CN115109588A - Rare earth doped hydrotalcite nanometer optical fertilizer and preparation method and application thereof - Google Patents
Rare earth doped hydrotalcite nanometer optical fertilizer and preparation method and application thereof Download PDFInfo
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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 109
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 108
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 108
- 239000003337 fertilizer Substances 0.000 title claims abstract description 88
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 68
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 66
- 230000003287 optical effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 29
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- -1 europium ions Chemical class 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 150000000918 Europium Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000029553 photosynthesis Effects 0.000 claims description 8
- 238000010672 photosynthesis Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 240000008067 Cucumis sativus Species 0.000 claims description 7
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 230000001737 promoting effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000005837 radical ions Chemical class 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
- 239000006002 Pepper Substances 0.000 claims description 3
- 235000016761 Piper aduncum Nutrition 0.000 claims description 3
- 235000017804 Piper guineense Nutrition 0.000 claims description 3
- 244000203593 Piper nigrum Species 0.000 claims description 3
- 235000008184 Piper nigrum Nutrition 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 8
- 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 4
- 230000006872 improvement 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 15
- 150000003839 salts Chemical class 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 5
- 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
- 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
- 238000001000 micrograph Methods 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
- 238000005303 weighing Methods 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
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052791 calcium Inorganic materials 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
- 230000008569 process Effects 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium 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
- 238000005034 decoration Methods 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
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000011229 interlayer Substances 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
- 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 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
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000009313 farming Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000007774 longterm Effects 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
- 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
- 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
Images
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
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- 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 and a preparation method and application thereof. The invention provides a rare earth doped hydrotalcite nanometer optical fertilizer, belonging to the technical field of pesticides and fertilizers. The rare earth doped hydrotalcite nano-optical fertilizer provided by the invention comprises hydrotalcite nanosheets and trivalent europium ions doped in the hydrotalcite nanosheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nano-optical fertilizer is 2-30%. Through structural design and optimization, the europium element can show good light conversion performance, can convert ultraviolet light in a natural spectrum into red light which can be efficiently utilized by plants, and improves the crop yield; according to the invention, the hydrotalcite nanosheets are used as the trivalent europium ion structural elements, and the trivalent europium ions are doped in the hydrotalcite nanosheet structure, 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; the two-dimensional confinement effect of the hydrotalcite nanosheets contributes to the improvement of the quantum efficiency of the light conversion material. The invention achieves the aim of accurately matching the growth requirement of crops by controlling the doping proportion of europium.
Description
Technical Field
The invention relates to the technical field of pesticides and fertilizers, and particularly relates to a rare earth doped hydrotalcite nano optical fertilizer as well as a preparation method and application thereof.
Background
With the continuous improvement of farming level, the crop yield approaches the limit, and the increase of water and fertilizer supply is not only difficult to greatly improve the crop yield, but also causes the environmental bearing capacity to face 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, and is more beneficial to reducing non-point source pollution and realizing the aim of sustainable development of agriculture.
Among various yield increasing means, the photosynthesis of crops is promoted through light environment regulation, and the realization of yield increase is widely concerned by researchers. The light environment plays an important role in plant growth, and plants can receive different light qualities through a light receptor to regulate and control the growth and development, photosynthesis and substance metabolism processes of the plants. Research results show that a blue-violet light area of 400-510 nm and a red-orange light area of 610-720 nm are main wavelength ranges of visible light absorbed by plants. 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 luminous environment is optimized, the photosynthesis of crops can be promoted, the water and fertilizer utilization rate is increased, the carbon content is increased on the basis of not increasing the additional water and fertilizer supply and not increasing the environmental bearing pressure, and the purpose of increasing the yield of crops is achieved.
In recent years, agricultural light conversion materials that have been widely studied include: quantum dots, rare earth metal complexes, and the like. 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 on a large scale; a light-converting material of rare-earth metal complex is a ternary complex of salicylic acid and o-phenanthroline, which is synthesized by using rare-earth ions of europium, samarium and terbium as center and salicylic acid and o-phenanthroline as ligand, and its composition is Eu (Hsal) 3 phen，Sm 1-x Tb x (TTA) 3 phen and the like have red exciting light with high matching property, but because most of the complexing ligands are organic molecules with cyclic mechanisms, the light stability of phen and the like is poor, the phn is easy to generate photolysis, and the long-acting stable spectrum optimization is difficult to realize.
Disclosure of Invention
In view of the above, the present invention aims to provide a rare earth-doped hydrotalcite nano optical fertilizer, which has long-term and 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 nano-optical fertilizer which comprises a hydrotalcite nanosheet and trivalent europium ions doped in the hydrotalcite nanosheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nano-optical fertilizer is 2-30%.
Preferably, the chemical composition of the hydrotalcite nano-sheets is (M) 1 ) x (M 2 ) 1-x (OH) 2 K y ·zH 2 O, wherein M 1 Is Mg 2 + 、Ca 2+ 、Zn 2+ One or more of the above;
M 2 is Fe 3+ 、Cr 3+ Or Al 3+ One or more of the above;
k is acid radical ion;
x is 0.2-0.5; y is equal to (M) 1 ) x (M 2 ) 1-x (OH) 2 K y ·zH 2 Charge conservation for O; and z is 1-20.
Preferably, the chemical composition of the rare earth doped hydrotalcite nano light fertilizer is (M) 1 ) x (EuM 2 ) 1-x (OH) 2 K y ·zH 2 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 the hydrotalcite nano-sheets, wherein the precursor solution comprises a soluble metal salt solution and a strong base solution;
mixing soluble trivalent europium salt, soluble metal salt solution and strong base solution, and carrying out coprecipitation reaction to obtain the rare earth doped hydrotalcite nano optical fertilizer.
Preferably, the coprecipitation reaction is carried out under a shearing condition, the shearing rate 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 alkali solution is 0.01-1.0 mol/L.
The invention provides application of the rare earth doped hydrotalcite nano light fertilizer in promoting crop photosynthesis.
Preferably, the crop is one or more of cucumber, pepper and tobacco.
Preferably, the application method comprises the following steps:
applying the rare earth doped hydrotalcite nano optical fertilizer water dispersion liquid to the surface of a crop leaf;
the concentration of the rare earth doped hydrotalcite nanometer optical fertilizer water dispersion liquid is 0.1-2 g/L;
the application amount of the rare earth doped hydrotalcite nanometer optical fertilizer is 5-20 g/mu.
The invention provides a rare earth doped hydrotalcite nano-optical fertilizer which comprises a hydrotalcite nanosheet and trivalent europium ions doped in the hydrotalcite nanosheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nano-optical fertilizer is 2-30%. In the invention, the europium element has good light conversion performance, and can convert ultraviolet light in a natural spectrum into red light which can be efficiently utilized by plants, thereby achieving the purposes of increasing the photosynthesis rate of crops, increasing the chlorophyll content, increasing the leaf area and improving the crop yield; the hydrotalcite is Layered Double Hydroxide (LDH) and has a two-dimensional Layered structure consisting of Layered plates and interlayer intercalation molecules, wherein the Layered plates are formed by metal atoms and hydroxyl according to a six-coordination principle and have positive charges; the interlayer intercalation molecules consist of acid radical ions and have negative charges. According to the invention, the hydrotalcite nanosheet is used as a trivalent europium ion loading matrix, and trivalent europium ions are doped in the hydrotalcite nanosheet structure, 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 confinement effect of the hydrotalcite nanosheets contributes to the improvement of the quantum efficiency of the light conversion material. The invention achieves the aim of accurately matching the growth requirement of crops by controlling the doping proportion of europium.
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 ICP analysis result 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 a hydrotalcite nanosheet and trivalent europium ions doped in the hydrotalcite nanosheet 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%, and more preferably 6-15%.
In the present invention, the chemical composition of the hydrotalcite nanosheet is preferably (M) 1 ) x (M 2 ) 1-x (OH) 2 K y ·zH 2 O, wherein M 1 Is Mg 2+ 、Ca 2+ 、Zn 2+ One or more of the above;
M 2 is Fe 3+ 、Cr 3+ Or Al 3+ One or more of the above;
k is an acid radical ion, preferably NO 3 - 、SO 4 2- 、Cl - And acetate;
x is 0.2 to 0.5, preferably 0.3 to 0.4;
y is equal to (M) 1 ) x (M 2 ) 1-x (OH) 2 K y ·zH 2 Charge conservation for O;
z is 1 to 20, preferably 3 to 15, and more preferably 5 to 10.
As a specific embodiment of the invention, the chemical composition of the hydrotalcite nano-sheets is Mg 0.45 Al 0.55 (OH) 2 (NO 3 ) 0.55 ·5H 2 O、Ca 0.4 Al 0.6 (OH) 2 (NO 3 ) 0.6 ·5H 2 O。
In the invention, the chemical composition of the rare earth doped hydrotalcite nano optical fertilizer is (M) 1 ) x (EuM 2 ) 1-x (OH) 2 K y ·zH 2 O, wherein M 1 、M 2 The selectable types of K are the same as those of the above, and are not described again; the value ranges of x, y and z are the same as above, and are not described herein again.
As a specific embodiment of the invention, the chemical composition of the rare earth doped hydrotalcite nano light fertilizer is Mg 0.45 EuAl 0.55 (OH) 2 (NO 3 ) 3.55 ·5H 2 O、Ca 0.4 EuAl 0.6 (OH) 2 (NO 3 ) 3.6 ·5H 2 O。
In the invention, the particle size of the rare earth doped hydrotalcite nano optical fertilizer is preferably 20-200 nm, and 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 the hydrotalcite nano-sheets, wherein the precursor solution comprises a soluble metal salt solution and a strong base solution;
mixing soluble trivalent europium salt, soluble metal salt solution and strong base solution, and carrying out coprecipitation reaction to obtain the rare earth doped hydrotalcite nano optical fertilizer.
The invention provides a precursor solution for preparing hydrotalcite nanosheets, which comprises a soluble metal salt solution and a strong base 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 invention, the soluble divalent metal salt is preferably one or more of soluble magnesium salt, soluble calcium salt and soluble zinc salt, and is particularly preferably one or more of magnesium chloride, calcium chloride, zinc chloride, magnesium sulfate and zinc acetate.
In the invention, the soluble trivalent metal salt is preferably one or more of soluble iron salt, soluble chromium salt and soluble aluminum salt, and is 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 0.4 mol/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, and more preferably 2 to 3: 1.
In the present invention, the strong alkaline solution is preferably a NaOH solution; in the invention, the concentration of the strong alkali solution is preferably 0.01-1.0 mol/L, more preferably 0.05-0.8 mol/L, and further preferably 0.1-0.5 mol/L.
The method mixes the soluble trivalent europium salt, the soluble metal salt solution and the strong base solution to carry out coprecipitation reaction, so as to obtain the rare earth doped hydrotalcite nanometer optical 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 the other soluble metal salt is preferably 1: 1-4, more preferably 1: 2 to 3.
In the invention, the coprecipitation reaction is preferably carried out under a shearing condition, and the shearing rate is preferably 3000-8000 r/min, more preferably 4000-6000 r/min, and more preferably 5000-6000 r/min. In the invention, the shearing time is preferably 1-5 min, and more preferably 2-4 min. In the invention, in the shearing process, the metal salt and the sodium hydroxide between the two solutions are subjected to coprecipitation reaction, and the growth process is controlled by high-speed shearing to enable the metal salt and the sodium hydroxide to reach the nanometer size.
After the coprecipitation reaction, the present invention preferably performs solid-liquid separation on the obtained coprecipitation reaction solution, and the solid-liquid separation is preferably centrifugation. In the invention, the speed of centrifugation is preferably 3000-8000 rpm, more preferably 4000-6000 rpm, and more preferably 8000 rpm. After the centrifugation, the solid obtained is preferably dispersed in water, and the centrifugation is repeated until the centrifuged liquid is neutral.
The invention provides application of the rare earth doped hydrotalcite nano light fertilizer in promoting crop photosynthesis. In the invention, the crops are preferably one or more of cucumber, pepper and tobacco.
In the present invention, the application method comprises the steps of:
and applying the rare earth doped hydrotalcite nano-grade light fertilizer water dispersion liquid to the surface of the crop leaf.
In the invention, the concentration of the rare earth doped hydrotalcite nano optical fertilizer water dispersion liquid is preferably 0.1-2 g/L, and more preferably 0.5-1.5 g/L; the application amount of the rare earth doped hydrotalcite nanometer optical fertilizer is preferably 5-20 g/mu, and 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 provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a rare earth doped hydrotalcite nanometer optical fertilizer comprises the following steps:
(1) weighing 25.6g of magnesium nitrate, 13.125g of aluminum nitrate and 6.69g of europium nitrate (molar ratio Mg: Al: Eu is 2:0.7:0.3) and dissolving 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 into 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 nanosheet solution;
(4) and (3) centrifuging the prepared rare earth hydrotalcite nanosheet solution at a high speed, keeping the rotating speed of 8000r/min, and reacting for 10 min. The supernatant was removed, redispersed by the addition of water and centrifuged again. And repeating the centrifugation operation for 3 times until the supernatant is neutral to obtain the rare earth doped hydrotalcite nano optical fertilizer.
And (3) 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 image is shown in figure 1, and the obtained transmission electron microscope image is shown in figure 2. As can be seen from fig. 1 and 2, the rare earth hydrotalcite nanosheets have a regular hexagonal plate structure and uniform particle size distribution of about 60 nm.
And (3) carrying out X-ray diffraction analysis on the obtained rare earth doped hydrotalcite nano light 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 structural crystal form, ideal crystallinity and high purity, and realizes effective doping of rare earth elements.
The obtained rare earth doped hydrotalcite nano light fertilizer is subjected to X-ray photoelectron analysis, and the obtained result is shown in figure 4. As can be seen from fig. 4, in the hydrotalcite structure, all of the europium elements are present in trivalent valence.
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 light fertilizer prepared in example 1, the contents of the magnesium element, the aluminum element and the europium element are 39.2%, 15.34% and 6.05%, respectively, the ratio is about 6.48:2.54:1, and the content of the europium element is about 9.9%.
And (3) testing the luminescence property of the obtained rare earth doped hydrotalcite nano light fertilizer, wherein the absorption spectrum of the rare earth doped hydrotalcite nano light 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 ultraviolet light with the wavelength is converted into red light with the wavelength of 620 nm and 700nm, so as to promote photosynthesis of crops.
Example 2
A preparation method of a rare earth doped hydrotalcite nanometer optical fertilizer comprises the following steps:
(1) weighing 14.16g of calcium nitrate, 3.75g of aluminum nitrate and 4.46g of europium nitrate (the molar ratio of Ca to Al to Eu is 3:0.5:0.5) and dissolving 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) weighing 6.4g of sodium hydroxide, and dissolving 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 rotating speed of 5000r/min, and reacting for 1min to obtain a hydrotalcite nanosheet solution;
(4) and (3) carrying out high-speed centrifugation on the prepared hydrotalcite nanosheet solution, keeping the rotating speed of 8000r/min, and reacting for 10 min. The supernatant was removed, redispersed by the addition of water and centrifuged again. And repeating the centrifugation operation for 3 to 5 times until the supernatant is neutral to obtain the rare earth doped hydrotalcite nano optical fertilizer.
The results of XRD, scanning electron microscope, transmission electron microscope and luminescence performance tests of the rare earth doped hydrotalcite nano optical fertilizer obtained in the example 2 are similar to those of the example 1. The ICP analysis was carried out, and as shown in FIG. 8, the contents of Ca, Al and Eu were 50.78%, 12.76% and 22.46%, respectively, in a ratio of about 3.98:1:1.76, and the content of Eu was about 26.1%.
Test example 1
The effect evaluation of the rare earth doped hydrotalcite nano light fertilizer prepared in the examples 1 and 2 is carried out by taking cucumber as an experimental crop. The test method comprises the following steps: preparing a rare earth doped hydrotalcite nano optical fertilizer into a water dispersion with the concentration of 1.0g/L, and taking a europium salt solution (europium nitrate) with the same concentration as a contrast; spraying is carried out when cucumber seedlings grow to 3 rd true leaves, spraying is carried out once every 3 days, and all physiological indexes of a control group sprayed with the nano light fertilizer and a control group not sprayed with the nano light fertilizer are counted 30 days after application. The results are shown in Table 1.
TABLE 1 results of rare earth doped hydrotalcite nano-optical fertilizer for promoting crop growth
Further, in order to verify the photostability of the rare earth-doped hydrotalcite nano-grade light fertilizer, after the rare earth-doped hydrotalcite nano-grade light fertilizer is subjected to ultraviolet aging for 120 hours, cucumber is used as an experimental crop, and the effect evaluation is performed on the rare earth-doped hydrotalcite nano-grade light fertilizer prepared in examples 1 and 2. The test method comprises the following steps: preparing a rare earth doped hydrotalcite nano optical fertilizer into a water dispersion with the concentration of 1.0g/L, and taking a europium salt solution (europium nitrate) with the same concentration as a contrast; spraying is carried out when cucumber seedlings grow to 3 rd true leaves, spraying is carried out once every 3 days, and all physiological indexes of a control group sprayed with the nano light fertilizer and a control group not sprayed with the nano light fertilizer are counted 40 days after application. The results are shown in Table 2.
TABLE 2 results of promoting crop growth by rare earth doped hydrotalcite nano optical fertilizer after ultraviolet irradiation
| 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 light fertilizer provided by the invention has long-acting and stable light conversion performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The rare earth doped hydrotalcite nanometer optical fertilizer comprises a hydrotalcite nanosheet and trivalent europium ions doped in the hydrotalcite nanosheet structure, wherein the mass content of the trivalent europium ions in the rare earth doped hydrotalcite nanometer optical fertilizer is 2-30%.
2. The rare earth-doped hydrotalcite nanophotonic of claim 1Fertilizer characterized in that the hydrotalcite nanosheets have a chemical composition of (M) 1 ) x (M 2 ) 1-x (OH) 2 K y ·zH 2 O, wherein M 1 Is Mg 2+ 、Ca 2+ 、Zn 2+ One or more of the above;
M 2 is Fe 3+ 、Cr 3+ Or Al 3+ One or more of the above;
k is acid radical ion;
x is 0.2-0.5; y is equal to (M) 1 ) x (M 2 ) 1-x (OH) 2 K y ·zH 2 Charge conservation for O; and z is 1-20.
3. The rare earth-doped hydrotalcite nano-optical fertilizer according to claim 2, wherein the chemical composition of the rare earth-doped hydrotalcite nano-optical fertilizer is (M) 1 ) x (EuM 2 ) 1-x (OH) 2 K y ·zH 2 O。
4. The rare earth-doped hydrotalcite nano optical fertilizer according to claim 1, wherein the particle size of the rare earth-doped hydrotalcite nano optical fertilizer is 20-200 nm.
5. The preparation method of the rare earth doped hydrotalcite nano optical fertilizer according to any one of claims 1 to 4, comprising the following steps:
providing a precursor solution for preparing the hydrotalcite nano-sheets, wherein the precursor solution comprises a soluble metal salt solution and a strong base solution;
mixing soluble trivalent europium salt, soluble metal salt solution and strong base solution, and carrying out coprecipitation reaction to obtain the rare earth doped hydrotalcite nano optical fertilizer.
6. The preparation method according to claim 5, wherein the coprecipitation reaction is carried out under a shearing condition, and the shearing rate is 3000-8000 r/min and the time is 1-5 min.
7. The method according to claim 5, wherein the concentration of the soluble metal salt solution is 0.005 to 0.5mol/L, and the concentration of the alkali solution is 0.01 to 1.0 mol/L.
8. Application of the rare earth doped hydrotalcite nano optical fertilizer according to any one of claims 1 to 4 or the rare earth doped hydrotalcite nano optical fertilizer prepared by the preparation method according to any one of claims 5 to 7 in promoting crop photosynthesis.
9. The use according to claim 8, wherein the crop is one or more of cucumber, pepper and tobacco.
10. The application according to claim 8, characterized in that the application method comprises the following steps:
applying the rare earth doped hydrotalcite nano optical fertilizer water dispersion liquid to the surface of a crop leaf;
the concentration of the rare earth doped hydrotalcite nanometer optical fertilizer water dispersion liquid is 0.1-2 g/L;
the application amount of the rare earth doped hydrotalcite nanometer optical fertilizer is 5-20 g/mu.
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