CN117019155B - Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof - Google Patents

Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof Download PDF

Info

Publication number
CN117019155B
CN117019155B CN202311304643.0A CN202311304643A CN117019155B CN 117019155 B CN117019155 B CN 117019155B CN 202311304643 A CN202311304643 A CN 202311304643A CN 117019155 B CN117019155 B CN 117019155B
Authority
CN
China
Prior art keywords
monoatomic
enzyme
carbon quantum
quantum dot
defect
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202311304643.0A
Other languages
Chinese (zh)
Other versions
CN117019155A (en
Inventor
张志杨
徐文龙
肖清波
丁子萱
冯迎辰
刘和军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Academy of Agricultural Sciences
Original Assignee
Jiangsu Academy of Agricultural Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Academy of Agricultural Sciences filed Critical Jiangsu Academy of Agricultural Sciences
Priority to CN202311304643.0A priority Critical patent/CN117019155B/en
Publication of CN117019155A publication Critical patent/CN117019155A/en
Application granted granted Critical
Publication of CN117019155B publication Critical patent/CN117019155B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P21/00Plant growth regulators
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Botany (AREA)
  • General Chemical & Material Sciences (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

The invention provides a single-atom-defect carbon quantum dot nano-enzyme with multienzyme catalytic activity, and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) Mixing o-phenylenediamine with metal precursor salt, and calcining at a low temperature under the protection of nitrogen to obtain an intermediate 1 with weak coordination of iron and nitrogen; 2) Adding an acid solution with a set concentration into the intermediate 1 obtained in the step 1), drying, washing with alcohol, filtering, and drying to obtain a monoatomic defect intermediate 2; 3) Calcining the monoatomic defect intermediate 2 obtained in the step 2) at a high temperature under the protection of nitrogen to obtain the monoatomic defect carbon quantum dot nano enzyme solid. The single-atom-defect carbon quantum dot nano enzyme structure designed by the invention is rich in multiple functions such as metal defects, single-atom active centers, down-conversion characteristics of carrier carbon quantum dots and the like, can be used for promoting plant growth in normal environment and stress environment, and has wide application prospect.

Description

Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof
Technical Field
The invention relates to the field of nano enzyme material design and preparation, in particular to a single-atom defect carbon quantum dot nano enzyme with multienzyme catalytic activity, a preparation method and application thereof.
Background
The nano-enzyme is an inorganic nano-material with enzyme-like catalytic action, and the catalytic principle is that nano-level enzyme molecules are utilized to catalyze chemical reactions, and the enzyme molecules have high catalytic activity and specificity and can catalyze the chemical reactions under mild conditions, so that the reaction rate and selectivity are improved. Compared with the traditional catalyst, the nano-enzyme has the characteristics of simple and stable preparation, strong environmental tolerance, high catalytic efficiency and the like, and is widely applied to a plurality of fields such as chemical industry, agriculture, medicine, environment and the like.
Most of the nano enzymes reported at present can be classified into inorganic nano materials (such as metal oxide nano enzymes, noble metal nano enzymes and carbon-based nano enzymes), only surface atoms of the materials participate in the enzyme-like catalytic process, the number of exposed active sites is small, the catalytic performance is single, the nano enzymes have no multi-enzyme catalytic activity, the nano enzymes lack of a natural enzyme multi-stage structure, agglomeration is easy to occur, and part of nano enzyme materials (such as nano CeO) 2 ) Even with physiological toxicity, which makes the performance of most nanoenzymes still have a large room for improvement.
Disclosure of Invention
The invention aims to provide the monoatomic defect carbon quantum dot nano enzyme with multienzyme catalytic activity, and the preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of single-atom-defect carbon quantum dot nano-enzyme with multi-enzyme catalytic activity, which comprises the following steps:
1) Mixing o-phenylenediamine with metal precursor salt, and calcining at a low temperature under the protection of nitrogen to obtain an intermediate 1 with weak coordination of iron and nitrogen;
2) Adding an acid solution with a set concentration into the intermediate 1 obtained in the step 1), drying, washing with alcohol, filtering, and drying to obtain a monoatomic defect intermediate 2;
3) Calcining the monoatomic defect intermediate 2 obtained in the step 2) at a high temperature under the protection of nitrogen to obtain the monoatomic defect carbon quantum dot nano enzyme solid.
Further, in step 1), the metal precursor salt is selected from one of ferric chloride, ferric sulfate, ferric nitrate, zinc chloride, zinc sulfate, zinc nitrate, manganese chloride, manganese sulfate and manganese nitrate.
Further, in the step 1), the mass ratio of the o-phenylenediamine to the metal precursor salt is 1: (0.01 to 0.1).
In step 1), the low-temperature calcination is performed at a calcination temperature of 150-200 ℃ for 1-12 hours.
Further, in the step 2), the acid solution is one of sulfuric acid and hydrochloric acid.
Further, in the step 2), the set concentration of the acid solution is 0.01-0.1 mol/L.
Further, in step 2), the alcohol is one of methanol, ethanol or propanol.
In step 2), a filter membrane with a pore diameter of 0.01-0.3 μm is used for filtering.
Further, in the step 2), the drying temperature of the two times of drying before and after is 50-100 ℃ and the time is 4-24 hours. Preferably, the drying temperature is 60-100 ℃, and the drying time is 4-12 hours. It will be appreciated that the temperature and time of the two bakes are not required to be exactly the same, but the same parameter settings are typically used to simplify the process flow.
In step 3), the calcination temperature of the high-temperature calcination is 250-350 ℃ and the calcination time is 1-6 h.
The invention also provides the monoatomic defect carbon quantum dot nano-enzyme prepared by the preparation method.
The size of the monoatomic defect carbon quantum dot nano enzyme is 3-10 nm, and the monoatomic defect carbon quantum dot nano enzyme is completely water-soluble and can smoothly enter a plant body.
The invention also provides application of the monoatomic defect carbon quantum dot nano-enzyme in promoting plant growth in normal environment and stress environment.
Further, the plant is rice, wheat or leaf vegetable.
Furthermore, the application method of the monoatomic defect carbon quantum dot nano enzyme is seed soaking, leaf surface spraying or a mixture of the seed soaking and the leaf surface spraying, the application concentration is 50-600 mg/L, and the solvent is water.
The beneficial effects of the invention are as follows:
the invention designs the monoatomic defect carbon quantum dot nano enzyme by combining defect catalysis, monoatomic catalysis and down-conversion luminescence concepts, wherein a metal defect site can show CAT-like enzyme activity, a monoatomic active site can show POD-like enzyme activity, a carrier carbon quantum dot can convert visible light into yellow light and has down-conversion characteristics, the visible light has double enzyme activity and has good micro-environment in a plant body and down-conversion characteristics so as to promote plant rooting, and the growth of the plant under normal environment and stress environment is greatly promoted by seed soaking and leaf surface spraying means. In addition, the nano enzyme provided by the invention has the advantages of safe constituent elements and high environmental safety, and can provide a feasible technical route for the design of novel multifunctional agricultural nano enzyme.
Drawings
FIG. 1 is a flow chart of a preparation method of the monoatomic defect carbon quantum dot nano-enzyme.
FIG. 2 is an optical photograph of the single-atom-defect carbon quantum dot nanoenzyme and an aqueous solution thereof according to the present invention.
FIG. 3 shows the growth of the nano-enzyme treated and untreated lettuce of the present invention in a normal growth environment.
FIG. 4 shows the growth of nanoenzyme treated and untreated rice of the invention in drought stress environments.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be described in further detail below with reference to examples and with reference to the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
With reference to fig. 1, the technical gist of the present invention includes:
1) Mixing o-phenylenediamine with metal precursor salt, and calcining at a low temperature under the protection of nitrogen; the coordination effect of the metal and nitrogen is weaker under the low-temperature calcination, and the intermediate 1 with weak coordination of iron and nitrogen is obtained.
2) Adding an acid solution with proper concentration into the intermediate 1 obtained in the step 1), drying, washing with alcohol, filtering and drying; the acid concentration is controlled to wash away part of the metal to form intermediate 2 containing metal defects.
3) Calcining the monoatomic defect intermediate 2 obtained in the step 2) at a high temperature under the protection of nitrogen; in high-temperature calcination, the metal and nitrogen form strong coordination, and metal vacancies are reserved, so that the monoatomic defect carbon quantum dot nano-enzyme with coexistent metal defect sites and metal monoatoms is formed. The nano-enzyme has a large amount of oxygen-containing functional groups, so that the nano-enzyme has good water solubility.
The metal defect site is formed by nonmetal suspended C-N, can show CAT-like enzyme activity, and the single-atom active site can show POD-like enzyme activity, so that microenvironment in a plant body can be improved through double enzyme activity. The carrier carbon quantum dots can convert visible light into yellow light, have the down conversion characteristic and can promote plant rooting. The comprehensive effect of the nano-enzyme can greatly promote the growth of plants in normal environment and stress environment.
The preparation method has the advantages of safe constituent elements, low cost and good environmental safety, has double functions of double enzyme catalysis and light conversion, can promote the growth of plants in normal environment and stress environment, and provides a feasible technical route for the design of novel multifunctional agricultural nano-enzyme.
Examples
(1) 2.0 g o-phenylenediamine and 0.02 g ferric sulfate (or 0.15 g ferric nitrate or 0.2 g ferric chloride can also be used), and calcining 12h at 150 ℃ under the protection of nitrogen gas, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.01 mol/L sulfuric acid, dried at 50℃for 24h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.01 μm nanofiltration membrane, and dried at 50℃for 24h to give intermediate 2.
(3) Calcining the intermediate 2 at 250 ℃ for 6 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion. The solid powder is brown and is bright yellow after being dissolved in water, the optical photo is shown in figure 2, and the nano enzyme prepared in the following example is consistent with the appearance characterization of the example.
Examples
(1) 2.0 g o-phenylenediamine and 0.02 g ferric sulfate (or 0.15 g ferric nitrate or 0.2 g ferric chloride can also be used), and calcining 12h at 150 ℃ under the protection of nitrogen gas, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.01 mol/L hydrochloric acid, dried at 50℃for 24h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.01 μm nanofiltration membrane, and dried at 50℃for 24h to give intermediate 2.
(3) Calcining the intermediate 2 at 250 ℃ for 6 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.2 g ferric sulfate (or 0.15 g ferric nitrate or 0.2 g ferric chloride can also be used), and calcining 1 h at 200 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.1mol/L sulfuric acid, dried at 100℃for 4h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.3 μm nanofiltration membrane, and dried at 100℃for 4h to give intermediate 2.
(3) Calcining the intermediate 2 at 350 ℃ for 1 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.2 g ferric sulfate (or 0.15 g ferric nitrate or 0.2 g ferric chloride can also be used), and calcining for 2 hours at 170 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.05mol/L sulfuric acid, dried at 60℃for 8h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.2 μm nanofiltration membrane, and dried at 60℃for 8h to give intermediate 2.
(3) Calcining the intermediate 2 at 300 ℃ for 2 hours to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.02 g zinc sulfate (or 0.15 g zinc nitrate or 0.2 g zinc chloride can also be used), and calcining 12h at 150 ℃ under the protection of nitrogen gas, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.01 mol/L sulfuric acid, dried at 50℃for 24h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.01 μm nanofiltration membrane, and dried at 50℃for 24h to give intermediate 2.
(3) Calcining the intermediate 2 at 250 ℃ for 6 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.02 g zinc sulfate (or 0.15 g zinc nitrate or 0.2 g zinc chloride can also be used), and calcining 12h at 150 ℃ under the protection of nitrogen gas, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.01 mol/L hydrochloric acid, dried at 50℃for 24h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.01 μm nanofiltration membrane, and dried at 50℃for 24h to give intermediate 2.
(3) Calcining the intermediate 2 at 250 ℃ for 6 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.2 g zinc sulfate (or 0.15 g zinc nitrate or 0.2 g zinc chloride can also be used), and calcining 1 h at 200 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.1mol/L sulfuric acid, dried at 100℃for 4h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.3 μm nanofiltration membrane, and dried at 100℃for 4h to give intermediate 2.
(3) Calcining the intermediate 2 at 350 ℃ for 1 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.2 g zinc sulfate (or 0.15 g zinc nitrate or 0.2 g zinc chloride can also be used), and calcining 2h at 170 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.05mol/L sulfuric acid, dried at 60℃for 8 hours, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.2 μm nanofiltration membrane, and dried at 60℃for 8h to give intermediate 2.
(3) Calcining the intermediate 2 at 300 ℃ for 2h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.02 g manganese sulfate (or 0.15 g manganese nitrate or 0.2 g manganese chloride can also be used), and calcining 12h at 150 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.01 mol/L sulfuric acid, dried at 50℃for 24h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.01 μm nanofiltration membrane, and dried at 50℃for 24h to give intermediate 2.
(3) Calcining the intermediate 2 at 250 ℃ for 6 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.02 g manganese sulfate (or 0.15 g manganese nitrate or 0.2 g manganese chloride can also be used), and calcining 12h at 150 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.01 mol/L hydrochloric acid, dried at 50℃for 24h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.01 μm nanofiltration membrane, and dried at 50℃for 24h to give intermediate 2.
(3) Calcining the intermediate 2 at 250 ℃ for 6 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.2 g manganese sulfate (or 0.15 g manganese nitrate or 0.2 g manganese chloride can also be used), and calcining 1 h at 200 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.1mol/L sulfuric acid, dried at 100℃for 4h, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.3 μm nanofiltration membrane, and dried at 100℃for 4h to give intermediate 2.
(3) Calcining the intermediate 2 at 350 ℃ for 1 h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
Examples
(1) 2.0 g o-phenylenediamine and 0.2 g manganese sulfate (or 0.15 g manganese nitrate or 0.2 g manganese chloride can also be used), and calcining 1 h at 200 ℃ under the protection of nitrogen, so as to obtain an intermediate 1.
(2) The intermediate 1 obtained above was added with 0.1mol/L sulfuric acid, dried at 60℃for 8 hours, added with 20 mL ethanol (or 20 mL methanol or 20 mL propanol may also be) and filtered through a 0.2 μm nanofiltration membrane, and dried at 60℃for 8 hours to give intermediate 2.
(3) Calcining the intermediate 2 at 300 ℃ for 2h to obtain the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and down-conversion.
The following test was performed to verify the performance of the nano-enzyme prepared in the present invention, taking the nano-enzyme prepared in example 1 as an example.
The method selects the lettuce as a test plant, and verifies the influence of the nano enzyme on the normal growth condition of the plant. Selecting seedling raising cotton, uniformly sowing the lettuce seeds into seedling raising cotton holes, covering the seedling raising cotton holes with a preservative film after watering thoroughly, and controlling the temperature indoors to enable seedlings to be seen about 7 days. And transplanting and planting the lettuce seedlings into a water planting box, spraying 300 mg/L atomic defect carbon quantum dot nano enzyme solution on the 7 th day after transplanting, and performing normal water planting until the lettuce grows. And setting a blank control group (CK) in the experiment, namely replacing the nano enzyme solution sprayed with the single-atom defect carbon quantum dots with an aqueous solution, and keeping the other conditions consistent. And comparing the growth condition of the lettuce after the experiment is finished. The culture conditions in the incubator are set to be 16-h in daytime, the temperature is 25 ℃, the humidity is 80%, and the illumination intensity is 10000lx; the culture was carried out at night at a temperature of 25℃and a humidity of 80% without illumination at 8h, 42 d.
As shown in fig. 3, after the lettuce is treated by the single-atom-defect carbon quantum dot nano enzyme solution, compared with an untreated sample, the single-atom-defect carbon quantum dot nano enzyme can obviously improve the growth condition of the lettuce, and shows a more developed root system and a higher fresh weight which are visible to naked eyes. Therefore, after 300 mg/L of the monoatomic defect carbon quantum dot nano enzyme solution is treated, the growth of the root system of the lettuce can be obviously promoted, and the growth condition of the lettuce can be improved.
Adopting PEG to simulate drought experiment, setting the culture condition in the incubator as illumination 16 h in daytime, the temperature is 25 ℃, the humidity is 80%, and the illumination intensity is 10000lx; the culture was carried out at night at a temperature of 25℃and a humidity of 80% without light at 8h, 21 d. 300 mg/L of atomic defect carbon quantum dot nano enzyme solution is sprayed in an experimental group, and a blank control group (CK) is arranged in the experiment, namely, the single atomic defect carbon quantum dot nano enzyme solution is sprayed and replaced by an aqueous solution, and other conditions are consistent.
As shown in fig. 4, after the rice seedlings are treated by the monoatomic defect carbon quantum dot nano enzyme solution, compared with untreated samples, the monoatomic defect carbon quantum dot nano enzyme can obviously improve the growth condition of the rice seedlings, and shows a more developed root system and a higher fresh weight which are visible to naked eyes. Therefore, after 300 mg/L of monoatomic defect carbon quantum dot nano enzyme solution is treated, the growth of rice seedling root systems can be obviously promoted, and the growth condition of lettuce can be improved.
Test examples 1 and 2 were tested using the nanoenzyme prepared in example 1 as an example to demonstrate the effect, and the test results of the other several examples were substantially identical to example 1.
It should be understood that the foregoing examples of the present invention are merely illustrative of the present invention and not limiting of the embodiments of the present invention, and that various other changes and modifications can be made by those skilled in the art based on the above description, and it is not intended to be exhaustive of all the embodiments of the present invention, and all obvious changes and modifications that come within the scope of the invention are defined by the following claims.

Claims (7)

1. The preparation method of the monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity is characterized by comprising the following steps:
1) Mixing o-phenylenediamine with metal precursor salt, and calcining at low temperature under the protection of nitrogen to obtain a metal and nitrogen weakly coordinated intermediate 1, wherein the calcining temperature of the low-temperature calcination is 150-200 ℃ and the calcining time is 1-12 hours, and the metal precursor salt is one of ferric chloride, ferric sulfate, ferric nitrate, zinc chloride, zinc sulfate, zinc nitrate, manganese chloride, manganese sulfate and manganese nitrate;
2) Adding an acid solution with a set concentration into the intermediate 1 obtained in the step 1), drying, washing with alcohol, filtering, and drying to obtain a monoatomic defect intermediate 2;
3) And (3) calcining the monoatomic defect intermediate 2 obtained in the step (2) at a high temperature under the protection of nitrogen to obtain monoatomic defect carbon quantum dot nano enzyme solid, wherein the calcining temperature of the high-temperature calcining is 250-350 ℃, and the calcining time is 1-6 h.
2. The preparation method according to claim 1, wherein in the step 1), the mass ratio of the o-phenylenediamine to the metal precursor salt is 1:0.01 to 0.1.
3. The method according to claim 1, wherein in step 2), the acid solution is one of sulfuric acid and hydrochloric acid; and/or the set concentration of the acid solution is 0.01-0.1 mol/L.
4. The method according to claim 1, wherein in step 2), the alcohol is one of methanol, ethanol and propanol; and/or filtering with a filter membrane with a pore size of 0.01-0.3 μm.
5. The preparation method according to claim 1, wherein in step 2), the drying temperatures of the two previous and subsequent drying steps are 50-100 ℃ and the time is 4-24 hours.
6. The monoatomic defect carbon quantum dot nano-enzyme prepared by the preparation method of any one of claims 1-5.
7. The use of the monoatomic defect carbon quantum dot nanoenzyme of claim 6 to promote plant growth in normal and stress environments.
CN202311304643.0A 2023-10-10 2023-10-10 Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof Active CN117019155B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311304643.0A CN117019155B (en) 2023-10-10 2023-10-10 Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311304643.0A CN117019155B (en) 2023-10-10 2023-10-10 Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN117019155A CN117019155A (en) 2023-11-10
CN117019155B true CN117019155B (en) 2023-12-29

Family

ID=88602768

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311304643.0A Active CN117019155B (en) 2023-10-10 2023-10-10 Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117019155B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0888005A (en) * 1994-09-20 1996-04-02 Tanaka Kagaku Kenkyusho:Kk Manufacture of cobalt monoxide powder
CN107768638A (en) * 2017-10-19 2018-03-06 北京理工大学 A kind of lithium sulfur battery anode material and the lithium-sulfur cell using the positive electrode
CN110665533A (en) * 2019-10-29 2020-01-10 深圳大学 Non-noble metal doped carbon fiber membrane for purifying formaldehyde at room temperature and preparation method and application thereof
CN116656350A (en) * 2023-03-28 2023-08-29 华南理工大学 Solid single-particle dispersed carbon dots, and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5777517B2 (en) * 2008-10-03 2015-09-09 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Perhydrolase stabilization
EP2535971B1 (en) * 2010-02-10 2018-10-24 Showa Denko K.K. Process for producing fuel cell electrode catalyst, process for producing transition metal oxycarbonitride, fuel cell electrode catalyst, and uses thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0888005A (en) * 1994-09-20 1996-04-02 Tanaka Kagaku Kenkyusho:Kk Manufacture of cobalt monoxide powder
CN107768638A (en) * 2017-10-19 2018-03-06 北京理工大学 A kind of lithium sulfur battery anode material and the lithium-sulfur cell using the positive electrode
CN110665533A (en) * 2019-10-29 2020-01-10 深圳大学 Non-noble metal doped carbon fiber membrane for purifying formaldehyde at room temperature and preparation method and application thereof
CN116656350A (en) * 2023-03-28 2023-08-29 华南理工大学 Solid single-particle dispersed carbon dots, and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Efficient oxygen reduction reaction electrocatalysts synthesized from an ironcoordinated aromatic polymer framework;Yong Zhao等;《Journal of Materials Chemistry A》;第4卷;全文 *
MOFs衍生复合材料的制备及其仿生催化性能研究;刘民;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第02期);全文 *
微波法制备HMS包络合铁配合物催化剂催化苯酚羟基化反应;吕爱霞;《工业催化》;第20卷(第5期);全文 *
碱性介质中Fe/N/C催化剂的氧气还原反应催化性能研究;郑龙珍 等;《化学学报》;第70卷;全文 *

Also Published As

Publication number Publication date
CN117019155A (en) 2023-11-10

Similar Documents

Publication Publication Date Title
CN108993548A (en) A kind of visible light responsive photocatalyst and application thereof, preparation method and application method
CN110183261A (en) A kind of nutrient solution and ciltivating process suitable for deep liquid stream water planting romaine lettuce
CN106111140B (en) Cobaltosic oxide micro belt and preparation method thereof with high peroxidase Activity and stabill
CN111527851B (en) Photocatalytic foliar fertilization method
CN112608190B (en) Preparation method of pH/salt-sensitive porous 3D structure slow-release nitrogen fertilizer based on MOF (Cu) @ biochar
CN112604690A (en) Method for preparing rare earth perovskite/biochar composite material by using agricultural and forestry wastes and application thereof
CN104604930A (en) Preparation method of plant selenium enrichment enhancer
CN114586614B (en) Application of manganese ferrite nano material in inducing premature flowering and yield increase of tomatoes
CN117019155B (en) Monoatomic defect carbon quantum dot nano-enzyme with multienzyme catalytic activity and preparation method and application thereof
CN116510777B (en) Plant microenvironment response type diatomic nanoenzyme and preparation method and application thereof
CN103641636A (en) Nano light carbon agent and preparation method thereof
CN111359615A (en) Carbon-doped material catalyst and preparation method and application thereof
CN113145124A (en) 3D core-shell beta-bismuth oxide/cobalt aluminum hydrotalcite direct Z-type heterojunction catalyst and preparation method and application thereof
AU2016334226B2 (en) Managing ethylene in plants using a synergistic agricultural formula comprising diacyl or diary urea and at least one metal complex
CN116751090A (en) PH responsive controlled-release iron fertilizer and preparation method thereof
CN113562804A (en) Method for degrading herbicide by visible light
CN1849870A (en) CO2 slow-release gas-fertilizer of two-component solid hanging-bag type and production method
IT9020310A1 (en) STIMULATION OF GROWTH OF PLANTS
CN107347541A (en) A kind of cultivation implantation methods of selenium-enriched rice
CN117069958B (en) Multielement defect iron-based MOFs nano-enzyme and preparation method and application thereof
CN115025789B (en) In-situ preparation method and application of high-activity copper sulfide biochar catalyst CuSx@BC
BR112020023456A2 (en) compositions, systems and methods for releasing an element in response to biological demand
CN106718813B (en) Slow-release fertilizer nutrition preparation suitable for sargassum thunbergii seedling collection attachment base
CN117139354B (en) Method for synchronously preventing and controlling arsenic accumulation of rice and reducing carbon emission of rice field
CN112844363B (en) Preparation of tubular ZnO-SnO by biological template method 2 Composite nanomaterial

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant