CN114324505B - Preparation of carbon electrode, detection method of phytomorin and application - Google Patents
Preparation of carbon electrode, detection method of phytomorin and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000001514 detection method Methods 0.000 title abstract description 25
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Abstract
The invention provides a preparation method of a carbon electrode and a detection method and application of phytomorin, wherein the preparation method of the carbon electrode comprises the following steps: 1) With Mo (CH) 3 COO) 2 ·4H 2 O aqueous solution, na 2 SnO 3 ·4H 2 Preparation of MoSn (OH) from aqueous O solution and NaOH 6 A nano precursor; 2) With sunflower seed husk biomass material, moSn (OH) 6 Preparing a molybdenum-tin bimetallic oxide-carbon hybrid material by using the nano precursor and KOH as raw materials; 3) Preparing a molybdenum-tin bimetallic oxide-carbon electrode by taking a molybdenum-tin bimetallic oxide-carbon hybrid material and a naphthol methanol solution as raw materials; 4) CHCl with Nickel Phthalocyanine 3 The solution and the molybdenum-tin bimetal oxide-carbon electrode are used as raw materials to prepare the nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode. The carbon electrode prepared by the invention can monitor the morin in plants in situ and in real time based on a biological sensing technology, solves the problems of complex sample pretreatment and in-vitro detection only in the prior art, and utilizes the hybrid material prepared by the green and environment-friendly biomass charcoal.
Description
Technical Field
The invention relates to the technical field of living body detection, in particular to a preparation method of a carbon electrode, a detection method of phytomorin and application of phytomorin.
Background
Ozone (O) 3 ) As the main component of the photooxidation agent, the photooxidation agent has the negative effects of inhibiting plant growth, dwarfing plants, reducing the leaf area of crops, premature senility of leaves, reducing the photosynthetic rate and the like, thereby reducing the yield of crops and reducing the quality. Especially in the areas of industrial development such as Beijing Ji area and Zhujiang Chang Yangzhou area, the average ozone concentration of more than 10% of the time is as high as 60 ng.L -1 . In view of this, studies on the biological mechanisms of plants under ozone stress have received extensive attention from students. Flavonoids are important phenolic secondary metabolites in plants. Flavonoid-morin can well remove superoxide anion (O) 2 - ) Hydroxyl radical ([ alpha ] OH) and singlet oxygen ] 1 O 2 ). Detecting dynamic concentration change of morin can reveal adaptation mechanism and response mechanism of secondary metabolite to ozone concentration increase.
The conventional technology for detecting the morin mainly comprises an ultraviolet spectrophotometry, a reverse high performance liquid chromatography technology, a capillary electrophoresis technology and the like, but in-situ living detection cannot be realized, the damage to plants is excessive, and the electrochemical method has the advantages of small volume, convenience in carrying, outdoor real-time monitoring, high sensitivity and strong anti-interference capability, and meets the detection requirement, so that the electrochemical technology is most suitable. Under ozone stress, the living dynamic concentration of the morin is particularly important so as to know the self-defense of plants and the change of nutrient elements and provide a basis for the ozone protection of the plants. At present, a new detection method for monitoring morin in plants in situ in real time is an important subject to be solved in the field.
Disclosure of Invention
The invention provides a preparation method of a carbon electrode and a detection method and application of phytomorin. The carbon electrode prepared by the invention can monitor the morin in plants in situ and in real time based on a biological sensing technology, solves the problems of complex sample pretreatment and in-vitro detection only in the prior art, and utilizes the hybrid material prepared by the green and environment-friendly biomass charcoal.
According to the invention, sunflower is one of the main commercial crops at present, and the planting area and yield account for a large proportion of the world. Sunflower seed hulls are byproducts of the production process of sunflower seed related products, have huge yield, are mostly directly abandoned at present, and a mature secondary utilization method of the sunflower seed hulls is not developed, so that great waste of biomass resources is caused. The sunflower seed skin is difficult to prepare a material with the characteristics of high specific surface area and abundant surface functional groups, and the unactivated sunflower seed skin is not suitable for in vivo detection. The sunflower seed coat serving as biomass charcoal is utilized for the first time to prepare the hybrid carbon material. The material has loose and porous structure, large specific surface area and green and sustainable properties, and can be applied to the field of biological sensing.
The invention provides a preparation method of a carbon electrode, which comprises the following steps:
1) With Mo (CH) 3 COO) 2 ·4H 2 O aqueous solution, na 2 SnO 3 ·4H 2 Preparation of MoSn (OH) from aqueous O solution and NaOH 6 A nano precursor;
2) With sunflower seed hull biomass material, moSn (OH) 6 Preparing a molybdenum-tin bimetallic oxide-carbon hybrid material by using the nano precursor and KOH as raw materials;
3) Preparing a molybdenum-tin bimetallic oxide-carbon electrode by taking the molybdenum-tin bimetallic oxide-carbon hybrid material and naphthol methanol solution as raw materials;
4) CHCl with Nickel Phthalocyanine 3 The solution and the molybdenum-tin bimetal oxide-carbon electrode are used as raw materials to prepare the nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode.
According to the invention, the molybdenum-tin bimetallic oxide-carbon hybrid material formed by green and environment-friendly biomass has a large specific surface area and strong electrocatalytic capacity, and the hybrid material and nickel phthalocyanine cooperate to realize high-sensitivity detection of morin. And finally, the carbon electrode monitors the morin in the plant in situ and in real time based on a biological sensing technology.
According to the preparation method of the carbon electrode provided by the invention, in the step 1), mo (CH 3 COO) 2 ·4H 2 Aqueous O solution and Na 2 SnO 3 ·4H 2 Mixing and stirring the O aqueous solution, adding the sodium hydroxide solution, and stirring for 1-2 h at room temperature; heating at 150-200 deg.c for 18-24 hr, cooling, centrifuging, washing and drying; and/or
In step 2), the sunflower seed hull biomass material, the MoSn (OH) 6 Mixing the nano precursor with potassium hydroxide solution, carrying out ultrasonic treatment for 0.5-20 h, preferably 2h, and drying at 80-110 ℃ for 3-6 h; then at 5 ℃ min -1 Heating to 750-950 ℃, preserving heat for 1-10 h, preferably 3h, and cooling; and/or
In the step 3), the molybdenum-tin bimetallic oxide-carbon hybrid material is mixed with 0.1 percent naphthol methanol solution, and the ultrasonic treatment is carried out for 0.5 to 1 hour; coating 2-5 mu L of dispersion liquid, preferably 4 mu L, on the surface of a substrate, drying at 35-55 ℃ preferably 48 ℃ for 3-5 min, preferably 4min, and repeating the coating for 3-6 times; and/or
In step 4), 4 to 15. Mu.L of CHCl, preferably 12. Mu.L of nickel phthalocyanine, are added 3 Solution coating on the molybdenum-tin bimetallic oxide-carbon electrode, CHCl 3 Volatilizing to obtain the final product.
According to the invention, the better porous sunflower seed husk biomass material is obtained by adopting the step 2), and the specific surface area and the active site of the sunflower seed husk are increased by adopting the potassium hydroxide solution, so that the performance of the sensor is further improved, and the better mulberry pigment detection can be realized.
According to the preparation method of the carbon electrode provided by the invention, in the step 1), mo (CH 3 COO) 2 ·4H 2 The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2mmol/mL, na 2 SnO 3 ·4H 2 The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2mmol/mL; the concentration of the sodium hydroxide solution is 0.05-0.2M, preferably 0.1M; mo (CH) 3 COO) 2 ·4H 2 Aqueous solution of O and Na 2 SnO 3 ·4H 2 The volume ratio of the aqueous solution of O is 10-35:10:6-10, preferably 20:10:8; and/or
In the step 2), the preparation of the sunflower seed husk biomass material comprises the following steps: washing sunflower seed coats, drying at 80-100 ℃ for 20-36 h, and grinding; said sunflower seed hull biomass material, said MoSn (OH) 6 The mass volume ratio of the nano precursor to the potassium hydroxide solution is 4-8 g: 2-6 g: 10-25 mL, preferably, said sunflower seed hull biomass material, said MoSn (OH) 6 The mass volume ratio of the nano precursor to the potassium hydroxide solution is 6g:4g:20mL; the concentration of the potassium hydroxide solution is 1M; and/or
In the step 3), the mass volume ratio of the molybdenum-tin bimetallic oxide-carbon hybrid material to the naphthol methanol solution is 2-5 mg, 1mL is preferable to 3mg, 1mL is preferable, and the substrate is preferably a ceramic sheet with the volume ratio of 1cm multiplied by 1 cm; and/or
In step 4), the CHCl of the nickel phthalocyanine 3 The concentration of the solution is 0.05 to 0.2M, preferably 0.1M.
In the present invention, mo (CH) in the above step 1) is used 3 COO) 2 ·4H 2 O、Na 2 SnO 3 ·4H 2 The concentration ratio of the O to the sodium hydroxide solution can better obtain MoSn (OH) 6 Thus, the further obtained molybdenum-tin bimetallic oxide can be used for better detection of morin. In particular, by using the potassium hydroxide solution in the above ratio in step 2), the molybdenum-tin bimetallic oxide forms a better porous structure, further improving the response to current.
The invention also provides a carbon electrode, and the nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode obtained by the preparation method of the carbon electrode.
The invention also provides a sensor comprising: a carbon electrode obtained by the method for producing a carbon electrode or the carbon electrode; preferably, platinum wires and Ag/AgCl are also included.
In the present invention, the above-mentioned step Mo (CH) 3 COO) 2 ·4H 2 The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2mmol/mL, na 2 SnO 3 ·4H 2 The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2mmol/mL; of sodium hydroxide solutionThe concentration is 0.05-0.2M, preferably 0.1M; mo (CH) 3 COO) 2 ·4H 2 Aqueous solution of O and Na 2 SnO 3 ·4H 2 The volume ratio of the aqueous solution of O is 10-35:10:6-10, preferably 20:10:8. The molybdenum-tin bimetallic oxide prepared by the parameters improves the electrocatalytic performance of the working electrode through the synergistic effect between two metals in the bimetallic oxide, and can be better detected compared with a single metal oxide.
The invention also provides a detection method of the phytomorin, which adopts the sensor to carry out electrochemical analysis on target plants to obtain the concentration of the phytomorin.
The detection method of the phytomorin provided by the invention comprises the following steps: correcting the sensor by using morin with standard concentration, and preferably calculating a slope a and an intercept b so that the slope deviation is within 15%; placing a working electrode at a position to be detected of a target plant, connecting an electrochemical workstation, and obtaining a working curve by using a current-time method; obtaining the concentration of the morin at the part to be detected of the target plant.
According to the method for detecting phytomorin provided by the invention, the working voltage for detecting morin is 0.3V.
According to the method for detecting phytomorin provided by the invention, the target plant is selected from one or more of crops, chinese herbal medicines, flowers and vegetables, preferably soybean; and/or detecting one or more of the roots, stems, leaves and fruits of the target plant, preferably the leaves; and/or detecting the target plant for different periods of growth and/or different growth environments; and/or the detected part of the target plant is free from in vitro and minimally invasive damage.
In the invention, by adopting the current-time method, the working voltage is 0.3V, and the morin can be better specifically identified.
The invention also provides an application of the carbon electrode obtained by the preparation method of the carbon electrode or the sensor in on-line analysis of dynamic concentration of morin in plants.
The invention has the advantages that: the invention can realize detection of morin on soybean leaves, and compared with other traditional detection means, the electrode can not cause substantial damage to plants due to the electrochemical living detection technology, the plant can continue to grow, and the response signal is rapid, and the detection limit is low. According to the invention, sunflower seed husks serving as biomass charcoal are utilized for preparing the hybrid carbon material for the first time, molybdenum-tin bimetallic oxide is prepared for the first time, and the synergistic effect of the two materials is used for successfully detecting the morin in real time.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a preparation flow of a carbon electrode according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. 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 specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The equipment used is not pointed out by manufacturers, and is a conventional product which can be purchased by a regular channel manufacturer. The methods are conventional methods unless otherwise specified, and the starting materials are commercially available from the public sources unless otherwise specified. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications.
In the embodiment of the invention, the high O is used 3 The sensitive crop-soybean is specifically Fengfeng No. 29 soybean, and the content of morin in leaves is taken as a research object; the electric signal is obtained by a current-time method of a Switzerland Ten Autolab electrochemical workstation.
Example 1
The present embodiment provides a preparation method of a nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode, as shown in fig. 1, which is a schematic diagram of a preparation flow of a carbon electrode in the embodiment, and specifically includes:
1)MoSn(OH) 6 preparation of nano-precursors
Mo (CH) with the concentration of 0.2mmol/mL is prepared respectively 3 COO) 2 ·4H 2 O and 0.2mmol/mL Na 2 SnO 3 ·4H 2 Aqueous solution of O. The two solutions are respectively taken to have the volumes of 20mL and 10mL, 8mL of sodium hydroxide with the concentration of 0.1M is dropwise added into the mixed solution by mixing and stirring, and the magnetic stirring is carried out for 1 to 2 hours at room temperature. Transferring the final solution into a stainless steel autoclave, placing the stainless steel autoclave in an oven at 150-200 ℃ for 18-24 hours, naturally cooling the autoclave, centrifugally collecting materials, washing the materials twice with water and absolute ethyl alcohol respectively, and drying the materials in a vacuum oven to obtain MoSn (OH) 6 A nano precursor.
2) Preparation of molybdenum-tin bimetallic oxide-carbon hybrid material
Picking sunflower seed peel, washing with clear water for several times to remove impurities, drying in a vacuum drying oven at 80-100 ℃ for 20-36 h, and grinding. Taking 6g of sunflower seed husk biomass material and 4g of MoSn (OH) 6 The nano particles are dispersed in 20mL of 1M potassium hydroxide solution, mixed and stirred, and dried for 3-6 hours at 80-110 ℃ in a blast drying box after being subjected to ultrasonic treatment for 2 hours. Placing the mixed material into a quartz boat, placing the quartz boat into a tube furnace, and placing the quartz boat into air at 5 ℃ for min -1 The temperature rising speed of the material is increased to 750-950 ℃, the temperature is kept for 3h, and the Mo-Sn bimetallic oxide-carbon hybrid material is obtained after the tube furnace is cooled to room temperature.
3) Preparation of molybdenum-tin bimetallic oxide-carbon electrode
3mg of molybdenum-tin bimetallic oxide-carbon hybrid material is placed in 1mL of 0.1% naphthol methanol solution, and uniformly dispersed by ultrasonic treatment for 0.5-1 h. The dispersion of 4. Mu.L was applied dropwise to a ceramic plate (1 cm. Times.1 mm), dried in a forced air drying oven at 48℃for 4min and taken out, and this procedure was repeated 3 to 6 times in total to obtain a molybdenum-tin bimetallic oxide-carbon electrode.
4) Preparation of nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode
Preparation of 0.1M Nickel Phthalocyanine (NiPc) CHCl 3 After the solution was completely dissolved by ultrasonic treatment, 12. Mu.L of the solution was uniformly dropped on the molybdenum-tin bimetal oxide-carbon electrode. And (3) at room temperature, after the chloroform is completely volatilized, forming a nickel phthalocyanine film to obtain the nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode.
The embodiment also provides a sensor constructed by utilizing the nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode in the embodiment, and the sensor adopts a three-electrode system composed of the working electrode of the nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode, a platinum wire and Ag/AgCl.
The embodiment also provides a sensor constructed by using the nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode in the embodiment for detecting the content of morin in soybean leaves, which comprises the following steps:
(1) High O is selected 3 The sensitive crop soybean, the test organ is leaf, the leaf is pricked with micron level hole, buffer solution is dropped to cover the hole, working electrode, platinum wire and Ag/AgCl are set under the leaf, and electrochemical test is started.
(2) Drawing a standard curve: standard solutions of morin were prepared with 0.1M BR (pH 6.8) buffer at concentrations of 0.1, 0.5, 1, 2, 5, 10, 20, 50, 75, 100, 150, 200, 300. Mu.M, respectively. The measurement of morin at different concentrations was performed using the above electrodes using a current-time method, with a voltage set at 0.3V for 600s. A set of concentration versus current curves is obtained, followed by calculation of a standard curve for the working electrode.
(3) In-line detection of living body: after all the electrodes (working electrode, reference electrode and counter electrode) are washed by ultrapure water, the electrode clamp is connected with the working electrode and is connected with an electrochemical workstation, firstly, two morin standard solutions (1 mu M,5 mu M) are respectively tested for electrochemical correction, the calculated slope of the working curve and the standard curve is within 15%, the electrodes can be considered to work normally, and after correction, I-t test is carried out for 600s in 0.1M BR buffer solution, and the background current is stable. Blade 15 holes were pricked with micron-sized platinum wires. The working electrode is stuck below the micropore of the blade, 100 mu L of BR buffer solution is dropped on the micropore, the platinum wire and AgCl/Ag electrode are stuck above the micropore of the blade, a glass slide is covered on the buffer solution to ensure to cover the micropore, a current-time curve (the potential is 0.3V, the resting time is 5s and the time is 600 s) is obtained, and the instant concentration of the soybean blade can be calculated through the corrected working curve by the obtained current signal.
(4) Comparison of experimental results: two treatments were placed in an open top air chamber (OTC). The control group is the concentration of the environment; ozone stress group: after soybean seedlings emerge for 30 days, an ozone fumigation experiment is carried out, and the ozone concentration is 100 ng.L -1 Fumigating for 8h each day until the instant concentration is measured in the branching period.
And respectively carrying out in-situ on-line detection on the leaves of the control group and the ozone stress group, and selecting the same leaf parts of soybeans. The comparison of the analysis results is shown in Table 1. The results indicate that the sensor of the present invention is reliable.
Table 1 comparison of test results
The mulberry pigment oxidation peak current and the concentration of the mulberry pigment are well linear, and the linear range is 1 multiplied by 10 -7 mol/L~1.5×10 -3 mol/L, linear regression equation is: i pa =0.152c+0.185, r=0.98, detection limit 8×10 -8 mol/L。
Comparative example 1
In this comparative example, the conventional double amperometric method for measuring the morin in ramulus Mori in the prior art was used, and a constant potential pre-anodized double platinum electrode was used, so that the oxidation current of morin and its concentration were 4.0X10 when the applied potential difference was 0V -6 ~1.0×10 -3 mol/L rangeThe inside of the enclosure is in a linear relationship (r=0.999 1, n=14). The detection limit was 1.0X10 -6 mol/L。
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (17)
1. A method for producing a carbon electrode, comprising:
1) With Mo (CH) 3 COO) 2 ·4H 2 O aqueous solution, na 2 SnO 3 ·4H 2 Preparation of MoSn (OH) from aqueous O solution and NaOH 6 A nano precursor;
2) With sunflower seed hull biomass material, moSn (OH) 6 Preparing a molybdenum-tin bimetallic oxide-carbon hybrid material by using the nano precursor and KOH as raw materials;
3) Preparing a molybdenum-tin bimetallic oxide-carbon electrode by taking the molybdenum-tin bimetallic oxide-carbon hybrid material and naphthol methanol solution as raw materials;
4) CHCl with Nickel Phthalocyanine 3 Preparing nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode by taking the solution and the molybdenum-tin bimetal oxide-carbon electrode as raw materials;
in step 1), mo (CH) 3 COO) 2 ·4H 2 Aqueous O solution and Na 2 SnO 3 ·4H 2 Mixing and stirring the O aqueous solution, adding a sodium hydroxide solution, and stirring for 1-2 hours at room temperature; heating at 150-200 ℃ for 18-24 h, cooling, centrifuging, washing and drying;
in step 2), the sunflower seed hull biomass material, the MoSn (OH) 6 Mixing the nano precursor with potassium hydroxide solution, performing ultrasonic treatment for 0.5-10 h, and performing ultrasonic treatment on the mixture at 80-110 h ◦ C, drying for 3-6 hours; then at 5 ℃ min −1 Heating to 750-950 ℃, preserving heat for 1-10 h, and cooling;
in the step 3), mixing the molybdenum-tin bimetallic oxide-carbon hybrid material with 0.1% naphthol methanol solution, and carrying out ultrasonic treatment for 0.5-1 h; coating 2-5 mu L of dispersion liquid on the surface of a substrate, drying for 3-5 min at 35-55 ℃, and repeating the coating for 3-6 times;
in step 4), 4-15 mu L of nickel phthalocyanine CHCl 3 Solution coating on the molybdenum-tin bimetallic oxide-carbon electrode, CHCl 3 Volatilizing to obtain the final product.
2. The method for producing a carbon electrode according to claim 1, wherein,
in step 2), the sunflower seed hull biomass material, the MoSn (OH) 6 Mixing the nano precursor with potassium hydroxide solution, performing ultrasonic treatment for 2 hours, and performing ultrasonic treatment on the mixture at 80-110 ◦ C, drying for 3-6 hours; then at 5 ℃ min −1 Heating to 750-950 ℃, preserving heat for 3h, and cooling; and/or
In the step 3), mixing the molybdenum-tin bimetallic oxide-carbon hybrid material with 0.1% naphthol methanol solution, and carrying out ultrasonic treatment for 0.5-1 h; coating 4 mu L of dispersion liquid on the surface of a substrate, drying for 4min at 48 ℃, and repeating the coating for 3-6 times; and/or
In step 4), 12. Mu.L of nickel phthalocyanine CHCl 3 Solution coating on the molybdenum-tin bimetallic oxide-carbon electrode, CHCl 3 Volatilizing to obtain the final product.
3. The method for producing a carbon electrode according to claim 2, wherein,
in step 1), mo (CH) 3 COO) 2 ·4H 2 The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, na 2 SnO 3 ·4H 2 The concentration of the O aqueous solution is 0.1-0.3 mmol/mL; the concentration of the sodium hydroxide solution is 0.05-0.2M; mo (CH) 3 COO) 2 ·4H 2 Aqueous solution of O and Na 2 SnO 3 ·4H 2 The volume ratio of the aqueous solution of O is 10-35:10:6-10; and/or
In step 2), the sunflower is used forThe preparation of the flower seed coat biomass material comprises the following steps: washing sunflower seed coats, drying at 80-100 ℃ for 20-36 h, and grinding; said sunflower seed hull biomass material, said MoSn (OH) 6 The mass volume ratio of the nano precursor to the potassium hydroxide solution is 4-8 g: 2-6 g: 10-25 mL; and/or
In the step 3), the mass volume ratio of the molybdenum-tin bimetallic oxide-carbon hybrid material to the naphthol methanol solution is 2-5 mg/1 mL; and/or
In step 4), the CHCl of the nickel phthalocyanine 3 The concentration of the solution is 0.05-0.2M.
4. The method for producing a carbon electrode according to claim 3, wherein,
in step 1), mo (CH) 3 COO) 2 ·4H 2 The concentration of the O aqueous solution was 0.2mmol/mL, na 2 SnO 3 ·4H 2 The concentration of the O aqueous solution is 0.2mmol/mL; the concentration of the sodium hydroxide solution is 0.1M; mo (CH) 3 COO) 2 ·4H 2 Aqueous solution of O and Na 2 SnO 3 ·4H 2 The volume ratio of the aqueous solution of O is 20:10:8; and/or
In step 2), the sunflower seed hull biomass material, the MoSn (OH) 6 The mass volume ratio of the nano precursor to the potassium hydroxide solution is 6g:4g:20mL; the concentration of the potassium hydroxide solution is 1M; and/or
In the step 3), the mass volume ratio of the molybdenum-tin bimetallic oxide-carbon hybrid material to the naphthol methanol solution is 3mg to 1mL, and the base material is a ceramic sheet with the volume ratio of 1cm to 1 cm; and/or
In step 4), the CHCl of the nickel phthalocyanine 3 The concentration of the solution was 0.1M.
5. A carbon electrode characterized by being a nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode obtained by the method for producing a carbon electrode according to any one of claims 1 to 4.
6. A sensor, comprising: a carbon electrode obtained by the method for producing a carbon electrode according to any one of claims 1 to 4 or a carbon electrode according to claim 5.
7. The sensor of claim 6, further comprising a platinum wire and Ag/AgCl.
8. A method for detecting phytomorin, characterized in that the sensor according to claim 6 or 7 is used for carrying out electrochemical analysis on target plants to obtain the concentration of morin.
9. The method for detecting phytomorin according to claim 8, comprising: correcting the sensor by using morin with standard concentration, and calculating a slope a and an intercept b to ensure that the slope deviation is within 15%; placing a working electrode at a position to be detected of a target plant, connecting an electrochemical workstation, and obtaining a working curve by using a current-time method; obtaining the concentration of the morin at the part to be detected of the target plant.
10. The method for detecting phytomorin according to claim 9, wherein the operating voltage for detecting morin is 0.3V.
11. The method for detecting phytomorin according to any one of claims 8 to 10, wherein the target plant is selected from one or more of crops, chinese herbal medicines, flowers and vegetables.
12. The method for detecting phytomorin according to claim 11, wherein the target plant is soybean.
13. The method for detecting phytomorin according to any one of claims 8 to 10, wherein one or more of roots, stems, leaves and fruits of the target plant are detected.
14. The method for detecting phytomorin according to claim 13, wherein the leaves of the target plant are detected.
15. The method for detecting phytomorin according to any one of claims 8 to 10, wherein the target plant is detected in different growth periods and/or different growth environments.
16. The method for detecting phytomorin according to any one of claims 8 to 10, wherein the detected part of the target plant is free from in vitro and minimally invasive damage.
17. Use of a carbon electrode obtained by the method for preparing a carbon electrode according to any one of claims 1 to 4 or a carbon electrode according to claim 5 or a sensor according to claim 6 or 7 for on-line analysis of dynamic concentration of morin in plants.
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