WO2023244187A1 - Procédé de synthèse de particules de sulfure de cuivre - Google Patents

Procédé de synthèse de particules de sulfure de cuivre Download PDF

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Publication number
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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WO
WIPO (PCT)
Prior art keywords
copper
synthesizing
copper sulfide
catalyst
synthesis
Prior art date
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PCT/TR2022/050609
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English (en)
Inventor
Annamaria MIKO
Halil KAVAKLI
Adem Levent DEMIREL
Aatif IJAZ
Yavuz Ali EKMEKCIOGLU
Original Assignee
Koc Universitesi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Koc Universitesi filed Critical Koc Universitesi
Priority to PCT/TR2022/050609 priority Critical patent/WO2023244187A1/fr
Publication of WO2023244187A1 publication Critical patent/WO2023244187A1/fr

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Classifications

    • 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

L'invention concerne un procédé de synthèse de particules et de nanoparticules de sulfure de cuivre (CuxS) présentant une surface spécifique élevée, une morphologie contrôlée, une activité antimicrobienne et une activité photocatalytique.
PCT/TR2022/050609 2022-06-17 2022-06-17 Procédé de synthèse de particules de sulfure de cuivre WO2023244187A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/TR2022/050609 WO2023244187A1 (fr) 2022-06-17 2022-06-17 Procédé de synthèse de particules de sulfure de cuivre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TR2022/050609 WO2023244187A1 (fr) 2022-06-17 2022-06-17 Procédé de synthèse de particules de sulfure de cuivre

Publications (1)

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WO2023244187A1 true WO2023244187A1 (fr) 2023-12-21

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Country Status (1)

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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GONZALEZ-LARA, J.M. ; ROCA, A. ; CRUELLS, M. ; PATINO, F.: "The oxidation of thiosulfates with copper sulfate. Application to an industrial fixing bath", HYDROMETALLURGY., ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM., NL, vol. 95, no. 1-2, 1 January 2009 (2009-01-01), NL , pages 8 - 14, XP025717115, ISSN: 0304-386X, DOI: 10.1016/j.hydromet.2008.04.001 *
GROZDANOV, I. ; BARLINGAY, C.K. ; DEY, S.K. ; RISTOV, M. ; NAJDOSKI, M.: "Experimental study of the copper thiosulfate system with respect to thin-film deposition", THIN SOLID FILMS, ELSEVIER, AMSTERDAM, NL, vol. 250, no. 1-2, 1 October 1994 (1994-10-01), AMSTERDAM, NL , pages 67 - 71, XP024739584, ISSN: 0040-6090, DOI: 10.1016/0040-6090(94)90167-8 *
XP93122606, Retrieved from the Internet <URL:https://uwaterloo.ca/cheml3-news-magazine/november-2012/activities/unusual-and-simply-prepared-compound-copper> [retrieved on 20230405] *

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