CN110376258B - Nitrite electrochemical sensor based on carbon fiber paper, preparation method and application - Google Patents

Nitrite electrochemical sensor based on carbon fiber paper, preparation method and application Download PDF

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CN110376258B
CN110376258B CN201910599144.6A CN201910599144A CN110376258B CN 110376258 B CN110376258 B CN 110376258B CN 201910599144 A CN201910599144 A CN 201910599144A CN 110376258 B CN110376258 B CN 110376258B
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carbon fiber
fiber paper
nitrite
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working electrode
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CN110376258A (en
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王建龙
张怡
朱文新
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Northwest A&F University
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Abstract

The invention discloses a nitrite electrochemical sensor based on carbon fiber paper, a preparation method and application thereof, wherein the sensor comprises a carbon fiber paper working electrode, a counter electrode and a reference electrode, wherein the preparation process of the carbon fiber paper working electrode is as follows: the method comprises the steps of firstly cleaning impurities on the surface of carbon fiber paper and drying, then preserving heat in air for 1-3 hours at 500-700 ℃, naturally cooling to room temperature to obtain modified carbon fiber paper, using the prepared carbon fiber paper working electrode for detecting nitrite, wherein the electrode has the advantages of quick response time, high sensitivity, wide linear response range and low detection lower limit, and the prepared electrochemical sensor has high specificity, excellent long-term stability and repeatability and strong anti-interference capability for detecting nitrite.

Description

Nitrite electrochemical sensor based on carbon fiber paper, preparation method and application
Technical Field
The invention belongs to the technical field of electrochemical sensors, and particularly relates to a nitrite electrochemical sensor based on carbon fiber paper, a preparation method and application.
Background
The excessive use of nitrite as fertilizer and food additive in agricultural and industrial sectors causes serious nitrite pollution to underground water and serious harm to human health. Nitrite can generate degradation reaction with amino acid to generate nitrosamine with strong carcinogenicity, and if a human body ingests food added with excessive nitrite, symptoms such as methemoglobin or blue infant syndrome and the like can be caused, and serious people even die. Due to the potential toxicity of nitrite, quantitative analysis of nitrite becomes more and more important, and the traditional nitrite detection method is difficult to realize on-site rapid detection. Therefore, it is crucial to establish a truly practical and feasible method for detecting nitrite.
In recent years, analytical methods for measuring nitrite have been mainly spectroscopic, chromatographic, electrochemical, and the like. Among them, electrochemical analysis methods are receiving more and more attention due to their advantages of high sensitivity, low cost, simple operation, on-site analysis, and the like.
At present, most of electrodes used in detecting nitrite by an electrochemical analysis method are formed by compounding an enzyme, a metal material (metal, metal oxide, metal sulfide, metal nitride nanoparticle, etc.), a metal organic framework, a conductive polymer, a carbon material (graphene, carbon nanotube, carbon nanoparticle, porous carbon), and the like. However, most electrodes have the defects of high cost, complex preparation process, poor stability and the like. In addition, a polymer binder is needed to fix the electrode modification layer on the surface of the electrode in the preparation process, so that the series resistance is increased, and the catalytic activity is reduced. Therefore, the preparation of a high-performance self-supporting electrode for nitrite detection is a major concern.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a nitrite electrochemical sensor based on carbon fiber paper, a preparation method and application thereof, and solves the problems of high cost, complex preparation method, low sensitivity, poor stability and the like of the conventional nitrite electrochemical sensor.
In order to achieve the purpose, the invention adopts the following technical scheme:
firstly, the invention discloses application of carbon fiber paper in nitrite detection, and the carbon fiber paper is used as a working electrode for nitrite detection.
The invention discloses a preparation method of a carbon fiber paper working electrode, which comprises the following steps: and cleaning impurities on the surface of the carbon fiber paper, drying, preserving heat in the air for 1-3 h at 500-700 ℃, and naturally cooling to room temperature to obtain the carbon fiber paper working electrode.
Specifically, the carbon fiber paper is washed by using an absolute ethyl alcohol solution and an acetone solution respectively.
Specifically, the drying temperature is 50-70 ℃, and the drying time is 15-30 min.
The invention also discloses a nitrite electrochemical sensor based on the carbon fiber paper, which comprises a working electrode, a counter electrode and a reference electrode, wherein the working electrode is the carbon fiber paper.
Specifically, the carbon fiber paper is subjected to oxidation annealing treatment at 500-700 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified carbon fiber paper is used as the working electrode of the nitrite electrochemical sensor for detecting nitrite, the response time of the electrode is fast (1s), and the sensitivity is high (930.4 muA mM)-1cm-2) The linear response range is wide (0.1-3838.5 mu M), the detection lower limit is low (0.1 mu M), and the prepared electrochemical sensor has high specificity, excellent long-term stability and repeatability and strong anti-interference capability on nitrite detection.
(2) The working electrode only needs high temperature one-step oxidation, no complex synthesis treatment process is needed, the preparation process is simple, and the problems of increase of series resistance and reduction of catalytic activity caused by the fact that a polymer binder is needed to fix the electrode modification layer on the surface of the electrode in the existing preparation process are solved.
Drawings
Fig. 1 is a schematic diagram of the principle of a modified carbon fiber paper electrochemical sensor.
FIG. 2 is a scanning electron micrograph of the modified carbon fiber paper of example 1.
FIG. 3 is a cyclic voltammogram of the modified carbon fiber paper of example 1 and the unoxidized carbon fiber paper of comparative example 1 in a nitrite solution.
FIG. 4 is a linear relationship between different concentrations of nitrite and response current density in example 1.
FIG. 5 is a graph of current versus time for the effect of interfering substances on the electrochemical determination of nitrite in example 1, wherein a is sodium nitrite; b is potassium nitrate; c is ammonium acetate; d is magnesium sulfate; e is sodium silicate; f is zinc sulfate; g is sodium carbonate; h is calcium chloride; i is glucose.
FIG. 6 is a data statistics chart of the stability and repeatability of the oxidized carbon fiber paper electrochemical sensor of example 1.
The invention is described in detail below with reference to the drawings and the detailed description.
Detailed Description
The nitrite electrochemical sensor comprises a working electrode, a counter electrode and a reference electrode, wherein a platinum wire and the like are selected as the counter electrode, a motor existing in the market at present such as saturated calomel and the like is selected as the reference electrode, and the working electrode is carbon fiber paper in the invention.
The carbon fiber paper used in the invention is commercially available carbon fiber paper, and the microstructure of the carbon fiber paper is a carbon fiber structure.
The carbon fiber paper is used as a carbon-based material with a three-dimensional macroporous skeleton, has the advantages of rich pore structure, environmental friendliness, good conductivity, stability, high temperature resistance, feasibility of surface chemical modification and the like. The invention uses the carbon fiber paper as the working electrode in the nitrite electrochemical detection. Compared with the traditional nitrite electrochemical sensor, the electrochemical sensor provided by the invention has the advantages of no complex synthesis treatment process, low cost and simplicity in operation. It can be seen from the example results that the working electrode of the present invention has better electrocatalytic activity.
The carbon fiber paper used in the invention is subjected to oxidation annealing treatment at 500-700 ℃, so that the carbon defect degree, oxygen-containing functional groups, roughness and wettability of the surface of the carbon fiber paper are improved.
When the carbon fiber paper is used as a working electrode, the prepared carbon fiber paper is cut into paper sheets, and the size and the shape of the paper sheets are not limited and can be adjusted according to needs.
The preparation process of the nitrite electrochemical sensor comprises the following steps:
step 1, preparing modified carbon fiber paper
Cleaning the carbon fiber paper by using an absolute ethyl alcohol solution and an acetone solution to remove impurities such as dust, insoluble grease and the like on the surface of the carbon fiber paper, then cleaning the carbon fiber paper by using deionized water, and drying the carbon fiber paper for 15-30 min at 50-70 ℃;
and (3) preserving the heat of the treated carbon fiber paper in the air at 500-700 ℃ for 1-3 h, and naturally cooling to room temperature to obtain the modified carbon fiber paper.
Step 2, preparing the nitrite electrochemical sensor
The modified carbon fiber paper is used as a working electrode, a standard three-electrode system is formed by the working electrode, a counter electrode and a reference electrode, and the three electrodes are respectively connected with an electrochemical workstation.
The carbon fiber prepared by the invention is used for detecting nitrite, and the specific process is as follows: and inserting standard three electrodes (a working electrode, a counter electrode and a reference electrode) into the PBS buffer solution, adding nitrite solution into the PBS buffer solution which is continuously stirred, and measuring electrochemical data through a current-time curve. Electrochemical studies in the examples show that the high-temperature annealed carbon fiber paper electrode has fast response time (1s) and high sensitivity (930.4 muA mM)-1cm-2) The electrochemical sensor has the advantages of wide linear response range (0.1-3838.5 mu M) and minimum detection lower limit (0.1 mu M), and has high specificity, excellent long-term stability and repeatability for nitrite detection.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1
Step 1, cleaning carbon fiber paper by using an absolute ethyl alcohol solution and an acetone solution, then cleaning by using deionized water, and drying for 30min at 60 ℃;
and (3) preserving the treated carbon fiber paper at 700 ℃ in the air for 2h, and naturally cooling to room temperature to obtain the modified carbon fiber paper, wherein a scanning electron microscope image of the obtained modified carbon fiber paper is shown in fig. 2.
Step 2, taking the modified carbon fiber paper as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum wire electrode as a counter electrode, and taking the area of the working electrode as 0.5 x 0.5cm2Each electrode is connected to an electrochemical workstation.
Testing catalytic oxidation performance of the carbon fiber paper working electrode on nitrite:
0.1M PBS buffer (pH 7.0) was prepared, added to the three-electrode cell of this example, and subjected to cyclic voltammetry at 50mV s-1The electrode was subjected to a catalytic oxidation performance test in a solution containing 1.0mM nitrite, and the test results are shown in fig. 3.
Testing the sensing performance of the nitrite electrochemical sensor based on the carbon fiber paper:
the three-electrode system of this example was inserted into 0.1M PBS buffer (pH 7.0), nitrite solutions of different concentrations were added to the continuously stirred PBS buffer every 100s under an applied potential of 0.8V, and electrochemical data were measured by a current-time curve. The test results are shown in FIG. 4, and the detection range of the present embodiment is within the nitrite concentration range of 0.1 μ M to 3838.5 μ M, which indicates that the electrochemical sensor based on oxidized carbon fiber paper of the present invention has a good detection performance for nitrite.
Testing the specific performance of the nitrite electrochemical sensor based on the carbon fiber paper:
the three-electrode system of this example was inserted into 0.1M PBS buffer (pH 7.0) and 50-fold and 100-fold nitrite concentration (2.5 μ M) of interfering substances were added at 50s intervals under an applied potential of 0.8V: potassium nitrate, ammonium acetate, magnesium sulfate, sodium silicate, zinc sulfate, sodium carbonate, calcium chloride and glucose, and the resulting current-time curve was recorded. The detection result is shown in fig. 5, and it can be seen that the electrochemical sensor based on the oxidized carbon fiber paper has excellent anti-interference capability for measuring nitrite.
Fourthly, testing the stability and the repeatability of the nitrite electrochemical sensor based on the carbon fiber paper:
the three-electrode system of this example was inserted into a 0.1M PBS bufferIn a solution (pH 7.0), cyclic voltammetry was carried out at 50mV s-1The same electrode was tested for stability in a solution containing 1.0mM nitrite for one month continuously. 6 different electrodes were independently prepared and tested for repeatability using the same method. The results are shown in fig. 6, and it can be seen that the electrochemical sensor based on carbon fiber paper has excellent stability and repeatability for the determination of nitrite.
Example 2
This example differs from example 1 in that: the oxidation temperature of the carbon fiber paper of this example was 500 ℃.
The surface of the oxidized carbon fiber paper of this example becomes relatively rough, but the degree of surface carbon defects, roughness, and wettability are inferior to those of the oxidized carbon fiber paper of example 1.
In addition, the performance of the electrochemical sensor for detecting nitrite of the embodiment, such as detection range, detection lower limit, response time, specificity, repeatability, stability, etc., is about the same as that of the electrochemical sensor for detecting nitrite of oxidized carbon fiber paper in embodiment 1, and there is no obvious difference.
Comparative example 1
This comparative example differs from example 1 in that: the carbon fiber of the present example was not subjected to the high-temperature oxidation treatment in step 1.
The catalytic oxidation performance test process for nitrite is the same as that of example 1, and the test result is shown in fig. 3, which shows that the oxidized carbon fiber paper electrode of example 1 has higher response current density and lower oxidation peak potential compared with the unoxidized carbon fiber paper electrode of the comparative example, and shows that the carbon fiber paper has higher capability of electrocatalytic oxidation for nitrite after being subjected to high-temperature oxidation treatment.
Comparative example 2
This comparative example differs from example 1 in that: the oxidation temperature of the carbon fiber paper is 800 ℃.
The oxidized carbon fiber paper obtained in this comparative example was inferior in mechanical strength to the oxidized carbon fiber paper in example 1. Because the oxidation temperature is higher and the material has limited high temperature bearing capacity, the carbon fiber paper of the comparative example has reduced mechanical strength, the use of the carbon fiber paper as a working electrode is influenced, and the preparation energy consumption is higher due to overhigh temperature.

Claims (4)

1. The application of the carbon fiber paper for detecting the nitrite is characterized in that the carbon fiber paper is used as a working electrode for detecting the nitrite, and the carbon fiber paper is processed by the following steps: and cleaning impurities on the surface of the carbon fiber paper, drying, keeping the temperature in the air for 2 hours at 500-700 ℃, and naturally cooling to room temperature to obtain the carbon fiber paper working electrode.
2. Use of the carbon fiber paper for detecting nitrite according to claim 1, wherein the carbon fiber paper is washed with an absolute ethanol solution and an acetone solution, respectively.
3. The application of the carbon fiber paper for detecting nitrite as claimed in claim 1, wherein the drying temperature is 50-70 ℃ and the drying time is 15-30 min.
4. The nitrite electrochemical sensor based on carbon fiber paper comprises a working electrode, a counter electrode and a reference electrode, and is characterized in that the working electrode is carbon fiber paper, and the carbon fiber paper is processed by the following steps: and cleaning impurities on the surface of the carbon fiber paper, drying, keeping the temperature in the air for 2 hours at 500-700 ℃, and naturally cooling to room temperature to obtain the carbon fiber paper working electrode.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008073167A2 (en) * 2006-08-24 2008-06-19 The University Of North Carolina At Chapel Hill Nitric oxide microsensors via fluorosilane-based xerogel membranes
WO2012125723A2 (en) * 2011-03-14 2012-09-20 The University Of North Carolina At Chapel Hill Microfluidic nitric oxide sensor
CN105403601A (en) * 2015-12-09 2016-03-16 浙江理工大学 A method of preparing a nitrite sensor by utilization of iron tetraamino phthalocyanine loaded by carbon paper
CN109750495A (en) * 2018-12-17 2019-05-14 山东大学 A kind of porosity and the controllable porous carbon fiber and preparation method thereof of aperture structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008073167A2 (en) * 2006-08-24 2008-06-19 The University Of North Carolina At Chapel Hill Nitric oxide microsensors via fluorosilane-based xerogel membranes
WO2012125723A2 (en) * 2011-03-14 2012-09-20 The University Of North Carolina At Chapel Hill Microfluidic nitric oxide sensor
CN105403601A (en) * 2015-12-09 2016-03-16 浙江理工大学 A method of preparing a nitrite sensor by utilization of iron tetraamino phthalocyanine loaded by carbon paper
CN109750495A (en) * 2018-12-17 2019-05-14 山东大学 A kind of porosity and the controllable porous carbon fiber and preparation method thereof of aperture structure

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Chunmei Liu et al..Enhancing the Performance of Microfluidic Fuel Cells by Modifying the Carbon-Fiber Paper Cathode by Air Annealing and Acid Oxidation.《Ind. Eng. Chem. Res.》.2018, *
Enhancing the Performance of Microfluidic Fuel Cells by Modifying the Carbon-Fiber Paper Cathode by Air Annealing and Acid Oxidation;Chunmei Liu et al.;《Ind. Eng. Chem. Res.》;20180911;第2节 *
High-performance electrochemical nitrite sensing enabled using commercial carbon fiber cloth;Yi Zhang et al.;《Inorg. Chem. Front.》;20190416;第6卷;第1502页左栏第2段、第1505页左栏第2段及图2-3 *
Yi Zhang et al..High-performance electrochemical nitrite sensing enabled using commercial carbon fiber cloth.《Inorg. Chem. Front.》.2019,第6卷 *

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