WO2016090507A1 - Synthèse chimique de nanoparticules de soufre de cuivre - Google Patents

Synthèse chimique de nanoparticules de soufre de cuivre Download PDF

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WO2016090507A1
WO2016090507A1 PCT/CL2014/000073 CL2014000073W WO2016090507A1 WO 2016090507 A1 WO2016090507 A1 WO 2016090507A1 CL 2014000073 W CL2014000073 W CL 2014000073W WO 2016090507 A1 WO2016090507 A1 WO 2016090507A1
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nps
copper
solution
concentration
copper sulfide
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PCT/CL2014/000073
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Spanish (es)
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José Manuel PEREZ-DONOSO
Luis SAONA ACUÑA
Nicolás Alexis ÓRDENES AENISHANSLINS
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Universidad Andrés Bello
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • 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
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold

Definitions

  • the present invention relates to a method for the chemical synthesis of fluorescent semiconductor nanoparticles of copper sulfide (quantum dots or quantum dots).
  • the method corresponds to a method of synthesis of nanoparticles (hereinafter, NPs) of copper sulfide in an aqueous environment.
  • the methodology includes using biological reagents (thiols such as cysteine, glutathione, mercaptosuccinic acid, among others), phosphate, low temperatures (from 28 ° C) and the presence of oxygen, to produce NPs of copper sulphide.
  • the copper sulfide NPs generated from the present invention are semiconductor, have low toxicity and are highly fluorescent. These characteristics allow its application in solar cells sensitized by quantum dofc (quantum dots) for the generation of electrical energy from solar energy, establishing a photovoltaic cell.
  • quantum dofc quantum dots
  • a nanoparticle is a microscopic particle with a size smaller than 100nm, of which there are different types and can be classified based on its composition:
  • Carbon based materials are spherical, ellipsoid or tubular. They are of low weight, high hardness, elasticity and electrical conductivity.
  • Metal based materials In this group are the so-called quantum dotso NPs of gold, silver or reactive materials such as titanium dioxide, among others.
  • Dendrimers Three-dimensional nanometric polymer of arborescent construction. These synthetic macromolecules are highly versatile and can be designed to obtain specific chemical and physical properties for a given application.
  • Composites Correspond to synthetic materials that are mixed heterogeneously and that form a compound. These materials can combine NPs with others or with larger materials.
  • Quantum Dots which correspond to inorganic nanometric bimetallic semiconductor crystals capable of emitting light.
  • One of its main characteristics is that the larger the particle size, the longer the wavelength they emit.
  • the first ones, Cu ° and CuO correspond to synthesis methods of NPs of different composition and with properties very different from those described in the present invention.
  • TMB tetramethylbenzidine
  • carbon disulfide among others
  • the copper sulfide NPs are synthesized from different reagents that mimic intracellular conditions (cell thiols and phosphate / citrate) which do not show greater toxicity. It has been described in WO 2012090161 A1, a method for the synthesis of quantum dots tellurium cadmium and glutathione (GSH-CdTe) in aqueous medium.
  • GSH-CdTe quantum dots tellurium cadmium and glutathione
  • the method includes the steps: a) prepare a precursor solution of cadmium in a citrate buffer, b) add glutathione (GSH) to the mixture by strong agitation, c) add an oxyanion of tellurium (sodium tellurium or potassium telluride) as a tellurium donor to the above mixture, d) allow the mixture to react, and e) stop the reaction by incubation at low temperatures.
  • GSH glutathione
  • tellurium sodium tellurium or potassium telluride
  • the aforementioned method is totally different from the proposed invention since in addition to the fact that the products generated are different (composition), the substrates, synthesis conditions and especially the properties of the NPs obtained are different.
  • the synthesis can be developed efficiently after approximately 20-24 h of incubation at low temperatures (37 ° C), which in the case of CdTe NPs does not occur since the synthesis at temperatures below 45 ° C is a very disadvantaged process that takes weeks to develop at low temperatures.
  • JP2006240900 refers to a method for synthesizing copper sulfide NPs, allowing their application in optically functional material and electronic devices. It is described that the method comprises mixing a copper-surfactant salt with a dodecanethiol sulphide solution in an organic solvent, particularly copper acetate or copper acetylacetonate, which is complexed by oleylamine or dodecanoetiol, to which sulfide is added by a sulfur compound dissolved in dodecanethiol.
  • This document does not specifically refer to the reagents or conditions indicated in the methodology and therefore obtains NPs with characteristics different from those obtained by the present method.
  • Copper sulfide nanoparticles for photothermal ablation of tumor cells describes a strategy to develop NPs of copper sulphide with the aim of generating a new type of photothermal ablation agent.
  • the synthesis of the copper sulfide NPs is described from a total of 0.017048 g of CuCl 2 -2H 2 0 (0.1 mmol), which was dissolved in 100 ml_ of distilled water. In the solution is added 0.2 mmol of triglycolic acid (-14.2 ⁇ _), this under stirring and pH adjustment (9.0). The solution was placed in a flask and degassed by bubbling argon for 20 min.
  • thioacetamide (8.0 mg, 0.1 mmol) was added in distilled water (20 mL), and the solution set was heated at 50 ° C for 2 h to promote growth of the NPs.
  • the NPs were characterized according to their structure and properties, and their cytotoxicity in cell culture was evaluated by MTT assay.
  • the copper sulfide NPs act as a photosensitizer in solar cells sensitized by quantum dots. These NPs present a broad spectrum of visible light absorption (absorption between 360 and 460 nm), which makes them excellent candidates for use in solar photovoltaic devices.
  • redox pair iodide-triiodide As an electronic mediator between the electrodes of the cell, different high-efficiency redox electrolytes are used (for example, redox pair iodide-triiodide) that does not affect the optical and semiconductor properties of the copper sulfide NPs.
  • the use of this type of electrolyte is not possible with other photosensitizers with similar properties and functions such as CdTe or CdS NPs, in which this electrolyte destabilizes its structure (M. Samadpouref al., 2011).
  • this redox pair must be replaced by others with lower efficiency, such as the sulfur-polysulfide electrolyte (R Tena-Zaera, 2010).
  • Our results indicate that when comparing solar cells under the same conditions, those sensitized with the copper sulfide NPs of the present invention have greater efficiency than those using CdTe fluorescent semiconductor NPs, of the state of the art.
  • the incorporation of the NPs of copper sulfide to the electrode is carried out by a simple method, known as direct adsorption, which does not require expensive and complicated processes.
  • direct adsorption is based on successive reactions or cycles of incorporation of each of the ions that are part of the nanoparticle. While direct adsorption, allows the large-scale collection of NPs and then, once synthesized, the photo-anode is manufactured.
  • the photovoltaic of the cell has a stable configuration given by the organic cover of the copper sulfide NPs, which ensures a close interaction with the broad band-gap semiconductor (film of Ti0 2 ).
  • copper NPs Although the use of copper NPs has been described in technological patent applications (US 8,048,477 B2, WO 2010135622.A1) and some publications ⁇ Mayur Valodkar et al. 2011,shrikant Harne et al. 2012), these applications involve copper NPs other than those developed by the method described in the present invention, with different compositions, different properties, higher levels of toxicity and produced by different methodologies. In fact, these are NPs not only based on copper, but also incorporate indium, gallium, zinc or selenium in their structure, which changes their properties and, in terms of photovoltaic technology, limits its use to solar cells of solid state as p-type semiconductors.
  • copper sulfide NPs generated by the present method, exhibit properties that allow them to be incorporated into another type of solar cell, a liquid state that stands out for being of low cost, sustainable and high efficiency known as Quantum Dot Sensitized Solar Cell (Arie Zaban et al., 2010). In this sense, it is possible to develop photovoltaic cells using copper sulfide NPs as obtained by the method described in the present invention.
  • the copper sulfide NPs developed in the present invention constitute a great contribution, since although NPs of copper have been reported in this solar cell model (Ming-Way Lee, 2011), the unique properties possessing the copper sulfide NPs generated by the method described in the present invention, allow incorporating them to the photovoltaic device by a simple method and fast not reported to date.
  • the copper sulfide NPs fulfill a role as a high efficiency photosensitizer by interacting smoothly with the iodide-triiodide electrolyte.
  • solar cells sensitized with NPs of copper sulphide produced by the method described here present greater efficiency than those involving other semiconductor NPs.
  • This solar cell requires low cost materials and low toxicity for its manufacture, in addition, the simplicity of the model and its easy assembly make possible the scaling of our prototypes. All this contributes to the fact that this solar cell based on NPs of copper sulfide is an efficient device, easy to produce and low cost.
  • WO2012015989A2 refers to a solar cell that includes: a substrate, a first layer composed of a copper based material deposited on the substrate, a second layer comprising a second copper material under the first layer or a second optional layer deposited between the first and second layer.
  • the copper-like material present in the first layer is selected from a group consisting of copper-indium-gallium-diselenide, copper-indium-selenium and cadmium sulfate, which are in the form of NPs.
  • NPs composed of copper are currently sold and there are industrial applications where they are used regularly, these commercialized NPs do not have the characteristics of NPs. developed by the method described in the present invention since they differ in composition, size, morphology, spectroscopic properties (fluorescence), and other properties derived from their size.
  • the nanoparticles produced by the proposed method have an absorbance pattern with a maximum absorbance of 410 nm, a fluorescence pattern with a maximum fluorescence of 520 nm when excited at 410 nm, and a size of nanoparticles between 6-10 nm.
  • Figure 1 Synthesis of NPs of copper sulphide at different pH conditions.
  • the image shows the result of the exposure of the final synthesis solutions of copper sulfide NPs (in duplicate) to UV light at a wavelength of 365 nm.
  • Figure 2 Absorbance spectra of copper sulfide NPs prepared with different concentrations of reagents.
  • PBS 1 (-) corresponds to an NPS preparation with a copper concentration of 0.15 mM and cysteine of 7 mM
  • PBS 2 ( ---) corresponds to a preparation of NPS with a concentration of copper of 0.2 mM and cysteine of 10 mM
  • PBS 3 (-) corresponds to a preparation of NPs using a copper concentration of 0.3 mM and cysteine of 14mM.
  • Figure 3 Fluorescence spectra of copper sulfide NPs prepared with different concentrations of reagents.
  • borax-citrate 1 corresponds to the preparation of NPs using a copper concentration of 0.15 mM and cysteine of 7 mM
  • borax-citrate 2 corresponds to the preparation of NPs using a copper concentration of 0.2 mM and 10 mM cysteine
  • borax-citrate 3 corresponds to the preparation of NPs using a copper concentration of 0.3 mM and 14 mM cysteine.
  • Figure 4 FT-IR spectrum of NPs of copper sulfide and cysteine.
  • the graph presents the comparison of the IR spectrum of copper sulfide NPs and the cysteine compound, where (-) corresponds to the FT-IR spectrum of copper sulfide NPs and the curve (-) corresponds to the FT-IR spectrum of the cysteine compound .
  • the numbers included in the spectrum indicate the presence of characteristic functional groups.
  • Figure 5 Transmission electron microscopy and dynamic light scattering (DLS) of copper sulfide NPs.
  • A) Presents a representative image of the study of transmission electron microscopy of a preparation of NPs of copper sulphide.
  • Figure 6 MTS viability test of OKF6-TERT2 cells stimulated with different concentrations of copper sulphide NPs.
  • the percentage of cell viability (y axis) is presented according to the treatment with different concentrations of copper sulphide NPs (pg / mL) (x axis).
  • Figure 7 Fluorescence emission spectra of copper sulphide NPs in the presence of different electrolytes and at different times.
  • Figure 8 Determination of intensity, voltage and power parameters for a solar cell sensitized with NPs of copper sulphide.
  • the active area of the cell was 1.0 cm 2 .
  • the curves were measured under constant sunlight ( ⁇ AM .5 and -100 mW cm "2 ).
  • the present invention relates to a method for the chemical synthesis of fluorescent semiconductor NPs of copper sulphide. This method is carried out in an aqueous environment and uses reducing agents, phosphate, low temperatures (from 28 ° C) and can be performed in its entirety both in the presence and absence of oxygen, to produce NPs of copper sulfide.
  • the methodology comprises the production of NPs of copper sulphide, by the use of a reducing agent, such as for example cysteine, as a source of sulfur and the addition of a base as phosphate, or different citrate salts.
  • a reducing agent such as for example cysteine
  • the method comprises the steps of: a) Preparing a solution of a copper salt together with a solution of a reducing agent that will be the source of sulfur, then mixing these two solutions; b) Add to the solution obtained in (a), a buffer solution at a concentration from 10 mM to 50 mM and pH between 7-10, by agitation; c) Incubate the solution obtained in (b), in a temperature range of 28 ° C to 100 ° C, during 18 to 24 h of incubation until achieving the formation of a yellow-gold solution indicative of the generation of sulfur NPs coppermade; and d) Stop the reaction at a temperature between 4 ° C and 25 ° C.
  • any copper salt preferably copper (II) salts such as, for example, and without being exclusive, CuS0 4 , CuCl 2 , Cu (CH 3 COO) 2 , Cu (N 3 ) 2 , can be used, CuBr 2 , CuF 2 , CuSe0 3 , Cu 2 P 2 0 7 , Cu (CI0 4 ) 2 , CuSCN, Cul, Cu (OH) 2 , CuCN, CuBr.
  • copper (II) salts such as, for example, and without being exclusive, CuS0 4 , CuCl 2 , Cu (CH 3 COO) 2 , Cu (N 3 ) 2
  • CuBr 2 CuF 2 , CuSe0 3 , Cu 2 P 2 0 7 , Cu (CI0 4 ) 2 , CuSCN, Cul, Cu (OH) 2 , CuCN, CuBr.
  • thiols can be used, for example, and without being exclusive, cysteine, glutathione, mercaptosuccinic acid, among others. It is preferably used as a reducing agent and source of sulfur to cysteine.
  • saline phosphate or Borax-citrate solutions can be used as a buffer solution.
  • Borax-citrate buffer is used.
  • the method requires that it be carried out in a buffer solution that absorbs the pH between 7 and 10, preferably pH 8, since it is important to control the pH of the reaction, since the acidic pH does not favor the formation and fluorescence of the NPs.
  • the preferred concentrations for each component involved in the method are the following:
  • Reducing agent as source of sulfur 7 to 14 mM, preferably 14 mM.
  • Buffer solution 10 to 50 mM, preferably 50 mM.
  • the nanoparticles produced by the proposed method present specific characteristics when analyzed by absorbance spectrophotometry, fluorescence, dynamic light scattering analysis (DLS) and transmission electron microscopy.
  • absorbance and fluorescence spectrophotometry it was determined that the nanoparticles absorb at 410 nm after being excited at a wavelength of 365 nm, and fluoresce at 520 nm when excited at 410 nm, respectively.
  • transmission electron microscopy the nanoparticles have an approximate size of 10 nm, and by DLS analysis they have a dispersion size of between 6 and 10 nm.
  • the copper sulfide NPs generated in the present invention its application in the detection of tumor cells and pathogens is possible.
  • a semiconductor material in film solar cells fine as against electrode (catalyst) in sensitized solar cells, as a photocatalyst for the treatment of water contaminated with organic compounds, as a nanosensor coupled to enzymes for the detection of compounds, as nanocomposites for controlled drug release systems, for the manufacture of nanofibers of copper sulphide by electrospining, as antibacterials, as acaricide, as antifungals (as for example in the aquaculture industry), in bioimages for the detection of cells of interest (carcinogenic, pathogenic, etc.) by fluorescence, as lubricants, as sintering agents, as catalysts in different chemical and enzymatic reactions, among many others.
  • Example 1 Method for the synthesis of NPs of copper sulfide.
  • the general methodology includes the production of NPs of copper sulphide, through the use of a reducing agent as a source of sulfur, the use of a copper source and the addition of a base, such as phosphate or different citrate salts among other bases.
  • the reducing agent used corresponds to a solution of cysteine at a concentration of 14 mM.
  • the copper source used was, without limitation, CuS0 4 , CuCl 2, Cu (CH 3 COO) 2 , Cu (N 3 ) 2, among other copper (II) salts, at a concentration of 0.3 mM.
  • the reaction was carried out in a buffer solution that buffered the pH between 7 and 10, such as phosphate buffered saline or Borax-citrate buffer.
  • a solution of a copper salt was prepared as a mixture between one of the copper salts mentioned as a copper source, at a concentration of 0.3 mM together with a 14 mM decistein solution, as a source of sulfur.
  • said solution of a copper salt was added to a solution of phosphate-buffered saline or Borax-citrate, at a concentration of 10 mM, at a pH of 7.
  • the proportion of thiol: copper reactants used was 14: 0.3 .
  • Example 2 Characterization of copper sulfide NPs through UV spectrophotometry, FT-IR spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy.
  • the characterization by UV-visible spectroscopy was carried out from the synthesis of 1 mL of suspension of NPs in Eppendorfs tubes, using different concentrations of Cu 2+ and cysteine (0,15: 7 - 0,2: 10 - 0,3 -14 mM Cu and cysteine respectively).
  • PBS buffered buffer was used at a concentration of 10 mM (pH 7.0) and Borax-Citrate at 50 mM (pH 9.4).
  • the solution was left under constant stirring at 37 ° C for 18 h. After the synthesis time, 200 ⁇ aliquots were taken and transferred to a multi-well plate. The test was carried out at different pHs (7.4 and 9.4).
  • NPs were prepared in a falcon tube under constant agitation for 18 h. Once the time had elapsed, they were dialyzed for one hour by a dialysis membrane of 3 kDa (Sigma Aldrich). Subsequently, the samples were frozen and lyophilized using a Virtis SP Scientific Sentry 2.0 lyophilizer to obtain a golden powder which was used to perform an infrared spectrum.
  • the FT-IR spectroscopy studies of the NPs confirm the assembly or adequate production of the NPs, distinguishing the appearance of the Cu-S metal bond, and the disappearance of bonds found in the initial reactants and not in the final NPs. Additionally, an IR pattern characteristic of the presence of -OH groups was observed, which may be due to molecules contributed by the citrate buffer or to the fact that the sample has H 2 0 molecules on its surface ( Figure 4). Therefore, the copper sulfide NPs produced by the method of the invention have organic molecules that favor their solubility.
  • MET Transmission electron microscopy
  • DLS dynamic light scattering
  • Example 3 Evaluation of the cytotoxicity of copper sulfide NPs on prokaryotic and eukaryotic cells.
  • the analyzes applied to determine the cytotoxicity of the copper sulfide NPs on prokaryotic cells (bacteria) and eukaryotic cells are presented.
  • NPs synthesized by the present invention are totally harmless, even at high concentrations (1000 ppm) for all tested microorganisms, since no inhibition zones were observed.
  • MTS assays in a model of eukaryotic cells of the OKF6-TERT2 type, which correspond to cells that derive from gingival epithelium.
  • the methodology consisted in planting 20,000 cells / well and incubated for 24 h in an environment at 37 ° C and 5% C0 2 to allow adhesion of the cells to the plate.
  • the cells were treated with different concentrations and dilutions of the copper sulfide NPs suspension. Again, the cells, this time treated, were incubated for 24 h in an environment at 37 ° C and 5% C0 2 . After the 24 h stimulation with the NPs, the cells were washed with phosphate buffered saline (3 times) and treated with 100 ⁇ of a mixture of the reagents PMS (phenazine methosulfate) and MTS; in the relations stipulated by the manufacturer (Promega). After 1 hour of incubation the absorbance was measured at 490 nm. The absorbance correlates with the viability of the cells, since the ability to process the reagents correlates with the mitochondrial activity of the cells and therefore with their viability.
  • PMS phenazine methosulfate
  • Example 4 Assembly of a solar cell with NPs of copper sulphide as photosensitizer.
  • the direct adsorption method was used, which allows a large amount of NPs to be obtained to then manufacture the photo-anode.
  • the photovoltaic of the cell has a stable configuration given by the organic cover of the copper sulfide NPs that ensures a close interaction with the wide bandwidth semiconductor (//// T? Of T ⁇ 0 2 ).
  • the electrodes of the cell were manufactured using FTO conductive glasses (Fluorine-doped Tin Oxide, Tin Oxide doped with fluoride), TEC15, surface resistivity 13 [ ⁇ / sq], 85% transmittance and size 25 x 25 x 2 mm .
  • FTO conductive glasses Fluorine-doped Tin Oxide, Tin Oxide doped with fluoride
  • TEC15 surface resistivity 13 [ ⁇ / sq]
  • 85% transmittance and size 25 x 25 x 2 mm For the anode, from a suspension in acetic acid of NPs of Ti0 2 a film of this suspension was deposited on the glass, by means of the spin-coating technique, at 2,000 rpm for 20 seconds. This 625 cm 2 electrode was subjected to a temperature of 450 ° C for 30 minutes, for the sintering of the material.
  • the cathode or platinum electrode was prepared from a 50 mM solution of H 2 PtCl 6 -6H 2 0 in isopropanol. 30 pL of the solution was placed on a FTO glass by spin coating and heated at 400 ° C for 20 minutes. The sensitization of the Ti0 2 film was carried out by direct deposition of the copper sulfide NPs on the electrode. The glass was heated at 40 ° C until the solvent evaporated.
  • both electrodes were spliced using a 127 mm thick Parafilm ® spacer.
  • 5 pL of the electrolyte solution was added.
  • An iodide / triiodide electrolyte (I7I 3 ) composed of 0.5 M of Kl and 50 mM of l 2 in ethylene glycol.
  • the resulting cell comprises an active surface area of 1.0 cm 2 .
  • Example 5 Characterization of a solar cell with NPs of copper sulphide as photosensitizer.
  • the characterization of the solar cell was carried out under conditions of constant temperature and irradiance, using sunlight as a constant source ( ⁇ AM1, 5 and -100 mW cm "2 ).
  • the photovoltaic parameters were determined, expressing as curves intensity-voltage (l-V) and efficiency-voltage (P-V) ( Figure 8). Additionally, Table 1 shows the photovoltaic parameters of the solar cell based on the copper sulfide NPs of the invention as photosensitizer.
  • the copper sulfide NPs of the invention when used in solar cells, they exhibit high stability over time in direct sunlight conditions, which ensures a prolonged use of the device. This has been demonstrated with UV and temperature stress tests carried out in our laboratory.
  • the NPs of the prior art have a limited use to solid state solar cells such as p-type semiconductors, which despite their high efficiency, have a complex manufacture, highly expensive and present certain danger.
  • the NPs of the invention can be easily incorporated into liquid state solar cells, which stand out for their low cost, sustainability and high efficiency.
  • the unique characteristics of this synthesis method translate into low-cost copper sulphide NPs (less than US $ 100 / g), synthesized in a fast, simple, safe way and with very low toxicity for both microorganisms and eukaryotic cells. increases its range of applications.
  • the copper sulfide NPs produced by the present method have semiconducting and fluorescence properties that do not possess the copper NPs previously described, which makes it feasible to use them in solid state and liquid state solar cells.

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Abstract

Selon l'invention, un procédé de préparation chimique de nanoparticules (NPs) de soufre de cuivre semi-conductrices fluorescentes consiste à : a) préparer une solution d'un sel de cuivre avec une solution d'un agent réducteur qui constitue la source de soufre, puis mélanger ces deux solutions ; b) ajouter, par agitation, à la solution obtenue à l'étape (a) une solution tampon à une concentration allant de 10 à 50 mM et à un pH compris entre 7 et 10 ; c) laisser incuber la solution obtenue à l'étape b) dans une fourchette de températures allant de 28°C à 100°C, pendant 18 à 24h d'incubation jusqu'à obtenir la formation d'une solution jaune-dorée indicatrice de la génération de nanoparticules de soufre de cuivre ; et d) maintenir la réaction à une température comprise enter 4°C et 25°C.
PCT/CL2014/000073 2014-12-11 2014-12-11 Synthèse chimique de nanoparticules de soufre de cuivre WO2016090507A1 (fr)

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CN108929678B (zh) * 2018-08-02 2021-06-25 淄博职业学院 一种工商管理用防伪油墨及其制备方法
CN112408457A (zh) * 2020-11-25 2021-02-26 东江环保股份有限公司 一种含氰化亚铜的固体废物制备硫酸铜的方法
CN113073464A (zh) * 2021-03-29 2021-07-06 江南大学 一种具有光热效应的纤维素纤维制品加工方法
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