CN115109588B - Rare earth doped hydrotalcite nano-optical fertilizer and preparation method and application thereof - Google Patents
Rare earth doped hydrotalcite nano-optical fertilizer and preparation method and application thereof Download PDFInfo
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- CN115109588B CN115109588B CN202210847638.3A CN202210847638A CN115109588B CN 115109588 B CN115109588 B CN 115109588B CN 202210847638 A CN202210847638 A CN 202210847638A CN 115109588 B CN115109588 B CN 115109588B
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 105
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 104
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 104
- 239000003337 fertilizer Substances 0.000 title claims abstract description 85
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 80
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003287 optical effect Effects 0.000 claims abstract description 45
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- -1 europium ions Chemical class 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000012266 salt solution Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 150000000918 Europium Chemical class 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000029553 photosynthesis Effects 0.000 claims description 8
- 238000010672 photosynthesis Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 240000008067 Cucumis sativus Species 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000005837 radical ions Chemical class 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 235000002566 Capsicum Nutrition 0.000 claims description 3
- 244000061176 Nicotiana tabacum Species 0.000 claims description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 239000006002 Pepper Substances 0.000 claims 1
- 235000016761 Piper aduncum Nutrition 0.000 claims 1
- 235000017804 Piper guineense Nutrition 0.000 claims 1
- 244000203593 Piper nigrum Species 0.000 claims 1
- 235000008184 Piper nigrum Nutrition 0.000 claims 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 230000012010 growth Effects 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 240000008574 Capsicum frutescens Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001390 capsicum minimum Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000009849 Cucumis sativus Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BJENZJLZGVHMTK-UHFFFAOYSA-N europium hydrochloride Chemical compound Cl.[Eu] BJENZJLZGVHMTK-UHFFFAOYSA-N 0.000 description 1
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008558 metabolic pathway by substance Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C21/00—Methods of fertilising, sowing or planting
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
- A01G7/06—Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Forests & Forestry (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Ecology (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Botany (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
A rare earth doped hydrotalcite nanometer optical fertilizer, a preparation method and application thereof. The invention provides a rare earth doped hydrotalcite nano-optical fertilizer, belonging to the technical field of pesticides and fertilizers. The rare earth doped hydrotalcite nanometer optical fertilizer provided by the invention comprises hydrotalcite nanometer sheets and trivalent europium ions doped in the hydrotalcite nanometer sheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nanometer optical fertilizer is 2-30%. Through structural design and optimization, europium element can show good light conversion performance, ultraviolet light in a natural spectrum can be converted into red light which can be efficiently utilized by plants, and crop yield is improved; according to the invention, the hydrotalcite nano-sheets are used as trivalent europium ion structural elements, trivalent europium ions are doped in the structures of the hydrotalcite nano-sheets, the structure is stable, photobleaching is not easy to occur, and the long-acting stability of the light-converting performance of the light fertilizer can be improved; the two-dimensional domain-limiting effect of the hydrotalcite nano-sheet is helpful for improving the quantum efficiency of the light conversion material. The invention achieves the accurate matching of the crop growth requirement through the control of the europium doping proportion.
Description
Technical Field
The invention relates to the technical field of pesticides and fertilizers, in particular to a rare earth doped hydrotalcite nano-optical fertilizer, a preparation method and application thereof.
Background
With the continuous improvement of cultivation level, the crop yield is approaching to the limit, and the crop yield is difficult to be greatly improved simply by increasing the water and fertilizer supply, and the environmental bearing capacity is also faced with great challenges. Therefore, the development of a new crop yield increasing means which does not depend on the increase of water and fertilizer supply has important significance for guaranteeing the grain safety, is more beneficial to reducing the non-point source pollution and realizes the aim of agricultural sustainable development.
In a plurality of yield increasing means, the photosynthesis of crops is promoted by light environment regulation, and the realization of yield increase is widely focused by scientific researchers. The light environment plays a vital role in plant growth, and plants can receive different light quality through light receptors to regulate the growth and development, photosynthesis and substance metabolism of the plants. The research result shows that the blue-violet light region of 400-510 nm and the red-orange light region of 610-720 nm are the main wavelength ranges for plants to absorb visible light. Therefore, through the use of the light conversion material, the spectrum with lower crop utilization rate in the natural spectrum is selectively converted into blue light or red light which can be efficiently utilized by plants, the light environment is optimized, and the purposes of promoting crop photosynthesis, improving the water and fertilizer utilization rate and increasing the carbon content on the basis of not increasing additional water and fertilizer supply and increasing environmental bearing pressure can be realized, thereby achieving the purpose of increasing the crop yield.
In recent years, widely studied agricultural light conversion materials include: quantum dots, rare earth metal complexes, and the like. The materials represented by various quantum dots have the advantages of good monochromaticity, high quantum efficiency and the like, but the quantum dot materials are high in price and difficult to prepare in a large scale; the light conversion material of the rare earth metal complex takes rare earth ions such as europium, samarium, terbium and the like as the center, salicylic acid, phenanthroline and the like as ligands, and the synthesized salicylic acid and phenanthroline ternary complex comprises Eu (Hsal) 3phen,Sm1-xTbx(TTA)3 phen and the like, and has red excitation light with higher matching performance, but the complex ligand is mainly an organic molecule with a ring mechanism, so that the light stability is poor, photolysis is easy to occur, and long-acting stable spectrum optimization is difficult to realize.
Disclosure of Invention
In view of the above, the invention aims to provide a rare earth doped hydrotalcite nano-optical fertilizer, which has long-acting stable light conversion performance.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a rare earth doped hydrotalcite nanometer optical fertilizer, which comprises hydrotalcite nanometer sheets and trivalent europium ions doped in the hydrotalcite nanometer sheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nanometer optical fertilizer is 2-30%.
Preferably, the chemical composition of the hydrotalcite nano-sheet is (M 1)x(M2)1-x(OH)2Ky·zH2 O, wherein M 1 is one or more of Mg 2 +、Ca2+、Zn2+;
M 2 is one or more of Fe 3+、Cr3+ and Al 3+;
K is an acid radical ion;
x=0.2 to 0.5; the value of y is such that (charge of M 1)x(M2)1-x(OH)2Ky·zH2 O remains conserved; z=1 to 20).
Preferably, the chemical composition of the rare earth doped hydrotalcite nano-optical fertilizer is (M 1)x(EuM2)1-x(OH)2Ky·zH2 O).
Preferably, the particle size of the rare earth doped hydrotalcite nano optical fertilizer is 20-200 nm.
The invention provides a preparation method of the rare earth doped hydrotalcite nano optical fertilizer, which comprises the following steps:
Providing a precursor solution for preparing hydrotalcite nano-sheets, wherein the precursor solution comprises a soluble metal salt solution and a strong alkali solution;
and mixing the soluble trivalent europium salt, the soluble metal salt solution and the strong alkali solution, and performing coprecipitation reaction to obtain the rare earth doped hydrotalcite nanometer light fertilizer.
Preferably, the coprecipitation reaction is carried out under shearing conditions, wherein the shearing speed is 3000-8000 r/min, and the time is 1-5 min.
Preferably, the concentration of the soluble metal salt solution is 0.005-0.5 mol/L, and the concentration of the strong base solution is 0.01-1.0 mol/L.
The invention provides application of the rare earth doped hydrotalcite nano-optical fertilizer in promoting photosynthesis of crops.
Preferably, the crop is one or more of cucumber, capsicum and tobacco.
Preferably, the application method comprises the following steps:
Applying the rare earth doped hydrotalcite nano optical fertilizer aqueous dispersion liquid to the surface of a crop leaf;
The concentration of the rare earth doped hydrotalcite nano optical fertilizer aqueous dispersion liquid is 0.1-2 g/L;
the application amount of the rare earth doped hydrotalcite nano optical fertilizer is 5-20 g/mu.
The invention provides a rare earth doped hydrotalcite nanometer optical fertilizer, which comprises hydrotalcite nanometer sheets and trivalent europium ions doped in the hydrotalcite nanometer sheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nanometer optical fertilizer is 2-30%. In the invention, europium element has good light-converting performance, can convert ultraviolet light in natural spectrum into red light which can be efficiently utilized by plants, and achieves the purposes of improving the photosynthesis rate of crops, improving chlorophyll content, increasing leaf area and improving crop yield; hydrotalcite is a layered double hydroxide (Layered double hydroxide, LDH) with a two-dimensional layered structure consisting of layers and interlayer intercalation molecules, wherein the layers consist of metal atoms and hydroxyl groups according to a hexacoordination principle and carry positive charges; the intercalation molecule is composed of acid radical ion and has negative charge. According to the invention, the hydrotalcite nano-sheet is used as a trivalent europium ion load matrix, and trivalent europium ions are doped in the structure of the hydrotalcite nano-sheet, so that the structure is stable, photobleaching is not easy to occur, and the long-acting stability of the light conversion performance of the light fertilizer can be improved; meanwhile, the two-dimensional finite field effect of the hydrotalcite nano-sheet is beneficial to the improvement of the quantum efficiency of the light conversion material. The invention achieves the accurate matching of the crop growth requirement through the control of the europium doping proportion.
Drawings
FIG. 1 is a scanning electron microscope image of the rare earth doped hydrotalcite nano optical fertilizer obtained in example 1;
FIG. 2 is a transmission electron microscope image of the rare earth doped hydrotalcite nano optical fertilizer obtained in example 1;
FIG. 3 is an XRD pattern of the rare earth doped hydrotalcite nano-optical fertilizer obtained in example 1;
FIG. 4 shows the result of X-ray photoelectron analysis of the rare earth doped hydrotalcite nano-optical fertilizer obtained in example 1;
FIG. 5 shows the results of ICP analysis of the rare earth doped hydrotalcite nano-optical fertilizer obtained in example 1;
FIG. 6 is an absorption spectrum of the rare earth doped hydrotalcite nano optical fertilizer obtained in example 1;
FIG. 7 is an excitation emission spectrum of the rare earth doped hydrotalcite nano-optical fertilizer obtained in example 1;
Fig. 8 is an ICP analysis result of the rare earth doped hydrotalcite nano optical fertilizer obtained in example 2.
Detailed Description
The invention provides a rare earth doped hydrotalcite nanometer optical fertilizer, which comprises hydrotalcite nanometer sheets and trivalent europium ions doped in the hydrotalcite nanometer sheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nanometer optical fertilizer is 2-30%, preferably 4-20%, more preferably 6-15%.
In the invention, the chemical composition of the hydrotalcite nano-sheet is preferably (M 1)x(M2)1-x(OH)2Ky·zH2 O, wherein M 1 is one or more of Mg 2+、Ca2+、Zn2+;
M 2 is one or more of Fe 3+、Cr3+ and Al 3+;
K is an acid radical ion, preferably one or more of NO 3 -、SO4 2-、Cl- and an acetate radical;
x=0.2 to 0.5, preferably 0.3 to 0.4;
The value of y keeps (M 1)x(M2)1-x(OH)2Ky·zH2 O charge;
z=1 to 20, preferably 3 to 15, more preferably 5 to 10.
As a specific embodiment of the invention, the hydrotalcite nano-sheets have the chemical composition of Mg0.45Al0.55(OH)2(NO3)0.55·5H2O、Ca0.4Al0.6(OH)2(NO3)0.6·5H2O.
In the invention, the chemical composition of the rare earth doped hydrotalcite nano optical fertilizer is (M 1)x(EuM2)1-x(OH)2Ky·zH2 O, wherein the optional types of M 1、M2 and K are the same as the above, and are not described in detail herein, and the value ranges of x, y and z are the same as the above, and are not described in detail herein.
As a specific embodiment of the invention, the rare earth doped hydrotalcite nano optical fertilizer comprises the following chemical components in percentage by weight Mg0.45EuAl0.55(OH)2(NO3)3.55·5H2O、Ca0.4EuAl0.6(OH)2(NO3)3.6·5H2O.
In the invention, the particle size of the rare earth doped hydrotalcite nano optical fertilizer is preferably 20-200 nm, more preferably 60-100 nm.
The invention provides a preparation method of the rare earth doped hydrotalcite nano optical fertilizer, which comprises the following steps:
Providing a precursor solution for preparing hydrotalcite nano-sheets, wherein the precursor solution comprises a soluble metal salt solution and a strong alkali solution;
and mixing the soluble trivalent europium salt, the soluble metal salt solution and the strong alkali solution, and performing coprecipitation reaction to obtain the rare earth doped hydrotalcite nanometer light fertilizer.
The invention provides a precursor solution for preparing hydrotalcite nano-sheets, wherein the precursor solution comprises a soluble metal salt solution and a strong alkali solution. In the present invention, the soluble metal salt solution preferably includes a soluble divalent metal salt and a soluble trivalent metal salt. In the present invention, the soluble divalent metal salt is preferably one or more of a soluble magnesium salt, a soluble calcium salt and a soluble zinc salt, and particularly preferably one or more of magnesium chloride, calcium chloride, zinc chloride, magnesium sulfate and zinc acetate.
In the present invention, the soluble trivalent metal salt is preferably one or more of a soluble iron salt, a soluble chromium salt and a soluble aluminum salt, and particularly preferably one or more of ferric nitrate, chromium nitrate and aluminum nitrate.
In the present invention, the concentration of the soluble metal salt solution is preferably 0.005 to 0.5mol/L, more preferably 0.01 to 0.45mol/L, and still more preferably 0.1 to 0.4mol/L. In the present invention, the molar ratio of the soluble divalent metal salt to the soluble trivalent metal salt in the soluble metal salt solution is preferably 1 to 4:1, more preferably 2 to 3:1.
In the present invention, the strong alkali solution is preferably NaOH solution; in the present invention, the concentration of the strong alkali solution is preferably 0.01 to 1.0mol/L, more preferably 0.05 to 0.8mol/L, and still more preferably 0.1 to 0.5mol/L.
The invention mixes the soluble trivalent europium salt, the soluble metal salt solution and the strong alkali solution, and carries out coprecipitation reaction to obtain the rare earth doped hydrotalcite nanometer light fertilizer. In the present invention, the soluble trivalent europium salt is preferably one or more of europium nitrate, europium hydrochloride and europium sulfate.
In the present invention, the molar ratio of the soluble trivalent europium salt to other soluble metal salt is preferably 1:1 to 4, more preferably 1:2 to 3.
In the present invention, the coprecipitation reaction is preferably carried out under shearing conditions, and the rate of shearing is preferably 3000 to 8000r/min, more preferably 4000 to 6000r/min, and still more preferably 5000 to 6000r/min. In the present invention, the time for shearing is preferably 1 to 5 minutes, more preferably 2 to 4 minutes. In the invention, in the shearing process, the metal salt between the two solutions and sodium hydroxide are subjected to coprecipitation reaction, and the growth process is controlled by high-speed shearing, so that the nano size is achieved.
After the coprecipitation reaction, the obtained coprecipitation reaction liquid is preferably subjected to solid-liquid separation, and the solid-liquid separation is preferably centrifugation. In the present invention, the rate of the centrifugation is preferably 3000 to 8000rpm, more preferably 4000 to 6000rpm, and still more preferably 8000rpm. After the centrifugation, the present invention preferably disperses the resulting solid in water and repeats the centrifugation until the centrifuged liquid is neutral.
The invention provides application of the rare earth doped hydrotalcite nano-optical fertilizer in promoting photosynthesis of crops. In the present invention, the crop is preferably one or more of cucumber, capsicum and tobacco.
In the invention, the application method comprises the following steps:
The rare earth doped hydrotalcite nanometer optical fertilizer aqueous dispersion is applied to the surface of a crop leaf.
In the invention, the concentration of the rare earth doped hydrotalcite nano optical fertilizer aqueous dispersion liquid is preferably 0.1-2 g/L, more preferably 0.5-1.5 g/L; the application amount of the rare earth doped hydrotalcite nano-optical fertilizer is preferably 5-20 g/mu, more preferably 10-15 g/mu. In the present invention, the application is preferably a spray application.
The rare earth doped hydrotalcite nano optical fertilizer, the preparation method and the application thereof provided by the invention are described in detail below by combining examples, but the rare earth doped hydrotalcite nano optical fertilizer is not to be construed as limiting the protection scope of the invention.
Example 1
The preparation method of the rare earth doped hydrotalcite nanometer optical fertilizer comprises the following steps:
(1) 25.6g of magnesium nitrate, 13.125g of aluminum nitrate and 6.69g of europium nitrate (molar ratio Mg: al: eu=2:0.7:0.3) are weighed and dissolved in 500mL of deionized water to prepare solutions a with the concentrations of 0.2mol/L, 0.07mol/L and 0.03mol/L respectively;
(2) Weighing 12g of sodium hydroxide, dissolving in 500mL of deionized water, and preparing a solution b with the concentration of 0.6 mol/L;
(3) Rapidly mixing the solution a and the solution b in a colloid mill, keeping the rotating speed of 3000r/min, and reacting for 2min to obtain a rare earth doped hydrotalcite nano-sheet solution;
(4) And (3) carrying out high-speed centrifugation on the prepared rare earth hydrotalcite nanosheet solution, keeping the rotating speed of 8000r/min, and reacting for 10min. The supernatant was removed, and after redispersion in water, centrifugation was continued. And repeating the centrifugal operation for 3 times until the supernatant is neutral, thereby obtaining the rare earth doped hydrotalcite nano optical fertilizer.
And carrying out scanning electron microscope and transmission electron microscope tests on the obtained rare earth doped hydrotalcite nano optical fertilizer, wherein the obtained scanning electron microscope is shown in figure 1, and the transmission electron microscope is shown in figure 2. As can be seen from fig. 1 and 2, the rare earth hydrotalcite nano-sheets have regular hexagonal sheet structures, and the particle size distribution is uniform and is about 60nm.
And carrying out X-ray diffraction analysis on the obtained rare earth doped hydrotalcite nano optical fertilizer, wherein the obtained XRD pattern is shown in figure 3. As can be seen from FIG. 3, the prepared rare earth doped hydrotalcite has complete crystal form, ideal crystallinity and high purity, and realizes the effective doping of rare earth elements.
And (3) performing X-ray photoelectron analysis on the obtained rare earth doped hydrotalcite nano optical fertilizer, wherein the obtained result is shown in figure 4. As can be seen from fig. 4, in the hydrotalcite structure, europium elements exist in trivalent form.
ICP analysis is carried out on the rare earth doped hydrotalcite nano optical fertilizer, and the obtained result is shown in figure 5. It can be seen that, in the hydrotalcite nano optical fertilizer prepared in example 1, the contents of magnesium element, aluminum element and europium element are 39.2%,15.34%,6.05%, the ratio is about 6.48:2.54:1, and the europium element content is about 9.9%.
And (3) testing the luminescence performance of the obtained rare earth doped hydrotalcite nano-optical fertilizer, wherein the absorption spectrum of the rare earth doped hydrotalcite nano-optical fertilizer is shown in figure 6, and the excitation emission spectrum is shown in figure 7. As can be seen from fig. 6 and 7, the maximum absorption spectrum of the rare earth doped hydrotalcite nano-optical fertilizer is 394nm, and meanwhile, ultraviolet light with the wavelength is converted into red light with the wavelength of about 620 nm and 700nm, so as to promote photosynthesis of crops.
Example 2
The preparation method of the rare earth doped hydrotalcite nanometer optical fertilizer comprises the following steps:
(1) 14.16g of calcium nitrate, 3.75g of aluminum nitrate and 4.46g of europium nitrate (molar ratio Ca: al: eu=3:0.5:0.5) are weighed and dissolved in 200mL of deionized water to prepare solutions a with the concentrations of 0.3mol/L, 0.05mol/L and 0.05mol/L respectively;
(2) 6.4g of sodium hydroxide is weighed and dissolved in 200mL of deionized water to prepare a solution b with the concentration of 0.8 mol/L;
(3) Rapidly mixing the solution a and the solution b in a colloid mill, keeping the rotation speed of 5000r/min, and reacting for 1min to obtain a hydrotalcite nano-sheet solution;
(4) And (3) carrying out high-speed centrifugation on the prepared hydrotalcite nano-sheet solution, keeping the rotating speed of 8000r/min, and reacting for 10min. The supernatant was removed, and after redispersion in water, centrifugation was continued. And repeating the centrifugal operation for 3 to 5 times until the supernatant is neutral, thereby obtaining the rare earth doped hydrotalcite nano optical fertilizer.
XRD, scanning electron microscope, transmission electron microscope and luminescence performance test results of the rare earth doped hydrotalcite nano optical fertilizer obtained in the embodiment 2 are similar to those of the embodiment 1. As shown in FIG. 8, the contents of calcium element, aluminum element and europium element were 50.78%,12.76% and 22.46%, respectively, in a ratio of about 3.98:1:1.76 and about 26.1%, respectively, by ICP analysis.
Test example 1
The effect evaluation was performed on the rare earth doped hydrotalcite nano-optical fertilizer prepared in examples 1 and 2 by using cucumber as an experimental crop. The testing method comprises the following steps: preparing rare earth doped hydrotalcite nano optical fertilizer into aqueous dispersion with the concentration of 1.0g/L, and taking europium salt solution (europium nitrate) with the same concentration as a reference; spraying when cucumber seedlings grow to 3 rd true leaves, spraying once every 3 days, and counting various physiological indexes of a control group sprayed with the nano-optical fertilizer and not sprayed with the nano-optical fertilizer on the 30 th day after application. The results are shown in Table 1.
Table 1 rare earth doped hydrotalcite nano-optical fertilizer promotes crop growth results
Further, in order to verify the light stability of the rare earth doped hydrotalcite nano-optical fertilizer, after ultraviolet aging is carried out on the rare earth doped hydrotalcite nano-optical fertilizer for 120 hours, cucumbers are used as experimental crops, and the effect evaluation is carried out on the rare earth doped hydrotalcite nano-optical fertilizer prepared in the examples 1 and 2. The testing method comprises the following steps: preparing rare earth doped hydrotalcite nano optical fertilizer into aqueous dispersion with the concentration of 1.0g/L, and taking europium salt solution (europium nitrate) with the same concentration as a reference; spraying when cucumber seedlings grow to 3 rd true leaves, spraying once every 3 days, and counting various physiological indexes of a control group sprayed with the nano-optical fertilizer and not sprayed with the nano-optical fertilizer on the 40 th day after application. The results are shown in Table 2.
TABLE 2 rare earth doped hydrotalcite nano-optical fertilizer after ultraviolet irradiation to promote crop growth result
| Fresh weight/g | Dry weight/g | Leaf area/cm 2 | Plant height/cm | |
| Control group | 12.86±1.04 | 3.28±0.26 | 456.15±22.55 | 13.85±2.04 |
| Example 1 | 14.75±0.61 | 3.83±0.28 | 604.97±30.53 | 16.01±2.49 |
| Example 2 | 14.13±1.74 | 3.72±0.98 | 584.46±47.18 | 15.67±1.96 |
| Europium salt solution | 12.98±0.65 | 3.40±0.27 | 472.60±13.37 | 14.00±1.88 |
As can be seen from tables 1 and 2, the rare earth doped hydrotalcite nano optical fertilizer provided by the invention has long-acting stable light conversion performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (3)
1. Application of rare earth doped hydrotalcite nano optical fertilizer in promoting photosynthesis of crops;
The application method comprises the following steps:
Applying the rare earth doped hydrotalcite nano optical fertilizer aqueous dispersion liquid to the surface of a crop leaf;
the concentration of the rare earth doped hydrotalcite nano optical fertilizer aqueous dispersion liquid is 0.1-2 g/L;
the application amount of the rare earth doped hydrotalcite nano optical fertilizer is 5-20 g/mu;
the rare earth doped hydrotalcite nano-optical fertilizer comprises hydrotalcite nano-sheets and trivalent europium ions doped in the hydrotalcite nano-sheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nano-optical fertilizer is 2-30%;
The chemical composition of the hydrotalcite nano-sheet is (M 1)x(M2)1-x(OH)2Ky∙zH2 O, wherein M 1 is one or more of Mg 2+、Ca2+;
M 2 is Al 3+;
K is acid radical ion, wherein the acid radical ion is one or more of NO 3 -、SO4 2-、Cl- and acetate radical;
x=0.2 to 0.5; the value of y keeps the charge of (M 1)x(M2)1-x(OH)2Ky∙zH2 O to be kept constant; z=1 to 20;
the particle size of the rare earth doped hydrotalcite nano optical fertilizer is 20-200 nm;
the preparation method of the rare earth doped hydrotalcite nano optical fertilizer comprises the following steps:
Providing a precursor solution for preparing hydrotalcite nano-sheets, wherein the precursor solution comprises a soluble metal salt solution and a strong alkali solution;
mixing soluble trivalent europium salt, soluble metal salt solution and strong alkali solution, and performing coprecipitation reaction to obtain rare earth doped hydrotalcite nano light fertilizer;
The coprecipitation reaction is carried out under a shearing condition, the shearing speed is 3000-8000 r/min, and the time is 1-5 min.
2. The use according to claim 1, wherein the concentration of the soluble metal salt solution is 0.005-0.5 mol/L and the concentration of the strong base solution is 0.01-1.0 mol/L.
3. The use according to claim 1, wherein the crop is one or more of cucumber, pepper and tobacco.
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