WO2023244187A1 - A method for synthesizing copper sulphide particles - Google Patents

A method for synthesizing copper sulphide particles Download PDF

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WO2023244187A1
WO2023244187A1 PCT/TR2022/050609 TR2022050609W WO2023244187A1 WO 2023244187 A1 WO2023244187 A1 WO 2023244187A1 TR 2022050609 W TR2022050609 W TR 2022050609W WO 2023244187 A1 WO2023244187 A1 WO 2023244187A1
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copper
synthesizing
copper sulfide
catalyst
synthesis
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PCT/TR2022/050609
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French (fr)
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Annamaria MIKO
Halil KAVAKLI
Adem Levent DEMIREL
Aatif IJAZ
Yavuz Ali EKMEKCIOGLU
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Koc Universitesi
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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow

Definitions

  • the invention relates to a synthesis method for copper sulfide (Cu x S) particles and nanoparticles with a high specific surface area, controlled morphology, antimicrobial activity and photocatalytic activity.
  • Copper sulfide has been extensively used in solar cells, sensors, and catalysis applications with having prominent photocatalytic activity, a small band gap, and is a p-type of semiconductor. Since copper sulfide exhibits antimicrobial activity accompanied by low toxicity, its particles are also used in biomedical applications for targeted drug delivery systems, imaging and diagnostic and therapeutic agents. While copper sulfide particles have many potential applications, most of the synthesis processes of such particles are complex. They tend to take longer synthesis time under a controlled environment, making them expensive for commercial applications. Copper sulfide can be synthesized with various methods. In general, the reaction of copper ions and sulfur-containing reactants can be directly carried out.
  • the copper ions are obtained from simple copper (II) salts (CT, SO4 2 , NO3 ) while the most common sulfur containing reactants are sodium sulfide [1], thiourea [2] or thioacetamide [3].
  • Sodium thiosulfate was used as a sulfur source in the electrochemical synthesis of copper sulfide [4, 5] or using hydrothermal treatment [6].
  • Various compounds and synthesis methods are also known to produce the copper sulfide nanoparticles [7], including hydrothermal/solvothermal, sonochemical, electrochemical or microwave-assisted heating or chemical bath deposition [8, 9, 10].
  • Zhang et al. in an article [17] presented the hydrothermal method for the synthesis of shape-controlled copper sulfide nanocrystals. They used copper sulfate and sodium thiosulfate in water without any template or additive at 150 °C for 12 hours.
  • CN102557107 A relates to the synthesis of flower-shaped copper sulfide nanocrystals.
  • Copper sulfide nanocrystals are prepared by dissolving copper salt in deionized water. Sulfourea is dissolved in the copper salt solution, followed by hexadecyl trimethyl ammonium bromide (CTAB). The precursor solution is poured into a microwave hydrothermal reaction kettle. The reaction kettle is kept in a pressure and temperature reactor and cooled down to room temperature after the reaction is finished. The temperature of the reaction reactor was 100-160 °C and pressure was kept at 0.1-1 MPa. The reaction mixture is centrifuged and washed with water and ethanol.
  • CAB hexadecyl trimethyl ammonium bromide
  • CN102320647A relates to the preparation method of copper sulfide nanopowders with various stoichiometric ratios.
  • Copper sulfide nanopowder is prepared by mixing elemental copper powder and elemental sulphur powder. The elemental mixture is ball milled for 5-600 min in argon atmosphere at a 100-425 rpm rotational speed. The size of nanoparticles is in the range of 1-500 nm.
  • WO2016068646A1 relates to the synthesis of microporous filters based on copper compounds. Copper sulfide is synthesized by reacting copper sulfate pentahydrate with sodium sulfide in an aqueous solution for 30 min at temperature ranges from 10-80 °C.
  • CN102863006A relates to the synthesis of copper sulfide ultra-long microwires. These copper sulfide microwires are synthesized by the chemical liquid phase synthesis method. For synthesizing microwires, polymeric template is dissolved by stirring at room temperature in aqueous solution of copper sulfate pentahydrate, then the solution is placed at 60-80 °C in vacuum oven for 2 h.
  • Ammonium thiocyanate is dissolved in the solution and stirred for 30 min. Then again, the mixture is placed at 60-120 °C in the oven for 24 h. The mixture is cooled down to room temperature and copper sulfide precipitates are formed. The product is centrifuged, washed with deionized water and ethanol and then dried at 60 °C for 12 h in a vacuum oven.
  • W02016090507 Al relates to the synthesis of fluorescent and semi-conductive nanoparticles of copper sulfide.
  • copper salt solution is mixed with a reducing agent solution, then a buffer solution at a concentration of 10-50 mM is added to the solution.
  • the solution is incubated at a temperature between 28-100 °C for 18-24 h.
  • the reaction is stopped between 4-25 °C.
  • various studies have been done to control the shape and size of copper sulfide particles.
  • the objective of the present invention is to synthesize copper sulfide in room temperature.
  • This room-temperature synthesis method is important because it is simple and allows the control over the properties of copper sulfide with a new pathway compared to the traditional hydrothermal or electrochemical synthesis methods.
  • the present invention focuses on synthesizing Cu x S nanoparticles with various compositions, sizes and shapes. In the invention, the control over shape, size, and specific surface area can be achieved by adjusting the composition the reactants.
  • the objective of the present invention is to develop the synthesis method that is based on the production of Cu x S particles and nanoparticles using copper salts and sodium thiosulfate.
  • sulphur can also form as a side product of the reaction, an active antimicrobial compound but can be readily extracted with hot toluene solution.
  • the proposed invention requires only 30 min to 24 h synthesis time (depending on the targeted morphology), uses simple water-soluble chemical salts of copper and thiosulphate, and sulphuric acid as a catalyst. The reaction also takes place at room temperature and results high yield (above 90%).
  • Copper sulfide nanoparticles results from the acid induced sodium thiosulfate decomposition in the presence of copper ions at room temperature.
  • This synthesis method is important because it is simple and allows easy control over the properties of CuS with a new pathway compared to the traditional hydrothermal or electrochemical synthesis methods.
  • the decomposition rate of thiosulfate can be adjusted with the acid concentration and therefore the overall reaction procedure can be regulated.
  • Figure 3 Core- shell structure of CuS nanoparticles and a corresponding Energy Dispersive Spectra.
  • Figure 4. N2 adsorption/desorption curve of a high surface area C UX S nanospheres (specific surface area 12.38 m 2 /g).
  • the mixing step in the method is performed between 0-300 °C. Elevated temperature decreases the size of the particles and affects the morphology. The temperature range is important for the sample property and therefore the CuS formation.
  • the catalyst is a mineral acid or organic acid such as HC1, HBr, HI, CH3COOH and mixtures.
  • catalyst is H2SO4 since there are no foreigner ions introduced to the system that would affect the final properties of the product (forming impurities and inclusion). This is especially important for photocatalytic properties.
  • the preferred catalyst can provide the advantage that no purification process in necessary.
  • the concentration of the catalyst is between 10’ 4 M - 18 M, more preferably between 0.1 M - 0.7 M to form controlled size high surface area Cu x S nanoparticles.
  • the concentration of copper salt is between 0.1 M - 0.4 M, more preferably 0.01 mg/mL - 0.30 mg/mL in the aqueous solution containing the catalyst.
  • the concentration of thiosulphate salt is between 0.2 M - 0.6 M, in the aqueous solution.
  • Samples of Cu x S were synthesized using varied concentration of copper sulphate, sulphuric acid and sodium thiosulphate at room temperature.
  • the composition of the solution is summarized in Table 1. Firstly, copper salt is dissolved in water in the presence of acid catalyst, and separately sodium thiosulphate is dissolved in water. By mixing these solutions as reactants at room temperature, a reaction took place and solid Cu x S particles were obtained.
  • Figure 1 represents a typical powder X-ray Diffraction pattern of the crude sample after synthesis without further purification.
  • the particles are built from small nanoplatelets as shown on a scanning electron microscopy image presented on Figure 2 with the average size changing between 10-30 nm in diameter and with subnanometer size width.
  • Figure 3 shows that these copper and suphur containing nanoplatelets can assemble with a more loose inner core to form spherical particles.
  • the specific surface area of the nanoparticles was determined as high as 12.38 m 2 /g presented on Figure 4.
  • the photocatalytic properties of the samples were investigated using a model dye methylene blue (75 mg/L concentration). The dye sample was decomposed within 30 min in the presence of CuS (1.25 mg/mL), solar simulator light and hydrogen peroxide (7.5 wt%) (shown on

Abstract

The invention relates to a synthesis method for copper sulfide (CuxS) particles and nanoparticles with a high specific surface area, controlled morphology, antimicrobial activity and photocatalytic activity.

Description

A METHOD FOR SYNTHESIZING COPPER SULPHIDE PARTICLES
Technical Field
The invention relates to a synthesis method for copper sulfide (CuxS) particles and nanoparticles with a high specific surface area, controlled morphology, antimicrobial activity and photocatalytic activity.
The State of Art
Copper sulfide (CuS) has been extensively used in solar cells, sensors, and catalysis applications with having prominent photocatalytic activity, a small band gap, and is a p-type of semiconductor. Since copper sulfide exhibits antimicrobial activity accompanied by low toxicity, its particles are also used in biomedical applications for targeted drug delivery systems, imaging and diagnostic and therapeutic agents. While copper sulfide particles have many potential applications, most of the synthesis processes of such particles are complex. They tend to take longer synthesis time under a controlled environment, making them expensive for commercial applications. Copper sulfide can be synthesized with various methods. In general, the reaction of copper ions and sulfur-containing reactants can be directly carried out.
In the state of the art, the copper ions are obtained from simple copper (II) salts (CT, SO42, NO3 ) while the most common sulfur containing reactants are sodium sulfide [1], thiourea [2] or thioacetamide [3]. Sodium thiosulfate was used as a sulfur source in the electrochemical synthesis of copper sulfide [4, 5] or using hydrothermal treatment [6]. Various compounds and synthesis methods are also known to produce the copper sulfide nanoparticles [7], including hydrothermal/solvothermal, sonochemical, electrochemical or microwave-assisted heating or chemical bath deposition [8, 9, 10].
Xie et al. in an article [11] prepared several stoichiometries in colloidal copper sulfide nanocrystals. The platelet- shaped nanocrystals of copper sulfide were prepared by reacting as synthesized covellite nanocrystals with a Cu(I) complex, tetrakis (acetonitrile) copper (I) hexafluorophosphate ([Cu(CH3CN)4]PF6). The parent covellite nanocrystals were synthesized by a heat-up procedure using the sulphur solution and copper chloride. The reaction was carried out at 200 °C under a nitrogen environment for 30-60 minutes. The reaction product was washed and re-dispersed in toluene in a N2 filled glovebox.
Popovici et al. in an article [12] investigated the electrical conductivity of copper sulfide films. Copper sulfide films were obtained using the spray pyrolysis technique from alcoholic-water solutions. Thiourea and copper chloride were used as sulphur and copper precursor, respectively. The temperature in the spray pyrolysis method was varied between 240-300 °C.
Ni et al. in an article [13] presented the synthesis of hollow copper sulfide microspheres by using a simple template-free route. The reaction mixture contains copper sulphate, sodium thiosulphate and water at ambient conditions. The reaction was carried out at ambient temperature and pressure for one week.
Hosseinpour et al. in an article [14] investigated the performance of two different copper sulfide structures as electrode materials in lithium-ion batteries. They used tubular and ball-like copper sulfide structures. These structures were synthesized by a facile colloidal approach based on the reaction between copper nitrate and thiosulphate in water or water-ethylene glycol mixture as solvent. The reaction mixture was vigorously stirred at 70 °C for 4 h. The product was dried at 60 °C after centrifuging at room temperature.
Zhang et al. in an article [15] presented the synthesis of various copper sulfide nanostructures and their photocatalytic activities. They synthesized copper sulfide powders with controllable microstructures using different copper and sulphur precursors under relatively mild conditions of 140 °C for 90 min. Ni et al. in an article [16] presented the one-step synthesis of copper sulfide with hollow, solid, spherical and tubular structures by microwave irradiations.
Zhang et al. in an article [17] presented the hydrothermal method for the synthesis of shape-controlled copper sulfide nanocrystals. They used copper sulfate and sodium thiosulfate in water without any template or additive at 150 °C for 12 hours.
Several work can be found in the literature to achieve desired size, shape and properties of copper sulfide, however none of these papers reports simple synthesis.
The size and shape of copper sulfide particles play an important role in determining their applications. For example, spherical copper sulfide nanoparticles have found diverse applications in biomedicine; hollow nanospheres and nanocages hold promising potential in drug delivery; copper sulfide nanorods and nanowires have been successfully utilized for sensing of a variety of small molecules, food pathogens, and immunologically relevant moieties [18]. Various methods exist for synthesizing copper sulfide particles of various sizes and shapes.
CN102557107 A relates to the synthesis of flower-shaped copper sulfide nanocrystals. Copper sulfide nanocrystals are prepared by dissolving copper salt in deionized water. Sulfourea is dissolved in the copper salt solution, followed by hexadecyl trimethyl ammonium bromide (CTAB). The precursor solution is poured into a microwave hydrothermal reaction kettle. The reaction kettle is kept in a pressure and temperature reactor and cooled down to room temperature after the reaction is finished. The temperature of the reaction reactor was 100-160 °C and pressure was kept at 0.1-1 MPa. The reaction mixture is centrifuged and washed with water and ethanol. CN100441509 C relates to the synthesis of low-cost, monodisperse and liposoluble copper sulfide nanoparticles. The prepared nanoparticles have controllable size and shape. The synthesis of copper sulfide nanoparticles is done by dissolving saturated fatty alcohol and sulphur phosphoric acid in toluene and conducting reflux stirring reaction. The mixture is dispersed in alcohol and an aqueous solution of copper salt was added to this. The reaction mixture is filtered, washed and air-dried to obtain the green powder of intermediate double alkylthio phosphoric acid mantoquita. The intermediate is reacted with organic solvents under nitrogen protection at 140-240 °C for 4-6 h. The black powder is precipitated by adding acetone to the reaction mixture. The gained black powder is filtered, washed and dried.
US20120045387 Al relates to the synthesis of porous copper sulfide micro/nanospheres. The hollow micro/nanospheres of copper sulfides are synthesized by mixing copper precursor with a chelating agent. Two sulfur based reducing agents are added to the solution and a reaction is carried out for 5-600 s at a temperature of 60-100 °C. The reaction product is obtained by filtration, washing with deionized water, and drying.
CN102320647A relates to the preparation method of copper sulfide nanopowders with various stoichiometric ratios. Copper sulfide nanopowder is prepared by mixing elemental copper powder and elemental sulphur powder. The elemental mixture is ball milled for 5-600 min in argon atmosphere at a 100-425 rpm rotational speed. The size of nanoparticles is in the range of 1-500 nm.
WO2016068646A1 relates to the synthesis of microporous filters based on copper compounds. Copper sulfide is synthesized by reacting copper sulfate pentahydrate with sodium sulfide in an aqueous solution for 30 min at temperature ranges from 10-80 °C. CN102863006A relates to the synthesis of copper sulfide ultra-long microwires. These copper sulfide microwires are synthesized by the chemical liquid phase synthesis method. For synthesizing microwires, polymeric template is dissolved by stirring at room temperature in aqueous solution of copper sulfate pentahydrate, then the solution is placed at 60-80 °C in vacuum oven for 2 h. Ammonium thiocyanate is dissolved in the solution and stirred for 30 min. Then again, the mixture is placed at 60-120 °C in the oven for 24 h. The mixture is cooled down to room temperature and copper sulfide precipitates are formed. The product is centrifuged, washed with deionized water and ethanol and then dried at 60 °C for 12 h in a vacuum oven.
CN1757602B relates to the synthesis of nanometer-sized hollow copper sulfide balls. Copper sulfide hollow balls are prepared by mixing inorganic salt of copper and sulphur in tensio-active agent microemulsion maintained at room temperature -95° C. The mixture is kept for 24 h at constant temperature, suction filtration and drying at 60-110 °C in vacuum oven for 3 h. The pH of solution is maintained at 5.5-12. The tension-active agent microemulsion contains sodium lauryl sulphate (SDS), poly-diisooctyl diacetate esters, Span-60, silicone oil-based surfactants.
US9561458B2 relates to an anti-bacterial filter containing a copper-based compound. The chemical structure of the copper sulfide is CuxSy satisfying x/y=0.8 to 1.5. Copper sulfide is prepared by reacting copper sulfate with a salt selected from sulfides, fluorides, and chlorides in an aqueous phase at a mole ratio of 1:1 at 10 to 80 °C.
CN101544394B relates to the method to prepare nano-micron hollow spheres of copper sulfide. These hollow spheres increase the reaction area and can be used in solar cells. Copper sulfide hollow spheres are prepared by mixing the bronze metal solution with a sequestrant, then two sulphur sources are added simultaneously at 65 °C, the reaction mixture is filtered, washed and dried. The sequestrant is selected from the group of N, N-dimethyl-ethylenediamine, 1,3- propylene diamine or quadrol.
W02016090507 Al relates to the synthesis of fluorescent and semi-conductive nanoparticles of copper sulfide. For synthesizing copper sulfide nanoparticles, copper salt solution is mixed with a reducing agent solution, then a buffer solution at a concentration of 10-50 mM is added to the solution. The solution is incubated at a temperature between 28-100 °C for 18-24 h. The reaction is stopped between 4-25 °C. In conclusion, various studies have been done to control the shape and size of copper sulfide particles.
However, there is no systematic study in the literature on the room temperature synthesis of copper sulfide nanoparticles with acid-induced sodium thiosulfate decomposition in the presence of copper ions.
Summary of the Invention
The main objective of the present invention is to provide a novel synthesis method of copper sulfide (CuxS) particles exhibiting high specific surface area. The formation of CuxS particles is controlled with the acid-induced decomposition of sodium thiosulfate in the presence of copper ions. The present invention discloses the effect of the decomposition rate of thiosulfate and ratio of the reactants as well as the effect of the additives on
• the reaction % yield,
• particle size,
• morphology,
• agglomeration rate of the particles,
• composition of CuxS.
The objective of the present invention is to synthesize copper sulfide in room temperature. This room-temperature synthesis method is important because it is simple and allows the control over the properties of copper sulfide with a new pathway compared to the traditional hydrothermal or electrochemical synthesis methods. The present invention focuses on synthesizing CuxS nanoparticles with various compositions, sizes and shapes. In the invention, the control over shape, size, and specific surface area can be achieved by adjusting the composition the reactants.
The objective of the present invention is to develop the synthesis method that is based on the production of CuxS particles and nanoparticles using copper salts and sodium thiosulfate. In addition, sulphur can also form as a side product of the reaction, an active antimicrobial compound but can be readily extracted with hot toluene solution. The proposed invention requires only 30 min to 24 h synthesis time (depending on the targeted morphology), uses simple water-soluble chemical salts of copper and thiosulphate, and sulphuric acid as a catalyst. The reaction also takes place at room temperature and results high yield (above 90%). Copper sulfide nanoparticles results from the acid induced sodium thiosulfate decomposition in the presence of copper ions at room temperature. This synthesis method is important because it is simple and allows easy control over the properties of CuS with a new pathway compared to the traditional hydrothermal or electrochemical synthesis methods. The decomposition rate of thiosulfate can be adjusted with the acid concentration and therefore the overall reaction procedure can be regulated.
Description of the Invention
“A METHOD FOR SYNTHESIZING COPPER SUEPHIDE PARTICLES” developed to fulfill the objectives of the present invention is illustrated in the accompanying figures, in which;
Figure 1. X-ray powder diffraction of the as- synthesized CuxS particles.
Figure 2. High resolution field emission scanning microscopy image of spherical particles built up from nano-platelets.
Figure 3. Core- shell structure of CuS nanoparticles and a corresponding Energy Dispersive Spectra. Figure 4. N2 adsorption/desorption curve of a high surface area CUXS nanospheres (specific surface area 12.38 m2/g).
Figure 5. Photocatalytic decomposition of methylene blue by CuxS photocatalysts.
Figure 6. Antimicrobial property demonstrated on Staphylococcus aureus bacteria with disc diffusion method.
The invention relates to a method for synthesizing copper sulphide particles having a high surface area, controlled morphology, antimicrobial activity and photocatalytic activity. This method comprises the steps of
• mixing at least one catalyst and salt of copper precursor respectively, in an aqueous solution to form a homogeneous solution,
• mixing at least one thiosulphate salt in an aqueous solution to form a homogeneous solution,
• combination of the copper salt solution with the thiosulphate solution at ambient condition.
In the method for synthesizing copper sulphide particles, as explained above, firstly copper salt is dissolved in water in the presence of acid catalyst, and separately sodium thiosulphate is dissolved in water. By mixing these solutions as reactants at room temperature, a reaction occurs to obtain solid CuxS particles in the form of nanoplatelets, nanoneedles, nanospheres, and core/shell particles due to the presence of acid catalysed decomposition of thiosulphate. The samples are left undisturbed between 30 minutes and 24 hours for the reaction to take place.
The mixing step in the method is performed between 0-300 °C. Elevated temperature decreases the size of the particles and affects the morphology. The temperature range is important for the sample property and therefore the CuS formation. In one embodiment of the invention, the catalyst is a mineral acid or organic acid such as HC1, HBr, HI, CH3COOH and mixtures. Preferably, catalyst is H2SO4 since there are no foreigner ions introduced to the system that would affect the final properties of the product (forming impurities and inclusion). This is especially important for photocatalytic properties. In addition, the preferred catalyst can provide the advantage that no purification process in necessary. The concentration of the catalyst is between 10’4 M - 18 M, more preferably between 0.1 M - 0.7 M to form controlled size high surface area CuxS nanoparticles.
The concentration of copper salt is between 0.1 M - 0.4 M, more preferably 0.01 mg/mL - 0.30 mg/mL in the aqueous solution containing the catalyst.
The concentration of thiosulphate salt is between 0.2 M - 0.6 M, in the aqueous solution.
EXPERIMENTAL DATA
Experiment 1.
Samples of CuxS were synthesized using varied concentration of copper sulphate, sulphuric acid and sodium thiosulphate at room temperature. The composition of the solution is summarized in Table 1. Firstly, copper salt is dissolved in water in the presence of acid catalyst, and separately sodium thiosulphate is dissolved in water. By mixing these solutions as reactants at room temperature, a reaction took place and solid CuxS particles were obtained.
Table 1. Composition of the reaction solutions for CuxS synthesis.
Figure imgf000011_0001
The samples were collected using gravitational filtration method. Figure 1 represents a typical powder X-ray Diffraction pattern of the crude sample after synthesis without further purification. The particles are built from small nanoplatelets as shown on a scanning electron microscopy image presented on Figure 2 with the average size changing between 10-30 nm in diameter and with subnanometer size width. Figure 3 shows that these copper and suphur containing nanoplatelets can assemble with a more loose inner core to form spherical particles. The specific surface area of the nanoparticles was determined as high as 12.38 m2/g presented on Figure 4. The photocatalytic properties of the samples were investigated using a model dye methylene blue (75 mg/L concentration). The dye sample was decomposed within 30 min in the presence of CuS (1.25 mg/mL), solar simulator light and hydrogen peroxide (7.5 wt%) (shown on
Figure 5). Antimicrobial activity of the samples presented clear inhibition zone for Staphylococcus aureus (Figure 6). REFERENCES
[1]. Ramadan S., Hollow Copper sulfide nanoparticle-mediated transdermal drug delivery, Small, 3143, 2012; Yu X., Nanometer- sized copper sulfide hollow spheres with strong optical-limiting properties, Advanced Functional Materials, 1397, 2007.
[2]. Ghahremaninezhad A., Electrodeposition and growth mechanism of copper sulfide nanowires, Journal of Physical Chemistry C, 9320, 2011.
[3]. Thongtem T., Formation of CuS with flower-like, hollow spherical, and tubular structures using the solvothermal-microwave process, Current Applied Physics, 195, 2009.
[4]. Wei J., A novel high-performance electrode: in- situ growth of copper sulfide film on copper foil for the application of supercapacitor, Journal of Materials Science: Materials in Electronics, 4185, 2015.
[5]. Yang Y. J., A facile electrochemical synthesis of covellite nanomaterials at room temperature, Journal Solid State Electrochemistry, 1405, 2008.
[6]. Hosseinpour Z., Morphology-dependent electrochemical properties of CuS hierarchical superstructures, ChemPhysChem, 3418, 2015.
[7]. Argueta-Figueroa L. Nanomaterials made of non-toxic metallic sulfides: A systematic review of their potential biomedical applications, Materials Science and Engineering C, 1305, 2017.
[8]. Wang Z., Biomineralization-inspired synthesis of copper sulfide-ferritin nanocages as cancer theranostics, ACS Nano, 3453, 2016. [9]. Zhou M., CuS nanodots with ultrahigh efficient renal clearance for positron emission tomography imaging and image-guided photothermal therapy, ACS Nano, 7085, 2015.
[10]. Lakshmanan S.B., Local field enhanced au/cus nanocomposites as efficient photothermal transducer agents for cancer treatment, Journal of Biomedical Nanotechnology, 883, 2012.
[11]. Xie, Yi, et al. Copper sulfide nanocrystals with tunable composition by reduction of covellite nanocrystals with Cu+ ions. Journal of the American Chemical Society, 2013.
[12]. Popovici, I.; Isac, L.; Duta, A. Electrical Conductivity in Copper Sulfides-
Influence of the Deposition Parameters and Precursor's Concentration. Bulletin of the Transilvania University of Brasov. Engineering Sciences. Series I, 2009.
[13]. Ni, Yonghong, et al. Fabrication and characterization of hollow cuprous sulfide (Cu2- xS) microspheres by a simple template-free route. Inorganic Chemistry Communications, 2003.
[14]. Hosseinpour, Zahra, et al. Morphology -dependent electrochemical properties of CuS Hierarchical Superstructures. ChemPhysChem, 2015.
[15]. Zhang, Yu-Qiao, et al. Preparation by solvothermal synthesis, growth mechanism, and photocatalytic performance of CuS nanopowders. European Journal of Inorganic Chemistry, 2014.
[16]. Ni et al. Self-assembly of copper sulfide nanoparticles to solid, hollow, spherical and tubular structures in a simple aqueous-phase reaction, Applied Physics A -Materials Science & Processing, 2007, 2004. [17]. Zhang, Yong Cai; Hu, Xiao Ya; Qiao, Tao. Shape-controlled synthesis of
CuS nanocrystallites via a facile hydrothermal route. Solid state communications, 2004.
[18]. Goel, Shreya; Chen, Feng; Cai, Weibo. Synthesis and biomedical applications of copper sulfide nanoparticles: from sensors to theranostics. Small, 2014.

Claims

CLAIMS A method for synthesizing CuxS particles characterized by comprising the steps of:
• mixing at least one catalyst and salt of copper precursor respectively, in an aqueous solution to form a homogeneous solution,
• mixing at least one thiosulphate salt in an aqueous solution to form a homogeneous solution,
• combination of the copper salt solution with the thiosulphate solution at ambient condition. The method for synthesizing CuxS particles according to claim 1, wherein the mixing step and reaction is performed between 0 - 300 °C. The method for synthesizing CuxS according to the preceding claims, wherein the catalyst is a mineral acid or organic acid such as HC1, HBr, HI, CH3COOH and mixtures. The method for synthesizing CuxS according to the preceding claims, wherein the catalyst is H2SO4. The method for synthesizing CuxS according to claim 4, wherein the concentration of the catalyst is between 10’4 M - 18 M to form controlled size high surface area CuxS nanoparticles. The method for synthesizing CuxS according to claim 4, wherein the concentration of the catalyst is between 0.1 M - 0.7 M to form controlled size high surface area CuxS nanoparticles.
7. The method for synthesizing CuxS according to the preceding claims, wherein the concentration of copper salt is between 0.1 M - 0.4 M in the aqueous solution containing the catalyst. 8. The method for synthesizing CuxS according to the preceding claims, wherein the concentration of copper salt is between 0.01 mg/mL - 0.30 mg/mL in the aqueous solution containing the catalyst.
9. The method for synthesizing CuxS according to the preceding claims, wherein the concentration of thiosulphate salt is between 0.2 M - 0.6 M in the aqueous solution.
PCT/TR2022/050609 2022-06-17 2022-06-17 A method for synthesizing copper sulphide particles WO2023244187A1 (en)

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