WO2015132802A2 - Procédé de synthèse de feuilles métalliques monocouches - Google Patents

Procédé de synthèse de feuilles métalliques monocouches Download PDF

Info

Publication number
WO2015132802A2
WO2015132802A2 PCT/IN2015/000117 IN2015000117W WO2015132802A2 WO 2015132802 A2 WO2015132802 A2 WO 2015132802A2 IN 2015000117 W IN2015000117 W IN 2015000117W WO 2015132802 A2 WO2015132802 A2 WO 2015132802A2
Authority
WO
WIPO (PCT)
Prior art keywords
metal
nanosheets
toluene
nickel
substrate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/IN2015/000117
Other languages
English (en)
Other versions
WO2015132802A3 (fr
Inventor
Prasad LAKSHMI VARA BHAGAVATULA
Balanagulu BUSUPALLI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
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.)
Filing date
Publication date
Application filed by Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Publication of WO2015132802A2 publication Critical patent/WO2015132802A2/fr
Publication of WO2015132802A3 publication Critical patent/WO2015132802A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds

Definitions

  • US 20080149322 Al discloses Graphite films with a metal coating of at most 100 nm thick and are produced, for example by a continuous vapor deposition process on graphite film.
  • the graphite films can be connected to one another or to other components of metal or metal-coated materials by soldering.
  • the thin metal coating protects the surface of the graphite film against particles breaking out or peeling or flaking off.
  • WO 1987001724 Al reports a composition for use in removing polysulfide sealants or coatings.
  • the composition comprises a thiolate such as an alkyl or phenyl thiolate with an alkali metal or Quaternary ammonium ion in a solution of dimethyl formamide or dimethyl acetamide either alone or in admixture with an aromatic solvent such as toluene or xylene.
  • a disulfide compound such as diphenyl disulfide or tert butyl disulfide in the composition provides a synergistic improvement in the desealing rate.
  • Nickel sulfide - nickel Ni 3 S 2 -Ni
  • step (a) delaminating the layered complex of step (a) into its individual sheets by immersing in a solvent
  • the transition metal is in the form of a metal salt.
  • the ligand is a moiety containing groups selected from thiols, amines and carboxylic acids, preferably, octanethiol, dodecanethiol, decanethiol, hexadecanethiol, and octadecanethiol, either alone or combination thereof.
  • the substrate is selected from the group consisting of glass, quartz, silicon and mica.
  • said process further provides nanosheets of metal sulphides.
  • Ni 3 S 2 and Ni 3 S 2 -Ni nanosheets exhibits ferromagnetic behaviour at room temperature with a saturation magnetization value of 10 emu/g.
  • Figure 2 represents a) DLS for samples at different concentrations viz. from 100% w/v to 1.67% w/v in toluene.
  • the solid lines represent fitting curves obtained using equation 2.
  • Figure 8 represents electrochemical hydrogen evolution reaction, a) Linear sweep voltammetry (LSV) curves for the nickel sulfide and nickel sulfide - nickel metal nanosheets and their corresponding nanodisks. b) Table summarizing the electrochemical hydrogen generation properties of the nanosheets and nanodisks.
  • LSV Linear sweep voltammetry
  • Fig 9 represents SQUID measurements, a) Room temperature magnetization plotted with magnetic field for the samples Ni 3 S 2 and Ni3S2-Ni show ferromagnetism in both the samples. Inset in the Figure a) is for clarity regarding the plot of the Ni 3 S 2 sample which shows a diamagnetic contribution along with the noticeable ferromagnetism. b) Fully magnified trace from the Figure a) reveals coercivity values of about 50 Oe for both the samples Ni 3 S 2 and Ni 3 S 2 -Ni. c) Plot of magnetization with temperature i.e.
  • the metal in the process is a transition metal selected from Ni, Pb, Pd, Au, Ag, Cu, Sn, Hg, Co, Fe, Mn, Cd, Pt or metal salts and such like, either alone or combination thereof.
  • the ligand is selected from thiols, preferably octanethiol, dodecanethiol, decanethiol, hexadecanethiol, and octadecanethiol) either alone or combination thereof.
  • the substrate is selected from silicon, glass, quartz, mica and such like.
  • the solvent for delaminating may be a non-polar solvent, selected from chloroform, toluene, hexane, cyclohexane, tert- butyl-toluene, carbon tetrachloride and such like.
  • the coating of the delaminated sheet may be carried out by processes selected from spin coating or dip coating.
  • the present invention provides a process for the preparation of Ni 3 S 2 and Ni 3 S 2 -Ni nanosheets from nickel octanethiolate comprising heating the sample in a tube- furnace equipped with gas flow maintaining a constant temperature of 750 °C and at a constant gas flow rate of 2 ml/ sec for 6 hours duration followed by cooling the sample back to room temperature to obtain the final product.
  • PTFE Polytetrafluoroethylene
  • DLS was then recorded on the 100% w/v sample.
  • the 100% w/v sample was then diluted scrupulously to get subsequent dilutions of 60% w/v, 50% w/v, 40% w/v, 30% w/v, 20% w/v, 10% w/v, 5% w/v, 1.667% w/v, 0.56 % w/v by filtering toluene (analytical reagent grade) into the preceding concentrated sample in the sample cell through a 0.2 ⁇ hydrophobic PTFE filter.
  • 100% w/v sample in solution was prepared separately by dissolving 1000 mg of the sample in 1000 ⁇ . of toluene. DLS measurements were then made on each sample at a constant angle 90° for 30 seconds.
  • Multi angle DLS was performed on Pd-octanethiolate sample at 50% w/v, 40% w/v, 30% w/v, 20% w/v and 10% w/v. The data were collected at angles 45-60-75-90- 105-120 degrees. This was repeated for at least three times and the results were consistent. (Table 1)
  • WAXD Wide angle X-ray diffraction
  • HDPE film high density polyethylene film used as a reference for all the samples was hanged between the sample and the beam stop and kept at constant position for all the samples.
  • WAXD experiments were performed on the individually prepared 500% w/v, 300% w/v, 100% w/v samples of palladium octanethiolate in toluene. The images were analyzed using 'image J' software from NIH and to plot the corresponding graphs in ID.
  • a high density polyethylene film (HDPE film) used as a standard was hung between the sample holder and the detector in the Rigaku rotating anode diffractometer. Initially scattering from only the cylindrical borosilicate glass capillary was measured, next the capillary filled with toluene was subjected to WAXD experiment. The scattering data from the empty glass capillary and the toluene containing glass capillary were used for correcting the sample scattering for the samples taken in the glass capillary in toluene solution. Then, the WAXD measurements were performed on samples 500%, 300% and 100% w/v concentrations respectively prepared separately in the same glass capillary. Thus subtraction of scattering from the empty glass and the glass containing toluene solvent could be possible for all the samples. As HDPE film was hung for all the measurements, there isn't any ambiguity in the data.
  • EDX Energy Dispersive X-ray Analysis
  • Nickel octanethiolate powder sample was heated in a tube-furnace equipped with Argon gas flow maintaining a constant temperature of 750°C and at a constant gas flow rate of 2 ml/ sec for 6 hours duration. After 6 hours of heating the sample was cooled back to room temperature and the final product was collected.
  • Nickel octanethiolate powder sample was heated in a tube-furnace equipped with Hydrogen + Argon (in 1:1 ratio) gas flow maintaining a constant temperature of 750 °C and at a constant gas flow rate of 2 ml/ sec for 6 hours duration. After 6 hours of heating the sample was cooled back to room temperature and the final product was collected.
  • Microstructural morphological features of the samples were obtained from a field emission scanning electron microscopy (FE-SEM) with FEI Nova nano SEM 450.
  • Nickel octanethiolate sample was subjected to thermogravimetric analysis utilizing a TG50 analyzer (Mettler-Toledo) or a SDT Q600 TG-DTA analyzer under nitrogen atmosphere at 10 °C m f 1 heating rate within a temperature range of 20-900 °C.
  • Electrochemical hydrogen evolution reaction (HER) (Fig: 8, 10)
  • Metal sulfide nanosheets resulted from the heating of their precursor metal thiolates coated from their solutions in organic apolar solvents such as chloroform, toluene etc. on to substrates like quartz.
  • Electrochemical hydrogen generation was achieved in the nickel sulfide-nickel nanosheets (Ni 3 S 2 -Ni) and also in the nickel sulfide (Ni 3 S 2 ) nanosheets.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemically Coating (AREA)

Abstract

L'invention concerne un procédé pour la préparation d'une couche métallique épaisse d'au moins un atome sur un substrat sous la forme d'une nanofeuille. L'invention concerne également un procédé pour la préparation de nanofeuilles contenant Ni3S2 et Ni3S2-Ni présentant un comportement ferromagnétique à température ambiante.
PCT/IN2015/000117 2014-03-05 2015-03-05 Procédé de synthèse de feuilles métalliques monocouches Ceased WO2015132802A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN612/DEL/2014 2014-03-05
IN612DE2014 2014-03-05

Publications (2)

Publication Number Publication Date
WO2015132802A2 true WO2015132802A2 (fr) 2015-09-11
WO2015132802A3 WO2015132802A3 (fr) 2015-11-19

Family

ID=53181317

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2015/000117 Ceased WO2015132802A2 (fr) 2014-03-05 2015-03-05 Procédé de synthèse de feuilles métalliques monocouches

Country Status (1)

Country Link
WO (1) WO2015132802A2 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987001724A1 (fr) 1985-09-18 1987-03-26 The Commonwealth Of Australia Compositions d'elimination d'agents d'etancheite
US5100737A (en) 1989-11-16 1992-03-31 Le Carbone Lorraine Multi-layer material comprising flexible graphite which is reinforced mechanically, electrically and thermally by a metal and a process for the production thereof
US5744245A (en) 1991-05-17 1998-04-28 Johnson Matthey Public Limited Company Precious metal composition
US20080149322A1 (en) 2005-06-21 2008-06-26 Sgl Carbon Aktiengesellschaft Metal Coated Graphite Sheet

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4405423C2 (de) * 1994-02-21 1996-05-30 Cerdec Ag Monoedelmetall-dithiolate, Verfahren zu deren Herstellung und deren Verwendung
EP0668265B1 (fr) * 1994-02-21 1997-06-18 Cerdec Aktiengesellschaft Keramische Farben Dithiolates de monometal noble et leur utilisation pour la préparation des décorations contenant des métaux nobles sur des substrats aptes à la cuisson

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987001724A1 (fr) 1985-09-18 1987-03-26 The Commonwealth Of Australia Compositions d'elimination d'agents d'etancheite
US5100737A (en) 1989-11-16 1992-03-31 Le Carbone Lorraine Multi-layer material comprising flexible graphite which is reinforced mechanically, electrically and thermally by a metal and a process for the production thereof
US5744245A (en) 1991-05-17 1998-04-28 Johnson Matthey Public Limited Company Precious metal composition
US20080149322A1 (en) 2005-06-21 2008-06-26 Sgl Carbon Aktiengesellschaft Metal Coated Graphite Sheet

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ABRAHAM ULMAN: "Thin Films, Monomolecular Layers", KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY REPORTS MONOMOLECULAR LAYERS, 2000
LEE: "Growth, solvent effects, and thermal desorption behavior of octylthiocyanate self-assembled monolayers on Au(I 11", PHYS. CHEM. CHEM. PHYS., vol. 15, 2013, pages 3609 - 3617
RIE MAKIURA: "|nterfacial growth of large-area single-layer metal-organic framework nanosheets", SCIENTIFIC REPORTS, vol. 3, 2013, pages 2506

Also Published As

Publication number Publication date
WO2015132802A3 (fr) 2015-11-19

Similar Documents

Publication Publication Date Title
KR101795088B1 (ko) 금속 잉크 조성물, 전도성 패턴, 방법, 및 장치
Shim et al. An organometallic route to highly monodispersed silver nanoparticles and their application to ink-jet printing
Chaudret Organometallic approach to nanoparticles synthesis and self-organization
Monteiro et al. Use of dialkyldithiocarbamato complexes of bismuth (III) for the preparation of nano-and microsized Bi2S3 particles and the X-ray crystal structures of [Bi {S2CN (CH3)(C6H13)} 3] and [Bi {S2CN (CH3)(C6H13)} 3 (C12H8N2)]
Tang et al. One-pot synthesis and self-assembly of colloidal copper (I) sulfide nanocrystals
Shen et al. Generalized synthesis of metal sulfide nanocrystals from single-source precursors: size, shape and chemical composition control and their properties
JP4284283B2 (ja) 銀の粒子粉末の製造法
JP5108502B2 (ja) 銀粒子粉末およびその製造法
Khan et al. Phase pure deposition of flower-like thin films by aerosol assisted chemical vapor deposition and solvent mediated structural transformation in copper sulfide nanostructures
Maji et al. Deposition of nanocrystalline CuS thin film from a single precursor: Structural, optical and electrical properties
Nithiyanantham et al. Shape-selective formation of MnWO 4 nanomaterials on a DNA scaffold: magnetic, catalytic and supercapacitor studies
Jana et al. Electrospray deposition-induced ambient phase transition in copper sulphide nanostructures
Palve Deposition of zinc sulfide thin films from zinc (II) thiosemicarbazones as single molecular precursors using aerosol assisted chemical vapor deposition technique
Rezaei et al. Electrodeposited silver nanodendrites electrode with strongly enhanced electrocatalytic activity
JP5861912B2 (ja) 有機化合物とナノ銅粒子との複合体、有機化合物とナノ酸化銅（ｉ）粒子との複合体、並びにそれらの製造方法
Bera et al. Nanocrystalline copper sulfide of varying morphologies and stoichiometries in a low temperature solvothermal process using a new single-source molecular precursor
Chen et al. Controlled Growth of Cubic Cadmium Sulfide Nanoparticles Using Patterned Self‐Assembled Monolayers as a Template
Fard et al. Sonochemical synthesis of new nano-two-dimensional lead (II) coordination polymer: As precursor for preparation of PbO nano-structure
Sadeghzadeh et al. Sonochemical synthesis and characterization of nano-belt lead (II) coordination polymer: new precursor to produce pure phase nano-sized lead (II) oxide
Xie et al. Formulating nickel metal organic decomposition ink with low sintering temperature and high conductivity for ink jet printing applications
Mlowe et al. Morphological influence of deposition routes on lead sulfide thin films
Akhbari et al. Preparation of silver nanoparticles from silver (I) nano-coordination polymer
Rashid et al. Low-temperature polymer-assisted synthesis of shape-tunable zinc oxide nanostructures dispersible in both aqueous and non-aqueous media
Trabelsi et al. Aerosol-assisted chemical vapor deposited Cu2S structured films with photo activated NO2 sensing properties
Welearegay et al. Fabrication and characterisation of ligand-functionalised ultrapure monodispersed metal nanoparticle nanoassemblies employing advanced gas deposition technique

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15723052

Country of ref document: EP

Kind code of ref document: A2