WO2015066691A1 - Compositions d'engrais à libération lente avec des films d'oxyde de graphène, et procédés de fabrication des compositions d'engrais à libération lente - Google Patents

Compositions d'engrais à libération lente avec des films d'oxyde de graphène, et procédés de fabrication des compositions d'engrais à libération lente Download PDF

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WO2015066691A1
WO2015066691A1 PCT/US2014/063867 US2014063867W WO2015066691A1 WO 2015066691 A1 WO2015066691 A1 WO 2015066691A1 US 2014063867 W US2014063867 W US 2014063867W WO 2015066691 A1 WO2015066691 A1 WO 2015066691A1
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Prior art keywords
sulfate
graphene oxide
fertilizer
ammonium
potassium
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PCT/US2014/063867
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English (en)
Inventor
Bin Gao
Ming Zhang
Yuncong Li
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University Of Florida Research Foundation, Inc.
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Publication of WO2015066691A1 publication Critical patent/WO2015066691A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings

Definitions

  • embodiments of the present disclosure provide timed-release fertilizer compositions and methods of making timed-release fertilizer compositions.
  • the present disclosure provides a slow-release fertilizer composition including fertilizer particles coated with graphene/graphene oxide/reduced-graphene oxide thin films.
  • the slow-release fertilizer composition includes fertilizer particles and a reduced-graphene oxide layer disposed on the surface of the particles. The present disclosure also provides methods for making slow-release fertilizer compositions of the present disclosure.
  • methods of making slow-release fertilizer compositions of the present disclosure include providing a plurality of fertilizer particles including at least one nutrient in salt form, where the salt is capable of reducing graphene oxide; forming one or more layers of graphene oxide on the fertilizer particle such that the fertilizer particle is at least partially coated with graphene oxide; and heating the graphene oxide-coated fertilizer particles to form a coating of reduced-graphene oxide on the particles.
  • the present disclosure further provides a slow-release fertilizer composition made by the methods of the present disclosure.
  • the slow-release fertilizer is made by the following steps: providing a plurality of fertilizer particles including at least one nutrient in salt form, where the salt is capable of reducing graphene oxide; forming one or more layers of graphene oxide on the fertilizer particle such that the fertilizer particle is at least partially coated with graphene oxide; and heating the graphene oxide-coated fertilizer particles to form a coating of reduced-graphene oxide on the particles.
  • FIG. 1 is a schematic illustration of preparation of an embodiment of a fertilizer composition of the present disclosure including re-GO-coated KN0 3 fertilizer particles. The figure includes images of various stages of preparation.
  • FIGS. 2A and 2B illustrate AFM analysis of GO sheets on a mica substrate.
  • FIG. 2A is an AFM image of the GO sheets
  • FIG. 2B is a sectional analysis of the AFM image in FIG. 2A along the white line (AFM channel). The cross in the figure helps to show the height of the graphene sheet.
  • FIGS. 3A-3C illustrate GO before and after heat treatment with KN0 3 .
  • FIG. 3A is a graph of the Raman spectra of GO before and after heat treatment with KN0 3 ;
  • FIG. 3B is a C1 s XPS spectra of GO before heat treatment with KN0 3 ;
  • FIG. 3C is a graph of C1 s XPS spectra of GO after heat treatment with KN0 3 .
  • FIGS. 4A-4D illustrate SEM-EDX analysis of : re-GO-coated KN0 3 (FIG. 4A (15.0kV, X20, WD 12.4 mm, scale bar 1 mm)), observation of shell section (FIGS.
  • FIGS. 5A and 5B illustrate a TEM image of a re-GO sheet taken from re-GO-coated KN0 3 (FIG. 5A), and a selected area electron diffraction (SAED) pattern of the re-GO sheet (FIG. 5B).
  • the insert in FIG. 5A is an HR-lattice image of re-GO.
  • FIG. 6A is a graph illustrating the slow-release of potassium ions from re-GO-coated KNO 3 and pure KN0 3 particles of the present disclosure.
  • FIG. 6B is a digital image showing the re-GO-coated KN0 3 particles before (left) and after (right) soaking in water for about 8 hours.
  • Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of molecular biology, microbiology, nanotechnology, organic chemistry, biochemistry, botany and the like, which are within the skill of the art. Such techniques are explained fully in the literature.
  • compositions like those disclosed herein, but which may contain additional structural groups, composition components or method steps (or analogs or derivatives thereof as discussed above). Such additional structural groups, composition components or method steps, etc., however, do not materially affect the basic and novel characteristic(s) of the compositions or methods, compared to those of the corresponding compositions or methods disclosed herein.
  • Consisting essentially of” or “consists essentially” or the like when applied to methods and compositions encompassed by the present disclosure have the meaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art embodiments.
  • Graphene refers to a thin sheet of carbon atoms (e.g., usually one-atom thick) arranged in a hexagonal format or a flat monolayer of carbon atoms that are tightly packed into a 2D honeycomb lattice (e.g., sp 2 -bonded carbon atoms).
  • Graphene oxide refers to oxidized graphene, which is often made by reacting graphite powders with strong oxidizing agents.
  • Reduced-graphene oxide refers to graphene oxide's reduced form, which can be produced via chemical and/or physical reactions. However, some oxidized regions (e.g., less than 20%, less than about 10%, less than about 5%, or less than about 1 %) may remain on the reduced-graphene oxide
  • reduced-graphene oxide shell or “re-GO shell” refers to a substantially continuous coating (e.g., one or more layers of GO that overlap or otherwise contact each other to form into a continuous coating) around a particle of fertilizer.
  • fertilizer refers to any additive containing organic and/or inorganic nutrients (synthetic and/or natural) that is added to soil to supply nutrients needed for plant growth and/or development.
  • fertilizer may include one or more nutrients (macro- and/or micro-nutrients), such as, but not limited to: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), and sulfur (S), boron (B), chlorine (CI), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn) and nickel (Ni).
  • nutrients such as those listed above, do not have to be in elemental form, but may be in the form of a salt or other compound.
  • fertilizer particle(s) refers to a particulate material (e.g., granules, powders, etc.), where the particles include one or more fertilizer nutrients, such as, but not limited to, those listed above.
  • the embodiments of the present disclosure encompass reduced graphene oxide (re- GO)-coated slow-release fertilizers and methods to prepare and use the re-GO-coated fertilizers.
  • re- GO reduced graphene oxide
  • Graphene an ultra-thin and ultra-light layered carbon material with high mechanical strength, super conductivity, and high surface area finds utility in various applications, including field effect transistors, sensors, transparent electrodes, batteries, supercapacitors, and composited materials. Also, recent advances in technologies make it possible to prepare graphene oxides with green methods, requiring no toxic starting materials or
  • graphene oxides can be produced in large scale via electrochemical exfoliation of pencil cores in aqueous electrolytes without a requirement for toxic chemical agents [33].
  • Guo et al reported a facile approach that can produce high quality graphene nanosheets in large scale through electrochemical reduction of exfoliated graphite oxide precursor at catholic potentials [34]. Because of its unique morphological structure and related properties, graphene has been considered as a possible carrier for various chemical compounds, thus holding potential opportunities for developing new controlled-release delivery systems [21-24].
  • Yang et al developed a method to chemically deposit Fe 3 0 4 nanoparticles onto Graphene oxide (GO). This hybrid can be loaded with the anti-cancer drug DXR with a high loading capacity [23].
  • little research has explored graphene-based slow- and controlled release systems for agricultural applications such as fertilizers, pesticides and so forth.
  • a procedure was tested to prepare re-GO coated fertilizer particles including a nutrient salt (e.g., KN0 3 ) by encapsulating the nutrient-salt fertilizer pellets with a GO film and then baking GO-coated fertilizer pellets under heat for an amount of time.
  • a nutrient salt e.g., KN0 3
  • the potassium ions are not only able to act as a "glue”, soldering adjacent graphene sheets but also reduce GO to re-GO.
  • This procedure allows GO films to form a shell around KN0 3 pellets inhibiting KN0 3 from fast release.
  • This new method is different from the conventional polymer coating methods, which need organic solvents and toxic initiators.
  • the re-GO-coated fertilizer pellets as prepared in the Example below took on improved slow-release properties. Because of its simplicity, feasibility and environmental friendliness, the fertilizer compositions and methods of making such fertilizer compositions of the present disclosure possess great potential as controlled-release fertilizers that provide plants with nutrients and ensure soil quality and crop productivity
  • the compositions include a controlled/slow-release fertilizer composition including fertilizer particle sand a reduced-graphene oxide layer deposited on the surface of the particles.
  • the fertilizer is in the form of a fertilizer particle (e.g., grain, granule, pellet, etc.).
  • the fertilizer particles include one or more nutrient.
  • each particle can include the same combination of one or more nutrients, and in other embodiments, some particles can include different nutrients or different combinations of nutrients. In each particle, at least one such nutrient can act as a reducing agent.
  • At least one nutrient in the particles is in a salt form suitable for acting as a reducing agent of the graphene oxide.
  • a reducing agent e.g., metal salt or ionic salt
  • at least one nutrient is a nutrient salt, such as a metal salt, ionic salt, or other form capable of acting as a reducing agent to reduce GO.
  • the fertilizer particle includes one or more nutrients (with at least one nutrient in salt form) including, but not limited to, nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), and sulfur (S), boron (B), chlorine (CI), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn) and nickel (Ni).
  • the fertilizer particle includes a combination of (e.g., two or more, three or more, etc.) such nutrients, with one or more of such nutrients in salt form.
  • the one or more nutrient salts include, but are not limited to: aluminum sulfate, amino acid salt, ammonium chloride, ammonium molybdate, ammonium nitrate, ammonium phosphate, ammonium phosphate-sulfate, ammonium sulfate, borax, boric acid, calcium ammonium nitrate, calcium silicate, calcium chloride, calcium cyanamide, calcium nitrate, copper acetate, copper nitrate, copper oxalate, copper oxide, copper sulfate, diammonium phosphate, iron- ethylenediamine-N,N'-bis (EDDHA-Fe), iron-ethylenediaminetetraacetic acid (EDTA-Fe), elemental sulfur, ferric sulfate, ferrous ammonium phosphate, ferrous ammonium sulfate, ferrous sulfate, gypsium, humic acid
  • the nutrient salt is capable of acting as a reducing agent under heat to reduce graphene oxide on the fertilizer particle.
  • the fertilizer composition also includes cations (e.g., from the nutrient salt) capable of connecting adjacent reduced- graphene oxide sheets to form a substantially continuous coating of reduced-graphene oxide on the particle.
  • the reduced-graphene oxide coating on the fertilizer particle can be single-layered, double-layered, few-layered, and multiple-layered re-GO.
  • the thickness of the re-GO shell can be in the rage of about 0.34 nm to 30 ⁇ . In embodiments, the thickness of a single-layer of re-GO can be about 0.34 to about 0.9 nm, with an average thickness of 0.7 ⁇ 0.2 nm. Two or more layers of re-GO can increase the thickness of the re-GO shell/coating on the fertilizer of the present disclosure.
  • the properties of the re-GO layers/coating can be controlled by the methods used to produce the fertilizer composition, such as by varying the parameters and conditions (such as ingredients, time, heat, and the like), as explained in greater detail below.
  • the thickness of the reduced-graphene oxide coating can be controlled by how much graphene oxide is combined with the fertilizer particles, the nutrient/reducing agent, the shape of the particles, the heating temperature, and the like.
  • the chemical and physical properties of reduced-graphene oxide coating can be changed by addition of the chemical reagents, reaction temperature, reaction time, pressure, gas atmosphere, gravity, graphene oxide, and/or pre/post-treatment
  • Methods of the present disclosure include methods of making slow-release fertilizer compositions of the present disclosure.
  • the methods include providing a fertilizer particle including at least one nutrient in salt form (such as described above) that is capable of reducing graphene oxide, forming one or more layers of graphene oxide on the fertilizer particle such that the fertilizer particle is at least partially coated with graphene oxide, and then heating the graphene oxide-coated fertilizer particles to form a coating of reduced- graphene oxide on the particles.
  • the fertilizer particles are combined with GO to form GO-coated particles, having fertilizer particles at least partially covered with GO (e.g., GO films, GO suspensions, GO slurry, etc.).
  • GO e.g., GO films, GO suspensions, GO slurry, etc.
  • the GO coatings are applied by physically wrapping prepared GO sheets on particles.
  • the GO coatings are applied to the particles by spray or dip coating with a GO composition.
  • the GO coatings may be continuous or made of partial layers/coatings.
  • cations in the fertilizer can act to fuse multiple CO layers or sections together to form a continuous coating.
  • the GO-coated particles are heated to enable the nutrient/reducing agent in the fertilizer to reduce the GO to form reduced GO coatings on the fertilizer particles.
  • the GO-coated particles are heated (e.g., in an oven, microwave, or with another heat source) at a temperature of about 25 to about 500 °C.
  • the GO-coated particles are heated at about 90 °C, or more.
  • the particles are heated for a period of time sufficient to reduce the GO coating to form a reduced GO coating.
  • the particles are heated from about 1 second to about 6 hours or longer. In embodiments the particles are heated for about 6 hours.
  • the re-GO coating acts as a controlled-release coating for the fertilizer, releasing the fertilizer nutrients to the environment (e.g., soil, water, etc.) in a controlled manner.
  • the reducing agent can be a metal salt or an organic molecule or any other ionic compound or a mixture of one or more types of reducing agents.
  • the metal in the metal salt can be magnesium, sodium, silver, iron, copper, silver, nickel, and the like.
  • the metal salt can include MgCI 2 , NaCI, AgN0 3 , FeS0 4 , CuCI 2 , AICI 3 , NiCI 2 , KN0 3, and the like.
  • ionic solutions such as MgCI 2 , NaCI, AgN0 3, FeS0 4 , CuCI 2 , KN0 3 and AICI 3 , not only reduce GO but also crosslink adjacent graphene sheets to form reduced GO (Re-GO) films on various substrates.
  • the nutrient(s) to be used as fertilizer can be used as the reducing agent.
  • fertilizer components such as, but not limited to, nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), and sulfur (S), boron (B), chlorine (CI), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn) and nickel (Ni) can be formulated into metal salts and/or ionic compounds to serve a double role as the reducing agent in forming reduced graphene oxide films to coat the fertilizer as well as the nutrient component of the fertilizer itself.
  • the nutrient/reducing agent is a salt ("nutrient salt") selected from metal salts and other ionic salts such as, but not limited to, aluminum sulfate amino acid, ammonium chloride, ammonium molybdate, ammonium nitrate, ammonium phosphate, ammonium phosphate-sulfate, ammonium sulfate, borax, boric acid, calcium ammonium nitrate, calcium silicate, calcium chloride, calcium cyanamide, calcium nitrate, copper acetate, copper nitrate, copper oxalate, copper oxide, copper sulfate, diammonium phosphate, EDDHA-Fe, EDTA-Fe, elemental sulfur, ferric sulfate, ferrous ammonium phosphate, ferrous ammonium sulfate, ferrous sulfate, gypsium, humic acid, iron ammonium polyphosphate, iron chelates, iron sulfate
  • the reduced-graphene oxide layer is formed by the reduction of the graphene oxide by the nutrient/reducing agent.
  • the nutrient/reducing agent can reduce the graphene oxide and act as a bridge between or among adjacent reduced-graphene oxide sheets to form a continuous reduced-graphene oxide layer/shell.
  • the reducing agent includes a divalent cation
  • the cation forms a cation bridge between reduced-graphene oxide sheets.
  • the present disclosure also includes slow-release fertilizer compositions having reduced-graphene oxide coatings made by the methods of the present disclosure described above.
  • the disclosure further provides products including the slow-release fertilizer compositions of the present disclosure.
  • the present disclosure further includes methods of using the slow-release fertilizer compositions of the present disclosures to treat soil and/or water for growing plants by adding the fertilizer compositions of the present disclosure to the solid and/or water before or during planting and/or cultivation/growth of the plants.
  • Embodiments of the present disclosure include slow-release re-GO coated fertilizer and methods to prepare re- GO-coated fertilizer.
  • the nutrient is potassium
  • the fertilizer includes KN0 3 particles. Additional details regarding the methods and compositions of the present disclosure are provided in the Examples below. The specific examples below are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. Without further elaboration, it is believed that one skilled in the art can, based on the description herein, utilize the present disclosure to its fullest extent.
  • ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a concentration range of "about 0.1 % to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1 %, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1 %, 2.2%, 3.3%, and 4.4%) within the indicated range.
  • the term “about” can include traditional rounding according to significant figures of the numerical value.
  • the phrase “about 'x' to 'y'” includes “about 'x' to about 'y "'.
  • the present example describes the development of a slow-release fertilizer prepared by encapsulating KN0 3 pellets with graphene oxide (GO) films. The material was then subjected to heat treatment, where adjacent GO sheets were soldered and reduced to reduced graphene oxide (re-GO) sheets by potassium. After the re-GO shell formed on KN0 3 pellets, the slow-release characteristics of the fertilizer dramatically improved. This new coating technology could hold great promise for environmentally-benign controlled- release fertilizer for crop production. Materials and methods
  • Graphene oxide (GO) and potassium nitrate (KN0 3 ) were obtained from ACS
  • GO solutions at the concentration of 2 mg/mL were prepared via 2 hours of ultrasound in 20 ml batches.
  • 10 mL of the resulting GO solutions was filtered through an Anodisc membrane filter (47 mm in diameter, 0.2 ⁇ pore size;
  • the microscopic features of re-GO-coated KN0 3 pellets were characterized with a field emission gun scanning electron microscopy (FEG-SEM, JEOL 6335F), transmission electron microscopy (JEOL 200CX TEM), and atomic force microscopy (SPM/AFM).
  • FEG-SEM field emission gun scanning electron microscopy
  • JEOL 6335F transmission electron microscopy
  • JEOL 200CX TEM transmission electron microscopy
  • SPM/AFM atomic force microscopy
  • X-Ray photoelectron spectra (XPS) of the samples were obtained with a Perkin Elmer 5100 XPS System. Raman spectra were recorded using a Renishaw Invia Bio Raman with excitation from a 785 nm diode laser.
  • FIG. 1 gives the schematic illustration of an embodiment of a method of the present disclosure developed to encapsulate KN0 3 pellets with GO films.
  • the color of GO film was matte brown, and the resultant re-GO-coated KN0 3 pellet is metallic grey.
  • the color of the films changed from matte brown (GO color) to metallic grey, probably due to the recovery of ⁇ -conjugated system from GO sheets upon hydrothermal reduction in the presence of cations (K + )[25]. Meanwhile, GO's exposure to cations might have led to ring-opening of the epoxide [29], which further reduced GO.
  • Atomic force microscopy (AFM) analysis of the dispersal state of GO individuals showed the presence of GO sheets on the mica surface and that the size of GO patches was in the micrometer range (FIG. 2A). Although a graphene sheet is thin, the AFM could easily characterize the morphological features of the graphene patches.
  • Cross-sectional images of the AFM revealed that the thickness of a single-layer graphene on the mica surface ranged from 0.5 to 0.9 nm with an average of 0.7 ⁇ 0.2 nm (FIG. 2B), which is in agreement with the typical thickness ( ⁇ 1 nm) observed elsewhere for monolayer graphene sheets 16 .
  • the analysis of cross-sectional re-GO-coated KN0 3 pellets by SEM shows the presence of both re-GO shell and KN0 3 core (FIG. 4A).
  • FIG. 5A shows TEM images of re-GO film of re-GO-coated KN0 3 , which clearly depict wrinkles and folding that indicates formation of a thin re-GO film.
  • the TEM images also showed large pieces of re-GO sheets with size of at least 10 ⁇ .
  • the sizes of the original GO sheets should be around 1 -5 ⁇ , which is confirmed by the AFM analysis.
  • the increase in size of re-GO sheets confirmed the ion-cross-linking mechanisms that the reducing ion reagent may act as a "cation bridge" or "glue", soldering adjacent graphene sheets.
  • FIG. 5B The corresponding selected area electron diffraction (SAED) pattern of the graphene film is shown in FIG. 5B, where the ring patterns along with point patterns of hexagonal symmetry are clearly seen.
  • the ring patterns indicate various orientations of re-GO sheets due to wrinkling and folding of a re-GO layer or overlapping with different re-GO layers, while the point patterns reflect the presence of a main single crystalline domain composed of sp 2 -hybridized carbons arranged in a hexagonal lattice [32].
  • the SAED results confirm that well-reduced GO films formed on KN0 3 could be few- or multi-layer graphene sheets.
  • the slow-release behavior of as-produced re-GO-coated KN0 3 was examined to demonstrate its potential application as an agent for fertilizer delivery.
  • the release characteristics of both the re-GO-coated KN0 3 and the pure KN0 3 were investigated. After soaking for 10 hours, the re-GO-coated KN0 3 pellets maintained substantially the same shape as prior to soaking, and some pellets appeared to drift on the solution without structural collapse. These observations indicate that, after thermal treatment, the GO film is capable of coating KN0 3 pellets.
  • the concentrations of potassium that are released over time from the samples are shown in FIG. 6A, where C K + denotes the concentration of potassium ions in the elutriant.
  • the cracks on the film likely lead to the burst release of potassium ions. After that, the release is restored to a slow rate, similar to that of the first 2 hours, with about 93.8% of the potassium ions released from the fertilizer composition.
  • the data also reveal that the release of potassium out of the re-GO shell to water reaches its equilibrium after about 8 hours, indicating that the shell has excellent controlled-release ability.
  • the release of potassium from the pure KN0 3 was rapid and reached equilibrium after only 1 hour. The results clearly demonstrate the reduction of GO films on the fertilizers provides a promising coating technique for the slow release characteristic.
  • the present example demonstrated a new method for developing fertilizer (KN0 3 ) that releases nutrients in a slow-release manner.
  • the exemplary fertilizer was developed by encapsulating KN0 3 pellets with graphene oxide (GO) films at 90 °C for 6 hours in air.
  • This new method is different from the conventional polymer coating methods, which uses organic solvents and toxic initiators.
  • the results of this example show that with the aid of potassium ions, separated GO sheets not only fuse together to form a shell on KN0 3 , but also reduce to re-GO sheets during the heat treatment.
  • the as-prepared re-GO-coated KN0 3 pellets exhibited slow-release behavior. Because of the unique characteristics of graphene, this newly developed method can be used for fertilizers that have controlled-release profiles, providing plants with nutrients, enhancing plant productivity, and minimizing nutrient loss.

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  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)

Abstract

L'invention concerne des compositions d'engrais à libération lente et des méthodes de fabrication et d'utilisation des engrais à libération lente.
PCT/US2014/063867 2013-11-04 2014-11-04 Compositions d'engrais à libération lente avec des films d'oxyde de graphène, et procédés de fabrication des compositions d'engrais à libération lente WO2015066691A1 (fr)

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CN109650999A (zh) * 2019-02-12 2019-04-19 东北农业大学 一种石墨烯废料包埋尿素的制备方法和应用
CN114668019A (zh) * 2022-04-12 2022-06-28 山东省农业科学院 一种除草剂增效助剂
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