CN114324505A - Preparation of carbon electrode and detection method and application of plant morin - Google Patents
Preparation of carbon electrode and detection method and application of plant morin Download PDFInfo
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- CN114324505A CN114324505A CN202111499130.0A CN202111499130A CN114324505A CN 114324505 A CN114324505 A CN 114324505A CN 202111499130 A CN202111499130 A CN 202111499130A CN 114324505 A CN114324505 A CN 114324505A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- YXOLAZRVSSWPPT-UHFFFAOYSA-N Morin Chemical compound OC1=CC(O)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 YXOLAZRVSSWPPT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 235000007708 morin Nutrition 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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Abstract
The invention provides a preparation method of a carbon electrode and a detection method and application of plant morin, wherein the preparation method of the carbon electrode comprises the following steps: 1) with Co (CH)3COO)2·4H2O aqueous solution, Na2SnO3·4H2Preparation of MoSn (OH) by using O aqueous solution and NaOH as raw materials6A nano precursor; 2) prepared from sunflower seed husk biomass material, MoSn (OH)6Preparing a molybdenum-tin bimetallic oxide-carbon hybrid material by using a nano precursor and KOH as raw materials; 3) preparing a molybdenum-tin bimetallic oxide-carbon electrode by using a molybdenum-tin bimetallic oxide-carbon hybrid material and a naphthol methanol solution as raw materials; 4) CHCl with nickel phthalocyanine3The solution and the molybdenum-tin bimetallic oxide-carbon electrode are used as raw materials to prepare the nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode. The carbon electrode prepared by the invention can monitor morin in plants in real time in situ based on the biosensing technology, and overcomes the defect that the prior art is complicated before samplesThe treatment and the in vitro detection can be realized only, and the green and environment-friendly hybrid material prepared from the biomass charcoal is utilized.
Description
Technical Field
The invention relates to the technical field of in-vivo detection, in particular to a preparation method of a carbon electrode and a detection method and application of plant morin.
Background
Ozone (O)3) As the main component of the photo-oxidant, the photo-oxidant causes negative effects of inhibiting plant growth, dwarfing plants, reducing the leaf area of crops, premature leaf senescence, reducing the photosynthetic rate and the like, thereby causing the reduction of the yield and the quality of the crops. Especially in industrially developed areas such as Jingjin Ji area and Zhujiang ChangDelta area, the average hour concentration of ozone is as high as 60 ng.L in more than 10% time-1. In view of this, the study of the biological mechanism of plants under ozone stress has received much attention from researchers. The flavonoids are important phenolic secondary metabolites in plants. The flavonoid compound, morin, can effectively remove superoxide anion (O)2 -) Hydroxyl radical (a OH) and singlet oxygen (a1O2). The dynamic concentration change of morin is detected, and an adaptive mechanism and a response mechanism of secondary metabolites to the increase of the ozone concentration can be revealed.
The conventional techniques for detecting morin mainly comprise an ultraviolet spectrophotometry, a reverse high-performance liquid chromatography technique, a capillary electrophoresis technique and the like, but in-situ in-vivo detection cannot be realized generally, the damage to plants is overlarge, and the electrochemical method has the advantages of small volume, convenience for carrying outdoor real-time monitoring, high sensitivity and strong anti-interference capability, meets the detection requirement and is most suitable for the electrochemical technique. Under the stress of ozone, the living body dynamic concentration of 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. The present invention provides a new detection method for in-situ real-time monitoring morin in plants, which is an important issue to be solved urgently in the field.
Disclosure of Invention
The invention provides a preparation method of a carbon electrode and a detection method and application of plant morin. The carbon electrode prepared by the invention can monitor morin in plants in situ and in real time based on a biosensing technology, solves the problems of complex sample pretreatment and only in-vitro detection in the prior art, and utilizes a green and environment-friendly hybrid material prepared from biomass charcoal.
According to the present invention, sunflower is one of the current major economic crops, and the planting area and yield are significant in the global scope. The sunflower seed hull is a byproduct of a production process of related sunflower seed products, has a huge yield, is mostly directly discarded at present, and a mature secondary utilization method of the sunflower seed hull is not developed, so that the waste of a biomass resource source is large. The sunflower seed peel is difficult to prepare into a material with the characteristics of high specific surface area and abundant surface functional groups, and the unactivated sunflower seed peel is not suitable for in vivo detection. The invention first utilizes sunflower seed husk as biomass charcoal to prepare the hybrid carbon material. The material has loose and porous structure, large specific surface area, green and sustainable property, and can be applied to the field of biosensing.
The invention provides a preparation method of a carbon electrode, which comprises the following steps:
1) with Co (CH)3COO)2·4H2O aqueous solution, Na2SnO3·4H2Preparation of MoSn (OH) by using O aqueous solution and NaOH as raw materials6A nano precursor;
2) with sunflower seed husk biomass material, said MoSn (OH)6Preparing a molybdenum-tin bimetallic oxide-carbon hybrid material by using a nano precursor and KOH as raw materials;
3) preparing a molybdenum-tin bimetallic oxide-carbon electrode by using the molybdenum-tin bimetallic oxide-carbon hybrid material and a naphthol methanol solution as raw materials;
4) CHCl with nickel phthalocyanine3Preparing the nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode by using the solution and the molybdenum-tin bimetal oxide-carbon electrode as raw materials.
In the invention, the molybdenum-tin bimetallic oxide-carbon hybrid material formed by green and environment-friendly biomass has large specific surface area and strong electrocatalytic capacity, and the high-sensitivity detection of the morin is realized by the synergistic effect of the hybrid material and nickel phthalocyanine. Finally, the carbon electrode monitors morin in the plants in situ in real time based on a biosensing technology.
According to the preparation method of the carbon electrode provided by the invention, in the step 1), Co (CH)3COO)2·4H2Aqueous solution of O and Na2SnO3·4H2Mixing and stirring the O aqueous solution, adding a sodium hydroxide solution, and stirring for 1-2 h at room temperature; then heating for 18-24 h at the temperature of 150-200 ℃, cooling, centrifuging, washing and drying; and/or
In step 2), the sunflower seed husk biomass material, the MoSn (OH)6Mixing the nano precursor with a 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-1Heating to 750-950 ℃, keeping the temperature for 1-10 hours, preferably 3 hours, 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 2-5 mul, preferably 4 mul of dispersion liquid on the surface of a base material, drying at 35-55 ℃, preferably 48 ℃, for 3-5 min, preferably 4min, and repeating the coating for 3-6 times; and/or
In the step 4), 4-15 muL, preferably 12 muL of CHCl of nickel phthalocyanine3Solution coating on the Mo-Sn bimetal oxide-carbon electrode, CHCl3And (5) volatilizing to obtain the product.
In the invention, the better porous sunflower seed husk biomass material is obtained by adopting the step 2), and the specific surface area and active sites 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 morin can be better detected.
Preparation of carbon electrodes provided according to the inventionMethod, step 1), Co (CH)3COO)2·4H2The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2mmol/mL, Na2SnO3·4H2The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2 mmol/mL; the concentration of the sodium hydroxide solution is 0.05-0.2M, and preferably 0.1M; co (CH)3COO)2·4H2Aqueous solution of O and Na2SnO3·4H2The volume ratio of the O aqueous solution is 10-35: 10: 6-10, preferably 20:10: 8; and/or
In the step 2), the preparation of the sunflower seed hull biomass material comprises the following steps: washing sunflower seed hulls, drying for 20-36 h at 80-100 ℃, and grinding; the sunflower seed husk biomass material, the MoSn (OH)6The mass-volume ratio of the nano precursor to the potassium hydroxide solution is 4-8 g: 2-6 g: 10-25 mL, preferably, the sunflower seed husk biomass material, the MoSn (OH)6The mass-volume ratio of the nano precursor to the potassium hydroxide solution is 6 g: 4 g: 20 mL; 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, preferably 3mg:1mL, and the base material is preferably a ceramic plate of 1cm × 1cm × 1 cm; and/or
In step 4), CHCl of the nickel phthalocyanine3The concentration of the solution is 0.05-0.2M, preferably 0.1M.
In the present invention, by using Co (CH) in the above step 1)3COO)2·4H2O、Na2SnO3·4H2The concentration ratio of O and the sodium hydroxide solution can better obtain MoSn (OH)6Therefore, the further obtained molybdenum-tin bimetal oxide can be used for better detecting morin. Particularly, by using the potassium hydroxide solution in the above ratio in the step 2), the molybdenum-tin bimetal oxide forms a better porous structure, and the response of the current is further improved.
The invention also provides a carbon electrode, and the nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode prepared by the preparation method of the carbon electrode.
The present 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, Co (CH) is obtained by adopting the above-mentioned step3COO)2·4H2The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2mmol/mL, Na2SnO3·4H2The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2 mmol/mL; the concentration of the sodium hydroxide solution is 0.05-0.2M, and preferably 0.1M; co (CH)3COO)2·4H2Aqueous solution of O and Na2SnO3·4H2The volume ratio of the O aqueous solution is 10-35: 10: 6-10, preferably 20:10: 8. The molybdenum-tin bimetal oxide prepared by the parameters improves the electrocatalytic performance of the working electrode through the synergistic effect of two metals in the bimetal oxide, and can be better detected compared with a single metal oxide.
The invention also provides a detection method of the plant morin, which adopts the sensor to carry out electrochemical analysis on the target plant to obtain the concentration of the morin.
The detection method of the plant morin provided by the invention comprises the following steps: correcting the sensor by morin with standard concentration, and preferably calculating slope a and intercept b to ensure that the slope deviation is within 15%; placing a working electrode at a part to be detected of a target plant, connecting the working electrode with an electrochemical workstation, and obtaining a working curve by using a current-time method; and obtaining the concentration of morin at the part to be detected of the target plant.
According to the method for detecting the phytochrome, provided by the invention, the working voltage for detecting the phytochrome is 0.3V.
According to the detection method of the phytochrome, the target plant is selected from one or more of crops, Chinese herbal medicines, flowers and vegetables, and is preferably soybean; and/or detecting one or more of roots, stems, leaves and fruits of the target plant, preferably leaves; and/or detecting the target plants in different growth periods and/or different growth environments; and/or the detected part of the target plant has no in vitro and minimally invasive injury.
In the present invention, by using the current-time method, the operating voltage is 0.3V, and morin can be more specifically recognized.
The invention also provides the application of the carbon electrode obtained by the preparation method of the carbon electrode or the sensor in online analysis of the dynamic concentration of morin in the plant body.
The invention has the beneficial effects that: the invention can realize the detection of morin on the soybean leaves, and compared with other traditional detection means, the electrode does not cause substantial damage to the plants due to the electrochemical in-vivo detection technology, the plants can continue to grow, the response signal is quick, and the detection limit is low. According to the invention, the sunflower seed husk used as the biomass charcoal is firstly utilized to prepare the hybrid carbon material, the molybdenum-tin bimetallic oxide is firstly prepared, and the synergistic effect of the two materials is successfully realized to detect the morin in real time.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a carbon electrode manufacturing process according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the examples of the present invention, high O is used3The sensitive crop-soybean is specifically Tiefeng No. 29 soybean, and the content of morin in leaves is taken as a research object; the electric signal is obtained by adopting a current-time method of a Switzerland Wantong Autolab electrochemical workstation.
Example 1
The present embodiment provides a preparation method of a nickel phthalocyanine/molybdenum-tin bimetallic oxide-carbon electrode, and as shown in fig. 1, the preparation method of the carbon electrode in the embodiment specifically includes:
1)MoSn(OH)6preparation of nano precursor
Co (CH) with a concentration of 0.2mmol/mL is prepared separately3COO)2·4H2O and 0.2mmol/mL Na2SnO3·4H2An aqueous solution of O. And respectively taking 20mL and 10mL of the two solutions, mixing and stirring, dropwise adding 8mL of 0.1M sodium hydroxide into the mixed solution, and magnetically stirring at room temperature for 1-2 h. Transferring the final solution into a stainless steel autoclave, placing the autoclave in an oven at 150-200 ℃ for 18-24 hours, naturally cooling the autoclave, centrifugally collecting materials, washing the materials twice by using water and absolute ethyl alcohol respectively, and drying the materials in a vacuum oven to obtain MoSn (OH)6And (3) nano precursor.
2) Preparation of molybdenum-tin bimetallic oxide-carbon hybrid material
Picking sunflower seed hulls, washing the sunflower seed hulls with clear water for several times to remove impurities, then drying the sunflower seed hulls in a vacuum drying oven at the temperature of 80-100 ℃ for 20-36 hours, and grinding the sunflower seed hulls. Taking 6g sunflower seed husk biomass material and 4g MoSn (OH)6Dispersing the nano particles in 20mL of 1M potassium hydroxide solution, mixing and stirring, and performing ultrasonic treatment for 2hAnd drying the mixture for 3 to 6 hours in a blast drying oven at the temperature of between 80 and 110 ℃. Placing the mixed material in a quartz boat, placing the quartz boat in a tube furnace, and heating at 5 deg.C/min in air-1The temperature rising speed is increased to 750-950 ℃, the temperature is kept for 3h, and the Mo-Sn bimetal oxide-carbon hybrid material is obtained after the tubular furnace is cooled to the room temperature.
3) Preparation of molybdenum-tin bimetallic oxide-carbon electrode
Putting 3mg of molybdenum-tin bimetallic oxide-carbon hybrid material into 1mL of 0.1% naphthol methanol solution, and uniformly dispersing by ultrasonic for 0.5-1 h. And dripping 4 mu L of dispersion liquid on a ceramic plate (1cm multiplied by 1mm), drying in a forced air drying oven at 48 ℃ for 4min, and taking out, wherein the step is repeated for 3-6 times to obtain the molybdenum-tin bimetallic oxide-carbon electrode.
4) Preparation of nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode
CHCl for preparing 0.1M nickel phthalocyanine (NiPc)3After the solution is dissolved completely by ultrasonic treatment, 12. mu.L of the solution is uniformly dripped on a molybdenum-tin bimetallic oxide-carbon electrode. And at room temperature, after the trichloromethane is completely volatilized, forming a nickel phthalocyanine film to obtain the nickel phthalocyanine/molybdenum-tin double metal oxide-carbon electrode.
This example also provides a sensor constructed using the nickel phthalocyanine/molybdenum-tin double metal oxide-carbon electrode of the example, which employs a three-electrode system composed of the working electrode of the above nickel phthalocyanine/molybdenum-tin double metal oxide-carbon electrode, a platinum wire, and Ag/AgCl.
The embodiment also provides a sensor constructed by the nickel phthalocyanine/molybdenum-tin double metal oxide-carbon electrode in the embodiment and used for detecting the content of morin in soybean leaves, which comprises the following steps:
(1) selecting high O3The sensitive crop soybean is tested by taking a leaf as a testing organ, pricking a micron-level hole on the leaf, dripping buffer solution to cover the hole, placing a working electrode, a platinum wire and Ag/AgCl under the leaf, and starting to perform electrochemical testing.
(2) Drawing a standard curve: the morin standard solutions were prepared with 0.1M BR (pH6.8) 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 carried out by the current-time method using the above-mentioned electrodes, and the voltage was set to 0.3V for 600 s. A set of concentration versus current curves is obtained, and a calibration curve for the working electrode is then calculated.
(3) In-vivo on-line detection: after all electrodes (working electrode, reference electrode and counter electrode) are washed by ultrapure water, the electrode clamps are connected with the working electrode and connected with an electrochemical workstation, firstly, two parts of morin standard solutions (1 mu M and 5 mu M) are respectively tested to carry out electrochemical correction, the calculated slope of the working curve and the standard curve is within 15 percent, the electrodes are considered to be capable of normally working, after correction, I-t test is firstly carried out in 0.1M BR buffer solution for 600s, and the background current is stable. The 15 holes of the blade are pricked by micron-sized platinum wires. Attaching a working electrode below a micropore of a blade, dropping 100 mu L of BR buffer solution on the micropore, attaching a platinum wire and an AgCl/Ag electrode above the micropore of the blade, covering the buffer solution with a glass slide to ensure that the micropore is covered, obtaining a current-time curve (potential 0.3V, rest time 5s and time 600s), and calculating the instant concentration of the soybean blade by the obtained current signal through the corrected working curve.
(4) And (3) comparing experimental results: two treatments were set in an Open Top Chamber (OTC). The control group is the concentration of the environment; ozone stress group: after soybean emergence for 30 days, carrying out an ozone fumigation experiment, wherein the ozone concentration is 100 ng.L-1Fumigating for 8h every day until the branch stage is measured for the instant concentration.
The control group and the ozone-stressed group are respectively subjected to living body on-line detection, and the same soybean leaf part is selected. The results of the analyses are shown in Table 1. The results indicate that the sensor of the present invention is reliable.
Table 1 comparison of test results
When morin in soybean leaves is measured by using the method of the embodiment, morin oxidation peak current and the concentration thereof have good linear relation, and the linear range is 1 multiplied by 10-7mol/L～1.5×10-3mol/L, linear regression equation: i ispa0.152C +0.185, 0.98, limit of detection 8 × 10-8mol/L。
Comparative example 1
The comparative example adopts the conventional double-ampere method on-line measurement of morin in mulberry twigs in the prior art, uses a double platinum electrode which is subjected to constant potential pre-anodization, and when the applied potential difference is 0V, the oxidation current and the concentration of the morin are 4.0 multiplied by 10-6～1.0×10-3The relationship between mol/L is linear (r is 0.9991, n is 14). Detection limit of 1.0 × 10-6mol/L。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method of making a carbon electrode, comprising:
1) with Co (CH)3COO)2·4H2O aqueous solution, Na2SnO3·4H2Preparation of MoSn (OH) by using O aqueous solution and NaOH as raw materials6A nano precursor;
2) with sunflower seed husk biomass material, said MoSn (OH)6Preparing a molybdenum-tin bimetallic oxide-carbon hybrid material by using a nano precursor and KOH as raw materials;
3) preparing a molybdenum-tin bimetallic oxide-carbon electrode by using the molybdenum-tin bimetallic oxide-carbon hybrid material and a naphthol methanol solution as raw materials;
4) CHCl with nickel phthalocyanine3Preparing the nickel phthalocyanine/molybdenum-tin bimetal oxide-carbon electrode by using the solution and the molybdenum-tin bimetal oxide-carbon electrode as raw materials.
2. The method for producing a carbon electrode according to claim 1,
in step 1), Co (CH)3COO)2·4H2Aqueous solution of O and Na2SnO3·4H2Mixing and stirring the O aqueous solution, adding a sodium hydroxide solution, and stirring for 1-2 h at room temperature; then heating for 18-24 h at the temperature of 150-200 ℃, cooling, centrifuging, washing and drying; and/or
In step 2), the sunflower seed husk biomass material, the MoSn (OH)6Mixing the nano precursor with a potassium hydroxide solution, carrying out ultrasonic treatment for 0.5-10 h, preferably 2h, and drying at 80-110 ℃ for 3-6 h; then at 5 ℃ min-1Heating to 750-950 ℃, keeping the temperature for 1-10 hours, preferably 3 hours, 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 2-5 mul, preferably 4 mul of dispersion liquid on the surface of a base material, drying at 35-55 ℃, preferably 48 ℃, for 3-5 min, preferably 4min, and repeating the coating for 3-6 times; and/or
In the step 4), 4-15 muL, preferably 12 muL of CHCl of nickel phthalocyanine3Solution coating on the Mo-Sn bimetal oxide-carbon electrode, CHCl3And (5) volatilizing to obtain the product.
3. The method for producing a carbon electrode according to claim 2,
in step 1), Co (CH)3COO)2·4H2The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2mmol/mL, Na2SnO3·4H2The concentration of the O aqueous solution is 0.1-0.3 mmol/mL, preferably 0.2 mmol/mL; the concentration of the sodium hydroxide solution is 0.05-0.2M, and preferably 0.1M; co (CH)3COO)2·4H2Aqueous solution of O and Na2SnO3·4H2The volume ratio of the O aqueous solution is 10-35: 10: 6-10, preferably 20:10: 8; and/or
In the step 2), the preparation of the sunflower seed hull biomass material comprises the following steps: washing sunflower seed hulls, drying for 20-36 h at 80-100 ℃, and grinding; the sunflowerSeed husk biomass material, said MoSn (OH)6The mass-volume ratio of the nano precursor to the potassium hydroxide solution is 4-8 g: 2-6 g: 10-25 mL, preferably, the sunflower seed husk biomass material, the MoSn (OH)6The mass-volume ratio of the nano precursor to the potassium hydroxide solution is 6 g: 4 g: 20 mL; 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, preferably 3mg:1mL, and the base material is preferably a ceramic plate of 1cm × 1cm × 1 cm; and/or
In step 4), CHCl of the nickel phthalocyanine3The concentration of the solution is 0.05-0.2M, preferably 0.1M.
4. A carbon electrode, characterized by being a nickel phthalocyanine/molybdenum-tin double metal oxide-carbon electrode obtained by the method for producing a carbon electrode according to any one of claims 1 to 3.
5. A sensor, comprising: a carbon electrode obtained by the method for producing a carbon electrode according to any one of claims 1 to 3 or the carbon electrode according to claim 4; preferably, platinum wires and Ag/AgCl are also included.
6. A method for detecting phytochrome, characterized in that the concentration of phytochrome is obtained by electrochemically analyzing a target plant with the sensor according to claim 5.
7. The method for detecting phytomorin according to claim 6, comprising: correcting the sensor by morin with standard concentration, and preferably calculating slope a and intercept b to ensure that the slope deviation is within 15%; placing a working electrode at a part to be detected of a target plant, connecting the working electrode with an electrochemical workstation, and obtaining a working curve by using a current-time method; and obtaining the concentration of morin at the part to be detected of the target plant.
8. The method according to claim 7, wherein the operating voltage for detecting morin is 0.3V.
9. The method for detecting plant morin according to any one of claims 6 to 8, wherein the target plant is one or more selected from the group consisting of crops, Chinese herbal medicines, flowers and vegetables, and is preferably soybean; and/or detecting one or more of roots, stems, leaves and fruits of the target plant, preferably leaves; and/or detecting the target plants in different growth periods and/or different growth environments; and/or the detected part of the target plant has no in vitro and minimally invasive injury.
10. Use of the carbon electrode obtained by the method for producing a carbon electrode according to any one of claims 1 to 3, or the carbon electrode according to claim 4, or the sensor according to claim 5 for the on-line analysis of the dynamic concentration of morin in plants.
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