80W to obtain nitrogen-doped/carbon nanofiber/carbon fiber treated by plasma;
the cobalt catalyst in the step 1) is prepared by the following method: adding a surfactant P123 or F127, ethanol, hydrochloric acid, deionized water and tetraethoxysilane into iron (or nickel) metal, and uniformly stirring to obtain the catalyst.
Example 5 preparation of N-P double-doped/carbon nanofiber/carbon fiber
A preparation method of nitrogen-phosphorus double-doped/carbon nanofiber/carbon fiber comprises the following specific steps:
1) 3000 carbon fibers are taken as a substrate material, and the substrate material is put into a muffle furnace to be calcined for 0.5 to 2 hours at the temperature of 450 ℃; taking out, sequentially leaching with acetone, ethanol and deionized water for 3-5 times, naturally drying, and soaking in cobalt catalyst for 2-24 h; taking out, quickly dispersing, uniformly spreading and airing, spreading the treated carbon fibers on a corundum boat, and allowing gas to pass through the upper side and the lower side of the carbon fibers simultaneously so as to ensure that the carbon nanofibers uniformly grow on the surfaces of the carbon fibers; putting the corundum boat into a uniform temperature zone of a tube furnace, and introducing N at the flow rate of 10-500 cc/min2(ii) a Within the time of 1.5-5H, the temperature is raised to 400-950 ℃, H is introduced at the flow rate of 10-300 cc/min2Maintaining for a period of time; introducing acetylene at the rate of 10-500 cc/min for 0.5-5 h, cooling, and cooling to room temperature to obtain carbon nanofiber/carbon fiber;
2) weighing a mixture of carbon nano fiber/carbon fiber, urea and phosphoric acid with the mass ratio of 1:6, placing the mixture in a uniform temperature zone of a tubular furnace, and adding 10-A rate of 500 cc/min N2Heating to 600 ℃, and keeping the temperature for 5 hours; cooling to room temperature to obtain nitrogen-phosphorus double-doped/carbon nanofiber/carbon fiber;
3) putting the sulfur-doped/carbon nanofiber/carbon fiber into a quartz boat, putting the quartz boat into a plasma instrument, and introducing N2、O2Ar, adjusting O2Treating for 30 s with the Ar flow ratio of 1:5-1:20 and the power of 80W to obtain nitrogen-doped/carbon nanofiber/carbon fiber treated by plasma;
the cobalt catalyst in the step 1) is prepared by the following method: adding a surfactant P123 or F127, ethanol, hydrochloric acid, deionized water and tetraethoxysilane into the cobalt metal, and uniformly stirring to obtain the catalyst.
Example 6 preparation of a heteroatom-doped/carbon nanofiber/carbon fiber biosensor
The carbon fiber, the carbon nanofiber/carbon fiber or the heteroatom-doped/carbon nanofiber/carbon fiber prepared in the embodiments 1 to 5 are respectively used as a working electrode, Ag/AgCl is used as a reference electrode, Pt is used as a counter electrode to form a standard three-electrode system, and the electrode system prepared by using the heteroatom-doped/carbon nanofiber/carbon fiber as the working electrode is the heteroatom-doped/carbon nanofiber/carbon fiber biosensor.
Example 7 heteroatom doping/carbon nanofiber/carbon fiber biosensor application experiment
Influence of controllable preparation of heteroatom-doped/carbon nanofiber/carbon fiber biosensor on electrochemical performance of dopamine detection
(1) Influence of the catalyst
Preparing carbon nanofiber/carbon fiber catalyzed by iron, cobalt or nickel by iron, cobalt and nickel catalysts respectively and by a chemical vapor deposition method, and detecting dopamine (0.1M) as a working electrode, wherein the result is shown in fig. 4; from the figure, it can be observed that the sensitivity of the bare Carbon Fiber (CFs) electrode for detecting dopamine is low, and the sensitivity of the CNFs/CFs prepared by iron, cobalt and nickel catalysts for detecting dopamine is sequentially increased (nickel > cobalt > iron), so that the nickel catalyst is selected for carrying out the following experiments.
(2) Influence of growth temperature
Soaking a nickel catalyst, airing, putting a sample into a small muffle furnace, calcining for 0.5h, putting the calcined sample into a corundum boat, putting the corundum boat in a constant-temperature area of a tubular furnace, introducing 150 cc/min nitrogen to remove air in the tubular furnace so as to avoid influencing the sample, then heating to 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 and 900 ℃ at the speed of 5 ℃/min, introducing 20 cc/min hydrogen to eliminate the influence caused by an oxide film on the surface of the sample, introducing 30cc/min acetylene after 0.5h, and keeping the temperature for 1 h. And (3) after growing the carbon nano fiber at constant temperature, closing acetylene and hydrogen, and cooling the sample to room temperature in a nitrogen atmosphere. As shown in fig. 5, it can be observed that the morphology difference between the carbon fibers grown at different temperatures is significant, and although the carbon nanofibers can be observed on the surface of the carbon fibers at a growth temperature of 400 ℃, the carbon nanofibers are very short and rare in length, and the analysis reason is that the nickel in the catalyst is not completely reduced to a simple nickel substance because the temperature is too low, and thus the nickel does not completely play a catalytic role, as shown in fig. 5 (a); when the growth temperature is raised to 500 ℃, the length of the carbon nanofiber is obviously increased and is more compact, the carbon nanofiber uniformly covers the surface of the carbon fiber, and the diameter of the carbon nanofiber is about 10-40 nm, as shown in fig. 5 (b); when the carbon nanofibers grow at 600 ℃, we can observe that the carbon nanofibers uniformly grow on the surface of the carbon fibers, and the diameter of the carbon nanofibers is about 10-50 nm, as shown in fig. 5 (c); when the temperature is increased to 700 ℃, the diameter of the carbon nanofiber is continuously increased to about 25-60 nm, the length of the carbon nanofiber on the surface of the carbon fiber is also obviously increased, the phenomenon is more obvious when the temperature is increased to 800 ℃, the diameter of the carbon nanofiber can reach 70-100 nm, and the analysis reason is that the reduced nickel simple substance is agglomerated to a certain extent along with the increase of the temperature, as shown in fig. 5(d) - (e); when the temperature is increased to 900 ℃, the carbon nanofiber can be found not growing on the surface of the carbon fiber, and the analysis reason is that the temperature is too high, the reduced nickel simple substance is seriously agglomerated, and the catalytic activity is lost, as shown in fig. 5 (f). Fig. 6 is a differential pulse voltammetry curve measured by the materials prepared at different temperatures in PBS (pH =7.4) buffer solution containing 0.1 mM dopamine, from which we can observe that the dopamine spike is at 0.285V, and the sensitivity of the prepared CNFs/CFs for detecting dopamine is the highest when the temperature is 500 ℃, so 500 ℃ is the optimal temperature for the carbon nanofiber grown by the nickel catalyst.
(3) Influence of growth time
Soaking a nickel catalyst, airing, putting a sample into a small muffle furnace, calcining for 0.5h, putting the calcined sample into a corundum boat, placing the corundum boat in a constant-temperature area of a tubular furnace, introducing 150 cc/min nitrogen to remove air in the tubular furnace so as to avoid influencing the sample, then heating to 500 ℃ at the speed of 5 ℃/min, introducing 20 cc/min hydrogen to eliminate the influence caused by an oxide film on the surface of the sample, introducing 30cc/min acetylene after 0.5h, wherein the acetylene introducing time is respectively 5 min, 10 min, 30min and 50 min. And (3) after growing the carbon nano-fiber at constant temperature, closing acetylene and hydrogen, and cooling the sample to room temperature in a nitrogen atmosphere to obtain the CNFs/CFs. Because the effect of the prepared material is the most ideal when the growth temperature is 500 ℃, the influence of the growth time on the carbon nano-fiber grown by nickel is continuously researched by selecting 500 ℃ for the growth temperature in the subsequent experiment. As shown in fig. 7(a), when the growth time is 5 min, the carbon fiber surface is uniformly covered with a layer of carbon nano material in the form of small particles, and the analysis reason is that the acetylene is introduced for too short time, so that the amount of the introduced acetylene is not enough to form carbon nano fibers; increasing the growth time to 10 min, flocculent carbon nanomaterials on the surface of the carbon fibers can be observed, and the transition state of the carbon nanofibers formed by amorphous carbon is analyzed, as shown in fig. 7 (b); when the growth time is continuously increased to 30min, the carbon nanofibers grown on the surface of the carbon fibers are uniform and dense, as shown in fig. 7 (c); and when the growth time is increased to 50min, the carbon nanofibers are significantly grown and a small part of the carbon nanofibers are agglomerated, and the analysis reason is that the carbon nanofibers continue to grow and are randomly wound due to the fact that the acetylene is introduced too much, as shown in fig. 7 (d). Fig. 8 is a differential pulse voltammetry curve measured in PBS (pH =7.4) buffer solution containing 0.1 mM dopamine for the materials prepared at different growth times, from which we can observe that the dopamine spike is at 0.27V, and the sensitivity of the prepared CNFs/CFs for detecting dopamine is the highest when the growth time is 30min, so 30min is the optimal growth time of the carbon nanofibers grown by the nickel catalyst.
(4) Influence of acetylene flow
Soaking a nickel catalyst, airing, putting a sample into a small muffle furnace, calcining for 0.5h, putting the calcined sample into a corundum boat, putting the corundum boat in a constant-temperature area of a tubular furnace, introducing 150 cc/min nitrogen to remove air in the tubular furnace so as to avoid influencing the sample, then heating to 500 ℃ at the speed of 5 ℃/min, introducing 20 cc/min hydrogen to eliminate the influence caused by an oxide film on the surface of the sample, introducing 10, 30 and 50 cc/min acetylene for 0.5h after 0.5h, closing the acetylene and the hydrogen after growing carbon nanofibers at constant temperature, and cooling the sample to room temperature in a nitrogen atmosphere to obtain the CNFs/CFs. The effect of the prepared material is optimal when the growth temperature is 500 ℃ and the growth time is 30min, so that the influence of the acetylene flow on the carbon nanofiber grown by nickel is continuously researched at the growth temperature of 500 ℃ and the growth time of 30min in the subsequent experiment. As shown in fig. 9(a), when the acetylene flow rate is 10 cc/min, the carbon fiber surface is uniformly covered with a layer of flocculent carbon material, and the reason for analysis is that the acetylene flow rate is too small, and the amount of acetylene introduced is not enough to form carbon nanofibers; increasing the growth time to 30cc/min, it can be observed that the carbon nanofibers are abundant on the surface of the carbon fiber and have more uniform diameter, as shown in fig. 9 (b); when the acetylene flow rate is continuously increased to 50 cc/min, the diameters of the carbon nanofibers grown on the surface of the carbon fibers are not uniform, the lengths of part of the carbon nanofibers are increased remarkably due to the excessive introduction of acetylene, and most of the carbon nanofibers are curled, as shown in fig. 9 (c). FIG. 10 is a differential pulse voltammetry curve of the materials prepared at different acetylene flow rates in PBS (pH =7.4) buffer solution containing 0.1 mM dopamine, from which we can observe that the dopamine spike is at 0.29V, and the sensitivity of the prepared CNFs/CFs for detecting dopamine is the highest when the acetylene flow rate is 30cc/min, so that 30cc/min is the optimal gas flow rate of the carbon nanofibers grown by the nickel catalyst.
(5) Influence of doping of heteroatom species
Further preparing a heteroatom-doped/carbon nanofiber/carbon fiber biosensor by using nickel as a catalyst, CNFs (carbon Nano fibers)/CFs (carbon fiber reinforced plastics) prepared at the growth temperature of 500 ℃, the growth time of 30min and the acetylene flow rate of 30cc/min as a substrate, and then detecting dopamine, wherein the result is shown in figure 11; from the results, comparing the sensitivity of the CNFs/CFs to dopamine, the sensitivity of the nitrogen-sulfur double-doped/carbon nanofiber/carbon fiber biosensor and the sensitivity of the sulfur-doped/carbon nanofiber/carbon fiber biosensor to detect dopamine are reduced, and the sensitivity of the nitrogen-doped/carbon nanofiber/carbon fiber biosensor to detect dopamine is further improved.
Secondly, the influence of the pH value of the buffer solution on the electrochemical performance of dopamine detection
The carbon fiber, the carbon nanofiber/carbon fiber and the nitrogen-doped/carbon nanofiber/carbon fiber prepared in example 1 were used as working electrodes, Ag/AgCl was used as a reference electrode, and Pt was used as a counter electrode to form a standard three-electrode system, and dopamine was detected in 0.01M PBS buffer solution.
FIG. 12 and FIG. 13 show the effect of pH value of buffer solution on dopamine detection; as shown in the figure, when the pH value is in the range of 5.0-9.0, the peak potential generates a negative shift phenomenon along with the increase of the pH value and is in a linear relation with the pH value (R)2=0.991) (fig. 13A), with a slope of 50.24 mV/pH, very close to Nernst's theoretical value of 59 mV/pH, proving that the reaction is a two electron/two proton electrochemical system. As pH increases, the peak current increases and then decreases, reaching a maximum at pH =7.4 (fig. 13B), which is very close to the pH of the environment in the human body, so pH =7.4 was selected as the optimum acidity value.
Influence of sweeping speed on electrochemical performance of detecting dopamine
The carbon fibers, carbon nanofibers/carbon fibers and nitrogen-doped/carbon nanofibers/carbon fibers prepared in example 1 were used as working electrodes, Ag/AgCl was used as a reference electrode, and Pt was used as a counter electrode to form a standard three-electrode system, and dopamine was detected in 0.01M PBS buffer solution with pH = 7.4.
The results are shown in FIG. 14, which is the effect of different sweeping speeds on the detection of dopamine; as shown in the figure, the sweep rate range is 10-200 mV/s, and as the sweep rate increases, the peak current also increases and is linear with the sweep rate (R)2=0.998), it can be seen that this reaction is an electrochemical process mainly involving adsorption.
Linear relationship of four, dopamine concentration
The carbon fibers, carbon nanofibers/carbon fibers and nitrogen-doped/carbon nanofibers/carbon fibers prepared in example 1 were used as working electrodes, Ag/AgCl was used as a reference electrode, and Pt was used as a counter electrode to form a standard three-electrode system, and dopamine was detected in 0.01M PBS buffer solution with pH = 7.4.
FIG. 15 is a DPV graph of dopamine in different concentrations in a pH =7.4 buffer solution, wherein the peak potential of the detected dopamine is about 0.22V, the concentration of the detected dopamine is within a range of 0.1-200 μ M, and the peak current increases with the increase of the concentration and is in a linear relation with the concentration (R)2=0.993), LOD =3s/M =0.0122 μ M by calculation.
Fifth, experiment of interference performance of high concentration ascorbic acid and uric acid on dopamine detection
Uric Acid (UA) and Dopamine (DA) are electroactive substances with important biological research values, commonly coexist in blood and urine of a human body, play an important role in maintaining normal metabolism of the human body, and the abnormal concentration of the Uric acid and the Dopamine in the body often causes corresponding diseases. Therefore, the detection of the concentration of UA and DA in human bodies has important practical value for the prevention and treatment of related diseases. However, other electroactive substances coexisting with UA and DA in the human body, such as ascorbic acid and reduced coenzyme I, have electrochemical activities similar to those of UA and DA, and it is difficult for the conventional electrode to eliminate interference and selectively detect UA and DA.
The carbon fiber, the carbon nanofiber/carbon fiber and the nitrogen-doped/carbon nanofiber/carbon fiber prepared in example 1 are used as working electrodes, Ag/AgCl is used as a reference electrode, Pt is used as a counter electrode to form a standard three-electrode system, and dopamine is detected in 0.01M PBS (phosphate buffered saline) buffer solution with pH = 7.4.
The nitrogen-doped/carbon nanofiber/carbon fiber electrode was used for simultaneous detection of dopamine (0.1 mM), ascorbic acid (2 mM) and uric acid (0.5 mM), as shown in FIG. 16, three peaks were observed in both CV and DPV plots, the dopamine peak potential was around 0.295V, the ascorbic acid peak potential was around 0.09V, the uric acid peak potential was around 0.455V, and EpAA-DA=205 mV，∆Ep DA-UA=160 mV, so that three simultaneous detections can be achieved; the experimental result proves that the high concentration of ascorbic acid and uric acid does not cause serious interference on dopamine detection.

Claims (10)

1. A nitrogen-doped/carbon nanofiber/carbon fiber is prepared by the following steps:
1) putting carbon fibers as a substrate material into a muffle furnace to be calcined for 0.5 to 2 hours at the temperature of 450 ℃; taking out, sequentially leaching with acetone, ethanol and deionized water for 3-5 times, drying, and soaking in catalyst for 2-24 hr; taking out, rapidly dispersing uniformly, and drying;
2) spreading the dried carbon fiber on a corundum boat; putting the corundum boat into a uniform temperature area of a tube furnace, and introducing inert gas at the flow rate of 10-500 cc/min; increasing the temperature to 400-950 ℃ within 1.5-5H, and introducing H at a flow rate of 10-300 cc/min2Maintaining for a period of time; introducing methane, acetylene or ethylene at the rate of 10-500 cc/min for 5 min-5 h, and cooling to room temperature to obtain carbon nanofiber/carbon fiber;
2) weighing carbon nanofiber/carbon fiber and urea in a mass ratio of 1-5:1-80, placing in a uniform temperature zone of a tubular furnace, and introducing N at a rate of 10-500 cc/min2Heating to 1100 deg.C, and maintaining the temperature for 2 h; cooling to room temperature to obtain nitrogen-doped/carbon nanofiber/carbon fiber;
3) putting nitrogen-doped/carbon nanofiber/carbon fiber into a quartz boat, putting the quartz boat into a plasma instrument, and adding N2In order to break the vacuum state after the protective gas is used for plasma treatment, O is introduced2Ar, adjusting O2Treating for 30 s with the Ar flow ratio of 1:5-20 and the power of 80W to obtain the nitrogen-doped/carbon nanofiber/carbon fiber treated by the plasma.
2. The nitrogen-doped/carbon nanofiber/carbon fiber according to claim 1, wherein: the catalyst in the step 1) is a nickel catalyst.
3. A nitrogen-doped/carbon nanofiber/carbon fiber according to claim 2, wherein: the nickel catalyst is obtained by adding a surfactant, ethanol, hydrochloric acid, deionized water and tetraethoxysilane into metal nickel and uniformly stirring; the surfactant is P123 or F127.
4. A nitrogen-doped/carbon nanofiber/carbon fiber according to claim 3, wherein: the molar mass ratio of the metal nickel, the surfactant, the ethanol, the hydrochloric acid, the deionized water and the tetraethoxysilane is 1: 0.022: 45.53: 0.085: 19.91: 2.13.
5. a nitrogen-doped/carbon nanofiber/carbon fiber according to claim 2, 3 or 4, characterized in that: and 2) introducing methane, acetylene or ethylene for 5-50 min.
6. The nitrogen-doped/carbon nanofiber/carbon fiber according to claim 5, wherein: the acetylene feeding rate is 30cc/min, and the time is 30 min.
7. The nitrogen-doped/carbon nanofiber/carbon fiber according to claim 5, wherein: the temperature as described in step 2) was raised to 500 ℃.
8. A nitrogen-doped/carbon nanofiber/carbon fiber biosensor is characterized in that: the method comprises a standard three-electrode system, wherein a working electrode is the nitrogen-doped/carbon nanofiber/carbon fiber according to claim 1, a reference electrode is Ag/AgCl, and a counter electrode is Pt.
9. The use of a nitrogen-doped/carbon nanofiber/carbon fiber as claimed in claim 1 for the detection of small biological molecules, metal cations and/or amino acids.
10. The use of claim 9, wherein: the biological micromolecule is adrenaline, noradrenaline, serotonin, dopamine, ascorbic acid or uric acid, and the amino acid is glutamic acidTyrosine, aspartic acid, gamma-aminobutyric acid, the metal cation Ca2+、Mg2+、Pb2+。
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