CN115818590B - Carbon nitride oxide/bismuth oxide composite electrode, preparation method thereof and Cl (copper oxide) composite electrode － Application in detection - Google Patents
Carbon nitride oxide/bismuth oxide composite electrode, preparation method thereof and Cl (copper oxide) composite electrode － Application in detection Download PDFInfo
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Abstract
The invention relates to a carbon nitride oxide/bismuth oxide composite electrode, a preparation method thereof and a preparation method thereof in Cl － The application in detection comprises the following steps: (1) Dispersing graphite-phase carbon nitride in concentrated sulfuric acid, stirring, adding a main oxidant under ice bath conditions, mixing for reaction, then dripping water, adding an auxiliary oxidant for reaction, and carrying out solid-liquid separation to obtain carbon nitride oxide; (2) Grinding and mixing carbon nitride oxide and bismuth oxide uniformly, adding chitosan, and grinding and mixing uniformly again to obtain a modified material; (3) And mixing the modification material with water to prepare a suspension, coating the suspension on the surface of the clean glassy carbon electrode, and airing to obtain the carbon nitride oxide/bismuth oxide composite electrode. The sensor is used as a volt-ampere sensor and is arranged in an electrolytic cell of a three-electrode system, and the base solution contains different chloride ionsThe concentration of PBS buffer solution is regulated to be acidic, and the concentration of trace chloride ions in the base solution is detected by cyclic voltammetry scanning and differential pulse voltammetry, so that the method has better response.
Description
Technical Field
The invention relates to the technical field of preparation of functional materials, in particular to a carbon nitride oxide/bismuth oxide composite electrode, a preparation method thereof and a preparation method thereof in Cl － Application in detection.
Background
Cl － By mixing with water containing Na + 、Ca 2+ 、Mg 2+ 、K + Phosphate ions of various metal salts interact simultaneously to form multi-metal chlorides, so that the groundwater of most lakes on the earth naturally forms a sedimentary stratum containing chloride salt ore deposits, and the water environment is seriously affected. The content of chloride ions exceeds the standard, so that huge harm is caused to living organisms, industrial production and ecological sustainability, the standard of detecting the chloride ions by human beings is higher and higher, and accurate measurement of the concentration of the chloride ions is a current urgent need.
The method for quantitatively detecting the concentration of chloride ions in water widely comprises a volume method, a potentiometric titration method, an electrochemical analysis method, a mercury amount method, a silver chloride visual turbidimetry method, a capillary electrophoresis method, an ion chromatography method and the like. Different Cl － The detection method has different applications, fields and detection precision, and each method has advantages and disadvantages. The end point of the volume method is insensitive, the operation requirement is strict, and the anti-interference capability is weak; the end of the nitrate mercury titration method has more discoloration, is more acute than silver nitrate titration, but is more influenced by the acidity of a tested sample; the mercury assay, although endpoint was evident, was Hg 2+ The toxicity is high, and meanwhile, the method can also cause pollution of heavy metal ions such as mercury and the like; ion chromatography has high sensitivity and selectivity, but has high analysis cost, the chromatographic column is easy to adsorb impurities, the permanent adsorption can cause the adsorption capacity of the separation column to be reduced, and the method is not suitable for the determination of quality test liquid and is difficult to useIs popular. Among the processing methods, the electrochemical analysis technology has the advantages of simple measurement method, rapid analysis, high sensitivity, low price of large analytical instrument and the like, can realize measurement by converting chemical parameters and chemical quantities which are difficult to directly measure and interpret into simple and easily-measured electrochemical parameters, and can obtain experimental data in an instant mode by transmitting the quick-converted electric signals to a computer for quantitative analysis while reacting. These advantages make electrochemical analysis technology a long-standing technique. Among them, electrochemical sensor possesses advantages such as intellectuality, informatization, microminiaturization and integration, and extremely high selectivity is the biggest characteristic of this kind of detection sensor. Many technologies related to electrochemical sensors in China are developed and mature, and particularly chip technologies, ultramicroelectrodes, multichannel technologies and combination technologies are marked that the electrochemical technologies in China reach international levels.
Graphite phase carbon nitride (g-C) 3 N 4 ) The nano-sheet has unique electrical characteristics and chemical stability, and has wide application prospect in the fields of environmental management and energy conversion. The surface of the modified polyurethane is rich in a large amount of oxygen-containing functional groups, and active sites are provided for chemical modification. In terms of cost, two-dimensional g-C 3 N 4 The nano-sheet has the advantages of easily available raw materials, low price and the like. Development of green, economical and efficient g-C 3 N 4 The nano sheet stripping strategy and the synthesis method are hot spot problems in the fields of catalysis, energy and materials. Bismuth oxide Bi 2 O 3 The crystal lattice has 1/4 oxygen ion position in the crystal lattice and thus has very high oxygen ion conducting performance, and may be used in making various solid oxide fuel cell, oxygen sensor, etc.
How to compound graphite phase carbon nitride with bismuth oxide to obtain electrode and apply the electrode as a sensor and trace Cl - The detection of (a) is a technical problem to be solved by the invention.
Disclosure of Invention
In order to solve the technical problems, the invention provides a carbon nitride oxide/bismuth oxide composite electrode, a preparation method thereof and a preparation method thereof in Cl － Application in detection. The invention is achieved by reacting highly oxidized nitrogenThe carbon nano-sheet is compounded with bismuth oxide, and the compound is modified on an electrode to prepare the volt-ampere sensor, so that the sensor has good responsiveness to the concentration of trace chloride ions in water, and can detect the trace chloride ions in water.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the preparation method of the carbon nitride oxide/bismuth oxide composite electrode comprises the following steps:
(1) Dispersing graphite-phase carbon nitride in concentrated sulfuric acid, stirring, adding a main oxidant under ice bath conditions, mixing for reaction, then dripping water, adding an auxiliary oxidant for reaction, and carrying out solid-liquid separation to obtain carbon nitride oxide;
(2) Grinding and mixing carbon nitride oxide and bismuth oxide uniformly, adding chitosan, and grinding and mixing uniformly again to obtain a modified material;
(3) And mixing the modification material with water to prepare a suspension, coating the suspension on the surface of a clean glassy carbon electrode, and airing to obtain the carbon nitride oxide/bismuth oxide composite electrode.
Further, the concentration of the graphite-phase carbon nitride in the concentrated sulfuric acid in the step 1 is 0.02-0.05g/mL; the main oxidant is potassium permanganate; the auxiliary oxidant is hydrogen peroxide with volume concentration of 5%; the dosage ratio of the graphite phase carbon nitride, the potassium permanganate and the water is 1g to 1.2g to 200mL.
Further, the reaction time after the main oxidant is added in the step 1 is 40-70min; the auxiliary oxidant is added in an amount such that the reaction system appears milky.
Further, in the step 2, the mass ratio of the carbon nitride oxide to the bismuth oxide to the chitosan is 4-6:1:1.
Further, the concentration of the modifying material in the suspension in the step 3 is 0.012-0.016g/mL.
Further, in the step 3, the coating amount of the suspension on the surface of the glassy carbon electrode is 3-8 mu L.
The application of 3-8 microliters of suspended liquefied carbon/bismuth oxide, preferably 5-7 microliters, works best.
In another aspect, the invention provides a carbon nitride oxide/bismuth oxide composite electrode obtained by the preparation method.
In the last aspect, the invention provides the oxidized carbon nitride/bismuth oxide composite electrode obtained by the preparation method in trace Cl - In the application of detection, the carbon nitride oxide/bismuth oxide composite electrode is used as a voltammetry sensor to be placed in an electrolytic cell of a three-electrode system, a base solution is PBS buffer solutions containing different chloride ion concentrations, the pH value is regulated to be an acidic condition, and the chloride ion concentration in the base solution is detected by cyclic voltammetry scanning and utilizing a differential pulse voltammetry.
Further, the concentration of the PBS buffer is 0.1M, pH =7.4; the acidic condition is ph=2.5-4, preferably the acidic condition is 3; the condition of cyclic voltammetry scanning is that the enrichment potential is-0.3V to-0.1V and the enrichment time is 50s to 200s; preferably, the enrichment potential is-0.2V and the enrichment time is 100s.
Further, the linear range of the chloride ion concentration in the water which can be detected by using the carbon nitride oxide/bismuth oxide composite electrode as a volt-ampere sensor is 1.0 multiplied by 10 -4 About 0.1mol/L, and the detection limit is 8.9X10 -5 mol/L。
The beneficial technical effects are as follows:
CNO/Bi prepared by the invention 2 O 3 The composite electrode used as the volt-ampere sensor for measuring trace chloride ions has the advantages of economy, practicality, easy operation, small secondary pollution, high sensitivity and the like, and can effectively, accurately and rapidly detect the chloride ions. CNO/Bi prepared by the invention 2 O 3 The composite electrode has the advantages that a large number of oxygen-containing functional groups are provided on the surface of the oxidized carbon nitride, the specific surface area of the composite material is increased, the adsorption of bismuth oxide to chloride ions is enhanced, the bismuth oxide and the chloride ions have synergistic effect, more active sites are provided for the determination of the chloride ions, and the surface of the electrode is greatly improved for anionic Cl — Is a rich property of (3).
Drawings
Fig. 1 is an XRD pattern of the oxidized carbon nitride/bismuth oxide composite material obtained in step 2 of example 1.
FIG. 2 is an EDS diagram of the oxidized carbon nitride/bismuth oxide composite electrode prepared in example 1.
FIG. 3 is a CV plot of the response of electrodes of different modified materials to 0.1mol/L chloride ions.
FIG. 4 is a graph of various experimental parameters of chlorine ion concentration detection and chlorine ion dissolution peak current for a carbon nitride oxide/bismuth oxide composite electrode, wherein (a) is an enrichment potential-dissolution peak current graph; (b) enriching a time-dissolution peak current profile; (c) a bottom pH-dissolution peak current profile; (d) And (3) a graph of the dosage of the suspension on the glassy carbon electrode and dissolution peak current.
FIG. 5 is a graph of DPV obtained by detecting different chloride ion concentrations by using a carbon nitride oxide/bismuth oxide composite electrode as a voltammetric sensor; wherein the a curve represents the chloride ion concentration of 0.0001mol/L, the b curve represents the chloride ion concentration of 0.001mol/L, the c curve represents the chloride ion concentration of 0.01mol/L, and the d curve represents the chloride ion concentration of 0.1mol/L.
Fig. 6 is an SEM image of the oxidized carbon nitride/bismuth oxide composite electrode of example 1 after enrichment of chloride ions.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the national standard is not corresponding, the method is carried out according to the general international standard or the standard requirements set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
The bismuth oxide used in the examples below is commercial bismuth oxide; or bismuth nitrate and sodium hydroxide are adopted to carry out precipitation reaction, and then the bismuth oxide is obtained after heating and dehydration.
The graphite phase carbon nitride used in the examples below was a commercial graphite phase carbon nitride; or the melamine is calcined in a muffle furnace, the calcining parameters are not different from those disclosed in the prior art, and the melamine is heated to 550 ℃ at a heating rate of 5 ℃/min and calcined for 3 hours.
The concentration of concentrated sulfuric acid used below was 98wt%.
Example 1
The preparation method of the carbon nitride oxide/bismuth oxide composite electrode comprises the following steps:
(1) Dispersing 1g of graphite phase carbon nitride in 30mL of concentrated sulfuric acid, adding 1.2g of potassium permanganate under stirring and ice bath conditions, mixing and stirring for reaction for 1h, then dropwise adding 200mL of ultrapure water, dropwise adding hydrogen peroxide with volume concentration of 5% until the reaction system is milky, and obtaining carbon nitride oxide after solid-liquid separation;
(2) Grinding and mixing 2.4g of carbon nitride oxide and 0.5g of bismuth oxide uniformly, adding 0.5g of chitosan as an adhesive to enable materials to be highly compounded, grinding and mixing uniformly again, and drying to obtain a modified material, wherein the modified material is the carbon nitride oxide/bismuth oxide composite material, and the XRD pattern of the composite material is shown in figure 1;
as can be seen from XRD patterns, the composite material contains Bi 2 O 3 And oxidation C 3 N 4 The diffraction peaks 2 theta are 25.644 degrees and 27.857 degrees, which correspond to the (310) crystal face and the (110) crystal face respectively, and the X-ray diffraction intensity of the two crystal faces is very high, which indicates Bi in a sample 2 O 3 And oxidation C 3 N 4 High content, so that the complex can be usedCNO/Bi with higher purity prepared from composite material 2 O 3 Is a composite electrode of (a);
(3) Mixing the modification material with water to prepare 250mL of suspension (the concentration of the suspension is about 0.0136 g/mL), uniformly coating 6 mu L of the suspension on the surface of the polished, polished and activated glassy carbon electrode, and airing to obtain the oxidized carbon nitride/bismuth oxide composite electrode; as shown in FIG. 2, the EDS graph of the composite electrode shows that the EDS surface of the oxidized carbon nitride/bismuth oxide composite electrode scans CNO/Bi on the surface of the glassy carbon electrode 2 O 3 The main elements of the composite material are Bi, O, C, N, the atomic percentages of which are 41.1%, 35.5%, 14.0%, 11.3%, bi and O are present in large amounts, and the relatively small amounts of C and N indicate that the majority of Bi is present in the composite material 2 O 3 And is doped with oxidized carbon nitride nanoplates.
The polishing process of the glassy carbon electrode is as follows: before polishing, the surface of the glassy carbon electrode needs to be lightly wiped by wet lens paper to remove dirt and ensure the smooth surface of the electrode; the glassy carbon electrode is rubbed and rotated back and forth on the velvet paper in a 8 shape (aluminum oxide powder is needed on the velvet paper, water is sprayed on the velvet paper), the steps are repeated after polishing for 10min, the aluminum oxide powder with the particle size (1 mu m, 0.3 mu m and 0.05 mu m in sequence) is replaced, distilled water is used for cleaning the surface of the glassy carbon after polishing, pure water, nitric acid and ethanol are used for washing in sequence, and ultra-pure water and absolute ethyl alcohol are used for ultrasonic cleaning. And then activating: connecting the polished electrode with an electrochemical workstation through three electrodes; preparing potassium ferricyanide PBS solution for voltammetric scanning (ensuring that the potential difference is within 100 mV), and obtaining the polished, polished and activated clean glassy carbon electrode by cycling the potassium ferricyanide PBS solution for 20 times within the range of-0.8 to +0.8V.
Comparative example 1
The comparative example is a bare glassy carbon electrode.
Comparative example 2
In this comparative example, bismuth oxide was used as a modifier for a glassy carbon electrode, and the composite electrode was the same as in step 3 of example 1.
Comparative example 3
In the comparative example, carbon nitride oxide is used as a modification material of a glassy carbon electrode, the preparation process of the carbon nitride oxide is the same as that in step 1 of the embodiment 1, and then a composite electrode is directly prepared and is the same as that in step 3 of the embodiment 1.
Example 2
And (5) searching the optimal conditions for detecting the chloride ions by using a cyclic voltammetry method.
(1) With enrichment potential as a variable
The carbon nitride oxide/bismuth oxide composite electrode (the preparation process is the same as that of the example 1, the coating amount of the suspension is 6 mu L) is taken as a voltammetric sensor to be placed in an electrolytic cell of a three-electrode system, the base solution is 250mL of PBS buffer solution containing 0.1mol/LNaCl, the pH value is adjusted to be 5, cyclic voltammetry scanning is carried out under the condition that the enrichment potential range is-0.8 to-0.1V, so that the carbon nitride oxide/bismuth oxide composite electrode enriches chloride ions for 100s, and finally, an enrichment potential-dissolution peak current curve graph of the composite electrode for the chloride ions is obtained, and the result is shown in (a) of fig. 4.
As shown in FIG. 4 (a), cl was added when the enrichment potential was changed from-0.1V to-0.2V － The elution peak current of (2) gradually increases because Cl when the electrode potential becomes negative － Can be effectively deposited on the surface of the electrode, so that Cl － The elution peak current of (2) increases. When the enrichment potential is-0.2V, the dissolution peak current reaches the maximum value, and the potential continues to move negatively, so that the peak current is reduced, and the reason is probably that the reduction of other substances in the solution, particularly the precipitation of hydrogen, generates huge interference, so that the peak current is reduced. The results showed the best enrichment potential to be-0.2V.
(2) With enrichment time as a variable
The carbon nitride oxide/bismuth oxide composite electrode (the preparation process is the same as that of the example 1, the coating amount of the suspension is 6 mu L) is taken as a voltammetric sensor to be placed in an electrolytic cell of a three-electrode system, the base solution is 250mL of PBS buffer solution containing 0.1mol/LNaCl, the pH value is adjusted to be 5, cyclic voltammetry scanning is carried out at the enrichment potential of-0.2V, so that the chlorine ions are enriched by the carbon nitride oxide/bismuth oxide composite electrode, the enrichment time is 50s, 100s, 200s, 300s and 400s, and finally a chlorine ion enrichment time-dissolution peak current curve graph of the composite electrode is obtained, and the result is shown in (b) of fig. 4.
As shown in FIG. 4 (b), the enrichment time was 50-400s, and the relationship between the elution peak current and time was studied. The results show that the longer the enrichment time, the Cl deposited on the electrode surface － The more the dissolution peak current is, the more Cl is deposited on the electrode surface － The amount of (C) is also limited by the number of active sites on the electrode surface, and Cl is contained in the electrode when the enrichment time is less than 100s － The peak current increases linearly with the enrichment time, and decreases after the enrichment time exceeds 100s, probably because the electrode surface active sites have reached saturation, and continued enrichment results in Cl － Oxidized. Considering the relation between the enrichment effect and time, 100s is selected as the optimal enrichment time.
(3) Takes the pH value of the base solution during enrichment as a variable
The carbon nitride oxide/bismuth oxide composite electrode (the preparation process is the same as that of the example 1, the coating amount of the suspension is 6 mu L) is taken as a voltammetric sensor to be placed in an electrolytic cell of a three-electrode system, the base solution is 250mL of PBS buffer solution containing 0.1mol/LNaCl, the pH value is regulated to be 2.5-5.5, cyclic voltammetry scanning is carried out under the condition that the enrichment potential is-0.2V, so that the carbon nitride oxide/bismuth oxide composite electrode enriches chloride ions for 100s, and finally, the pH value-dissolution peak current curve graph of the base solution when the composite electrode enriches the chloride ions is obtained, and the result is shown in (c) of fig. 4.
As shown in FIG. 4 (C), when the pH value is changed from 2.5 to 5.5, the elution peak current increases with the increase of the pH value, and when the pH value is low, C 3 N 4 The hydrogen bond between the nitrogen atom and the hydrogen atom in the CNO leads to the reduction of the number of N active sites in the CNO, thereby weakening the reaction of Cl － And therefore the elution peak current is low. At pH above 3, because of Bi 3+ Hydrolysis results in Cl － The peak current decreases with increasing pH. The detection of chloride ions is more advantageous at a pH of 3.
(4) The coating amount of the suspension on the glassy carbon electrode is taken as a variable
The preparation process is the same as that of example 1, except that the coating amount of the suspension is 2-8 mu L), the carbon nitride/bismuth oxide composite electrode is used as a voltammetric sensor and placed in a three-electrode system electrolytic cell, the base solution is 250mL of PBS buffer solution containing 0.1mol/L NaCl, the pH value is regulated to be 3, cyclic voltammetry scanning is carried out under the voltage of-0.2V, so that the carbon nitride/bismuth oxide composite electrode enriches chloride ions for 100s, and finally, the enrichment-dissolution peak current curve graph of the carbon nitride/bismuth oxide composite electrode with different modification amounts on chloride ions is obtained, and the result is shown in (d) of fig. 4.
As shown in FIG. 4 (d), when the coating amount of the suspension is increased in the range of 2. Mu.L to 6. Mu.L, the peak current is increased with the increase of the modification amount, because the increase of the electrode surface modification amount increases the active area of the modified electrode to increase the active sites, electrostatic adsorption and complexing Cl － The capacity of (2) is enhanced, and the elution peak current is increased. CNO/Bi modified on glassy carbon electrode 2 O 3 When the suspension volume reached 6. Mu.L, the peak current of elution was maximum. Further increase in the amount of the suspension may cause the current in the electrolytic cell to fail to normally contact the electrode surface, resulting in a sharp decrease in the response value of the electrode to the base liquid. Thus contains CNO/Bi 2 O 3 The optimum condition is that the modified amount of the suspension is 6. Mu.L.
Example 3
The electrodes of example 1 and comparative examples 1-3 are used as voltammetric sensors and placed in an electrolytic cell of a three-electrode system, the base solution is 250mL of PBS buffer solution containing 0.1mol/L NaCl, the pH value is adjusted to 3, cyclic voltammetry scanning is carried out under the voltage of-0.2V, the electrodes of example 1 and comparative examples 1-3 are respectively used for enriching chloride ions for 100 seconds, and CV response diagrams of different electrodes to 0.1mol/L chloride ions are obtained, and the result is shown in figure 3.
As can be seen from fig. 3, the CV diagram of the bare glassy carbon electrode, bismuth oxide electrode, and carbon nitride oxide electrode for chlorine ion enrichment detection has no obvious oxidation-reduction peak, and cannot be used as a good chlorine ion concentration sensor. The carbon nitride oxide/bismuth oxide (CNO/Bi) of the present invention 2 O 3 ) The cyclic voltammogram of the composite electrode as a sensor shows that obvious oxidation-reduction peaks exist at the electrode potential of-0.47V and 0.08V in a CV curve, which indicates that the CNO/Bi prepared by the invention 2 O 3 The composite electrode has higher determination of the concentration of chloride ionsAnd (5) responding. The oxidized carbon nitride provides more oxygen-containing functional groups, increases the specific surface area of the material, enhances the adsorption of bismuth oxide to chloride ions, has synergistic effect, and is expected to be further used for measuring the chloride ions.
SEM observation was performed after enriching chloride ions on the carbon nitride oxide/bismuth oxide composite electrode of example 1, and the results are shown in FIG. 6, and SEM results further after detecting chloride ions indicate that CNO/Bi is present on the surface of the composite electrode 2 O 3 The composite material is mainly in a rod-shaped structure, has regular shape, is loaded with carbon nitride oxide nano particles, and is further oxidized after electrochemical reaction to form a highly oxidized carbon nitride oxide/bismuth oxide composite electrode.
Application example 1
The carbon nitride oxide/bismuth oxide composite electrode in example 1 is used as a voltammetry sensor to be placed in an electrolytic cell of a three-electrode system, a base solution is PBS buffer solution containing different chloride ion concentrations, pH value 3 is regulated, enrichment potential is-0.2V, cyclic voltammetry scanning is carried out under the enrichment time of 100s, and the linear range of the chloride ion concentration in the base solution is detected by using a differential pulse voltammetry. The DPV graph obtained by detecting different chloride ion concentrations with the carbon nitride oxide/bismuth oxide composite electrode of example 1 as a voltammetric sensor is shown in fig. 5, and a standard curve is obtained by calculating a dissolution peak current (the dissolution peak current represents a current released at a specific oxidation reaction voltage of chloride ions) and the chloride ion concentration, and fitting the calculated dissolution peak current and chloride ion concentration. The linear range of chloride ion concentration in the base solution can be detected to be 1.0X10 by differential pulse voltammetry -4 mol/L～1.0×10 -1 mol/L, detection limit (S/N=3) of 8.9X10 -5 mol/L。
The result shows that the composite electrode has extremely high sensitivity to trace-level chloride ion detection, and can be further applied to the determination of actual chloride ions.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The preparation method of the carbon nitride oxide/bismuth oxide composite electrode is characterized by comprising the following steps:
(1) Dispersing graphite-phase carbon nitride in concentrated sulfuric acid, stirring, adding a main oxidant under ice bath conditions, mixing for reaction, then dripping water, adding an auxiliary oxidant for reaction, and carrying out solid-liquid separation to obtain carbon nitride oxide;
the main oxidant is potassium permanganate; the auxiliary oxidant is hydrogen peroxide with volume concentration of 5%;
the reaction time after the main oxidant is added is 40-70min; the auxiliary oxidant is added in an amount such that the reaction system appears milky;
(2) Grinding and mixing carbon nitride oxide and bismuth oxide uniformly, adding chitosan, and grinding and mixing uniformly again to obtain a modified material;
(3) And mixing the modification material with water to prepare a suspension, coating the suspension on the surface of a clean glassy carbon electrode, and airing to obtain the carbon nitride oxide/bismuth oxide composite electrode.
2. The method for producing a carbon nitride oxide/bismuth oxide composite electrode according to claim 1, wherein the concentration of the graphite-phase carbon nitride in the concentrated sulfuric acid in step 1 is 0.02 to 0.05g/mL; the dosage ratio of the graphite phase carbon nitride, the potassium permanganate and the water is 1g to 1.2g to 200mL.
3. The method for preparing a carbon nitride oxide/bismuth oxide composite electrode according to claim 1, wherein the mass ratio of the carbon nitride oxide to the bismuth oxide to the chitosan in the step 2 is 4-6:1:1.
4. The method for producing a carbon nitride oxide/bismuth oxide composite electrode according to claim 1, wherein the concentration of the modifying material in the suspension in step 3 is 0.012-0.016g/mL; the coating amount of the suspension on the surface of the glassy carbon electrode is 3-8 mu L.
5. A carbon nitride oxide/bismuth oxide composite electrode obtained by the production method according to any one of claims 1 to 4.
6. The carbon nitride oxide/bismuth oxide composite electrode obtained by the preparation method according to any one of claims 1 to 4 in Cl － The application in detection is characterized in that the carbon nitride oxide/bismuth oxide composite electrode is used as a voltammetric sensor to be placed in an electrolytic cell of a three-electrode system, a base solution is PBS buffer solutions containing different chloride ion concentrations, the pH value is adjusted to be an acidic condition, and the chloride ion concentration in the base solution is detected by cyclic voltammetry scanning and differential pulse voltammetry.
7. The use according to claim 6, wherein the acidic condition is pH = 2.5-4; the condition of cyclic voltammetry scanning is that the enrichment potential is-0.3V to-0.1V and the enrichment time is 50s to 200s.
8. The use according to claim 6, wherein the linear range of chloride ion concentration in water detectable by the carbon nitride oxide/bismuth oxide composite electrode as a voltammetric sensor is 1.0 x 10 -4 About 0.1mol/L, and the detection limit is 8.9X10 -5 mol/L。
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