CN110376258A - 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 PDFInfo
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- CN110376258A CN110376258A CN201910599144.6A CN201910599144A CN110376258A CN 110376258 A CN110376258 A CN 110376258A CN 201910599144 A CN201910599144 A CN 201910599144A CN 110376258 A CN110376258 A CN 110376258A
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Abstract
The invention discloses the nitrite electrochemical sensors based on carbon fiber paper, preparation method and application, the sensor includes carbon fiber paper working electrode, to electrode and reference electrode, the wherein preparation process of carbon fiber paper working electrode are as follows: the impurity of cleaning carbon fiber paper surface and drying first, then at 500~700 DEG C, 1~3h is kept the temperature in air, it is naturally cooling to room temperature, obtain modified carbon fiber paper, it is used for the carbon fiber paper working electrode of preparation to detect nitrite, electrode response time is fast, high sensitivity, linear response range is wide and Monitoring lower-cut is low, the electrochemical sensor of preparation detects specificity with higher to nitrite, excellent long-time stability and repeatability, and strong antijamming capability, and working electrode of the invention only needs one step of high temperature to aoxidize, no any complicated synthesis processing Process, preparation process are simple.
Description
Technical field
The invention belongs to electrochemical sensor technology fields, and in particular to a kind of nitrite electrification based on carbon fiber paper
Learn sensor, preparation method and application.
Background technique
Nitrite is excessively used as fertilizer and food additives in agricultural sector and industrial department, causes to underground water
Serious nitrite pollution causes serious harm to human health.With amino acid degradation reaction can occur for nitrite,
The nitrosamine for having strong carcinogenicity is generated, if the food of human body intake excessive addition nitrite, may result in siderosis red eggs
The generation of the illnesss such as the either blue infant syndrome of white disease, serious person are even dead.Due to the genotoxic potential of nitrite, determine
Amount analysis becomes more and more important, and traditional nitrite detection method is difficult to realize field quick detection.Therefore, one is established
The method of kind real practical is come to detect nitrite be vital.
In recent years, the analysis method for measuring nitrite mainly has spectroscopic methodology, chromatography and electrochemical process etc..Wherein, electric
Chemical analysis method with its high sensitivity, it is at low cost, easy to operate, can be received more and more attention the advantages that field assay.
Currently, electrode used in electrochemical analysis method detection nitrite is mostly by enzyme, metal material (metal, gold
Belong to oxide, metal sulfide, metal nitride nano particle etc.), metal organic frame, conducting polymer and carbon material (stone
Black alkene, carbon nanotube, carbon nano-particle, porous carbon) etc. be combined.However, there is with high costs, preparations for most of electrodes
The defects of process is complicated, and stability is poor.In addition, needing to fix electrode modification layer using polymeric binder during the preparation process
In electrode surface, so as to cause the increase of series resistance, catalytic activity decline.Therefore, a kind of high performance self-supporting is prepared
Detection of the electrode for nitrite becomes emphasis concerned by people.
Summary of the invention
In view of the drawbacks of the prior art and insufficient, the object of the present invention is to provide a kind of nitrite based on carbon fiber paper
Electrochemical sensor, preparation method and application solve with high costs, preparation existing for existing nitrite electrochemical sensor
The problems such as method is complicated, sensitivity is low, stability is poor.
To achieve the goals above, the present invention is realised by adopting the following technical scheme:
Firstly, the invention discloses the applications that carbon fiber paper is used to detect nitrite, using carbon fiber paper as work
Electrode detection nitrite.
The invention discloses a kind of preparation methods of carbon fiber paper working electrode, comprising: cleans the miscellaneous of carbon fiber paper surface
Matter is simultaneously dried, and 1~3h is kept the temperature in 500~700 DEG C, air, room temperature is naturally cooling to, obtains carbon fiber paper working electrode.
Specifically, being cleaned respectively using ethanol solution and acetone soln to carbon fiber paper.
Specifically, the drying temperature is 50~70 DEG C, drying time is 15~30min.
The invention also discloses a kind of nitrite electrochemical sensor based on carbon fiber paper, including it is working electrode, right
Electrode and reference electrode, the working electrode are carbon fiber paper.
Specifically, the carbon fiber paper is handled by 500~700 DEG C of oxidizing annealing.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention uses modified carbon fiber paper as the working electrode of nitrite electrochemical sensor, for detecting
Nitrite, electrode response time fast (1s), high sensitivity (930.4 μ A mM-1cm-2), linear response range it is wide (0.1~
3838.5 μM) and Monitoring lower-cut it is low (0.1 μM), the electrochemical sensor of preparation is with higher to nitrite detection special
Property, excellent long-time stability and repeatability and strong antijamming capability.
(2) working electrode of the invention only needs one step of high temperature to aoxidize, no any complicated synthesis treatment process, preparation process
Simply, it while solving and needs that electrode modification layer is fixed on electrode surface using polymeric binder in existing preparation process,
The problem of resulting in increase, the catalytic activity decline of series resistance.
Detailed description of the invention
Fig. 1 is the schematic illustration of modified carbon fiber paper electrochemical sensor.
Fig. 2 is the scanning electron microscope (SEM) photograph of modified carbon fiber paper in embodiment 1.
Fig. 3 is the circulation of 1 modified carbon fiber paper of embodiment and the non-carbon oxide fiber paper of comparative example 1 in nitrite solution
Voltammogram.
Fig. 4 is the linear relationship in embodiment 1 between various concentration nitrite and responsive current density.
Fig. 5 is the current versus time curve figure that interfering substance influences nitrite electrochemical gaging in embodiment 1, wherein
A is sodium nitrite；B is potassium nitrate；C is ammonium acetate；D is magnesium sulfate；E is sodium metasilicate；F is zinc sulfate；G is sodium carbonate；H is chlorine
Change calcium；I is glucose.
Fig. 6 is the stability of carbon oxide fiber paper electrochemical sensor and repeated data statistics figure in embodiment 1.
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Specific embodiment
Nitrite electrochemical sensor in the present invention includes working electrode, to electrode and reference electrode, wherein selecting
Platinum filament etc. is as to electrode, and being saturated calomel etc., for existing motor as reference electrode, working electrode is the present invention on the market at present
In carbon fiber paper.
The carbon fiber paper that the present invention uses is commercially available carbon fiber paper, and microstructure is carbon fiber structural.
For carbon fiber paper as the carbon-based material with three-dimensional big hole on framework, pore structure is abundant, environmental-friendly, has good
Electric conductivity, stability, heat-resisting quantity and the advantages that the feasibility of surface chemical modification.The present invention is by making carbon fiber paper
For the working electrode in nitrite Electrochemical Detection.Relative to traditional nitrite electrochemical sensor, electricity of the invention
Chemical sensor synthesizes treatment process without any complexity, low in cost, easy to operate.It can be seen that this by embodiment result
The working electrode of invention has better electro catalytic activity.
The carbon fiber paper that the present invention uses is handled by 500~700 DEG C of oxidizing annealing, improves carbon fiber paper surface
Carbon defects degree, oxygen-containing functional group, roughness and degree of wetting.
When carbon fiber paper of the invention is as working electrode, the carbon fiber paper prepared is cut to the scraps of paper, the scraps of paper
Size and shape do not limit to, as needed adjust.
The preparation process of nitrite electrochemical sensor of the invention includes:
Step 1, modified carbon fiber paper is prepared
Carbon fiber paper is cleaned using ethanol solution and acetone soln, remove carbon fiber paper surface dust,
The impurity such as insoluble grease, are then cleaned up with deionized water, in 50~70 DEG C of 15~30min of drying；
The carbon fiber paper handled well is kept the temperature into 1~3h in 500~700 DEG C, air, room temperature is naturally cooling to, is changed
Carbon fiber paper after property.
Step 2, nitrite electrochemical sensor is prepared
Using modified carbon fiber paper as working electrode, a standard three electrode system is formed with to electrode, reference electrode, it will
Three electrodes are connect with electrochemical workstation respectively.
Carbon fiber prepared by the present invention is used to detect nitrite, detailed process are as follows: by standard three electrode (work electricity
Pole, to electrode and reference electrode) insertion PBS buffer solution in, nitrite solution is added to continuously stir PBS buffering it is molten
In liquid, by current versus time curve, electrochemical data is measured.Shown by the electrochemical research in embodiment through high annealing
Carbon fiber paper electrode response time fast (1s), high sensitivity (930.4 μ A mM-1cm-2), linear response range it is wide (0.1~
3838.5 μM) and lowest detection lower limit (0.1 μM), the electrochemical sensor is with higher to nitrite detection special
Property, excellent long-time stability and repeatability.
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to following specific embodiments
In, all equivalent transformations made on the basis of the technical solutions of the present application each falls within protection scope of the present invention.
Embodiment 1
Step 1, carbon fiber paper is cleaned using ethanol solution and acetone soln, is then cleaned with deionized water
Completely, in 60 DEG C of drying 30min；
The carbon fiber paper handled well is kept the temperature into 2h in 700 DEG C, air, room temperature is naturally cooling to, obtains modified carbon
Fibrous paper is illustrated in figure 2 the scanning electron microscope (SEM) photograph of the modified carbon fiber paper of acquisition.
Step 2, using modified carbon fiber paper as working electrode, saturated calomel electrode is reference electrode, and platinum electrode is pair
Electrode, the area of working electrode are 0.5*0.5cm2, each electrode is connected with electrochemical workstation.
1. carbon fiber paper working electrode tests the catalytic oxidation performance of nitrite:
The PBS buffer solution (pH=7.0) for preparing 0.1M, is added in three electrode electrolysers of the present embodiment, passes through circulation
Voltammetry, with 50mV s-1Sweep speed, containing carrying out catalytic oxidation performance survey to electrode in 1.0mM nitrite solution
Examination, test results are shown in figure 3.
2. the sensing capabilities of the nitrite electrochemical sensor based on carbon fiber paper are tested:
The three-electrode system of the present embodiment is inserted into the PBS buffer solution (pH=7.0) of 0.1M, in the outer power-up of 0.8V
Under position, the nitrite solution of various concentration is added in the PBS buffer solution continuously stirred every 100s, passes through electric current-
Time graph measures electrochemical data.Test result is shown in Fig. 4, Asia of the detection range of the present embodiment at 0.1 μM~3838.5 μM
Within the scope of nitrate concentration, illustrating that the present invention is based on the electrochemical sensors of carbon oxide fiber paper has preferably nitrite
Detection performance.
3. the specific performance of the nitrite electrochemical sensor based on carbon fiber paper is tested:
The three-electrode system of the present embodiment is inserted into the PBS buffer solution (pH=7.0) of 0.1M, in the outer power-up of 0.8V
Under position, the interfering substance of 50 times and 100 times nitrite concentrations (2.5 μM): potassium nitrate, ammonium acetate, sulphur is separately added into every 50s
Sour magnesium, sodium metasilicate, zinc sulfate, sodium carbonate, calcium chloride and glucose, the current versus time curve recorded.Testing result is shown in figure
5, it can be seen that the electrochemical sensor based on carbon oxide fiber paper has excellent anti-interference energy to the measurement of nitrite
Power.
4. the stability and reperformance test of the nitrite electrochemical sensor based on carbon fiber paper:
By in the PBS buffer solution (pH=7.0) of the three-electrode system insertion 0.1M of the present embodiment, pass through cyclic voltammetric
Method, with 50mV s-1Continuous one month of sweep speed containing carrying out stability to same electrode in 1.0mM nitrite solution
Test.Using identical method, independently prepared 6 different electrodes carry out reperformance test to it.Testing result is shown in Fig. 6, can
To find out, the measurement of nitrite is had excellent stability based on the electrochemical sensor of carbon fiber paper and repeated.
Embodiment 2
The present embodiment the difference from embodiment 1 is that: the oxidizing temperature of the present embodiment carbon fiber paper be 500 DEG C.
The carbon oxide fiber paper surface of the present embodiment becomes relative coarseness, but its surface carbon defect level, degree of roughness with
And degree of wetting is not as good as the carbon oxide fiber paper in embodiment 1.
In addition, the performance such as detection range of the nitrite electrochemical sensor detection nitrite of the present embodiment, detection
Lower limit, response time, specificity, repeatability and stability etc. and the carbon oxide fiber paper nitrite electrochemistry in embodiment 1
Sensor is roughly the same, no significant difference.
Comparative example 1
This comparative example the difference from embodiment 1 is that: the carbon fiber of the present embodiment does not carry out the high-temperature oxydation in step 1
Processing.
To the catalytic oxidation performance test process of nitrite with embodiment 1, test results are shown in figure 3, it can be seen that
The carbon oxide fiber paper electrode of embodiment 1 has higher response electricity compared to the unoxidized carbon fiber paper electrode of this comparative example
Current density and lower oxidation spike potential show its carbon fiber paper electrocatalytic oxidation with higher after high temperature oxidation process
Nitrite ability.
Comparative example 2
This comparative example the difference from embodiment 1 is that: the oxidizing temperature of carbon fiber paper be 800 DEG C.
The carbon oxide fiber paper mechanical strength obtained in this comparative example is not as good as the carbon oxide fiber paper in embodiment 1.Due to
It is limited that oxidizing temperature is higher, material itself bears high temperature capabilities, therefore this comparative example carbon fiber paper mechanical strength reduces, and influences it
As the use of working electrode, and temperature is excessively high that will lead to preparation energy consumption higher.
Claims (6)
1. the application that carbon fiber paper is used to detect nitrite, which is characterized in that detected using carbon fiber paper as working electrode sub-
Nitrate.
2. the preparation method of carbon fiber paper working electrode characterized by comprising clean the impurity of carbon fiber paper surface and baking
It is dry, 1~3h is kept the temperature in 500~700 DEG C, air, is naturally cooling to room temperature, is obtained carbon fiber paper working electrode.
3. the preparation method of working electrode as claimed in claim 2, which is characterized in that use ethanol solution and third respectively
Ketone solution cleans carbon fiber paper.
4. the preparation method of working electrode as claimed in claim 2, which is characterized in that the drying temperature is 50~70
DEG C, drying time is 15~30min.
5. a kind of nitrite electrochemical sensor based on carbon fiber paper, including working electrode, to electrode and reference electrode,
It is characterized in that, the working electrode is carbon fiber paper.
6. the nitrite electrochemical sensor based on carbon fiber paper as claimed in claim 5, which is characterized in that the carbon
Fibrous paper is handled by 500~700 DEG C of oxidizing annealing.
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Citations (4)
| 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 |
-
2019
- 2019-07-04 CN CN201910599144.6A patent/CN110376258B/en active Active
Patent Citations (4)
| 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 (2)
| 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.》 * |
| YI ZHANG ET AL.: "High-performance electrochemical nitrite sensing enabled using commercial carbon fiber cloth", 《INORG. CHEM. FRONT.》 * |
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