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 PDFInfo
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- 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
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- 230000007547 defect Effects 0.000 title claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000001354 calcination Methods 0.000 claims abstract description 43
- 102000004190 Enzymes Human genes 0.000 claims abstract description 42
- 108090000790 Enzymes Proteins 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 230000008635 plant growth Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000012010 growth Effects 0.000 description 12
- 238000001728 nano-filtration Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 241000208822 Lactuca Species 0.000 description 11
- 235000003228 Lactuca sativa Nutrition 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008641 drought stress Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- Chemical & Material Sciences (AREA)
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- 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
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.
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