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
  • C23C18/08—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
  • C23C18/1208—Oxides, e.g. ceramics
  • C23C18/1216—Metal oxides
• • 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
  • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
  • C23C18/127—Preformed particles
• • 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
  • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
• • 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
  • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
  • C23C18/145—Radiation by charged particles, e.g. electron beams or ion irradiation

Definitions

• the present invention relates to a method for (simultaneously forming and) depositing nanoparticles on nanoscopic and microscopic substrates, such as carbon nanotubes, or porous substrates.
• the present invention relates to a method for (simultaneously forming and) depositing nanoparticles using liquid or solid (organometallic) precursors and ((very) low temperature) plasma treatment.
• Carbon nanotubes attract scientist attentions during more than last 15 years due to their extraordinary physical, chemical, and mechanical properties, and their, almost one-dimensional, structure.
• SW single-wall
• MW multi- wall
• NPs nanoparticles
• decoration or deposition
• carbon nanotubes to form (nano ) hybrids .
• CVD Chemical Vapour Deposition
• MOCVD Metallo-Organic Chemical Vapour Deposition
• PECVD Plasma-Enhanced Chemical Vapour Deposition
• Thermal CVD Thermal CVD
• CVD of volatile organometallic compounds is widely used for formation of metallic and oxide coatings (or continuous films) on different substrates.
• JP 2009 167031 for example describes the use of an arc plasma at elevated temperatures (of not less than 3000 K) for the manufacturing of metal-including carbon nanotubes.
• Nanometer powders can be produced by microwave plasma, as described in e.g. TW248328, where the precursor gas is decomposed by the microwave plasma.
• the precursor gas can even be decomposed by a dense fluid medium, as described in e.g. US2008169182.
• a high temperature plasma (above 300°C) is used where iron and nickel (nano ) powders were inserted into the high temperature microwave plasma reactor using a hydrogen carrier gas.
• Plasma especially cold plasma (or low temperature plasma) , seems to be a very promising tool in the case of the decoration of carbon nanotubes.
• EP 1 323 846 describes a process for preparing metal coatings upon porous substrate surfaces from liquid solutions utilizing a cold plasma.
• US 2008/0145553 describes a process for the in- flight surface treatment of powders using a Dielectric Barrier Discharge Torch operating at atmospheric pressures or soft vacuum conditions.
• the process comprises feeding a powder material into the Dielectric Barrier Discharge Torch yielding powder particles; in-flight modifying the surface properties of the particles; and collecting coated powder particles .
• the present invention provides a method particularly advantageous for (simultaneously forming and) depositing nanoparticles on nanoscopic and microscopic substrates, such as carbon nanotubes, or porous, or flat substrates, wherein the method involves fewer steps than the processes known in the art.
• the present invention provides an improved method for depositing nanoparticles on nanoscopic and microscopic substrates, when compared to processes known in the art.
• the method of the present invention has the advantage over existing methods in prior art that it is a simplified method. [0032]
• the method provided by the present invention avoids the use of a gas-comprising (or containing) precursor flow, and avoids the injection of the precursors into the plasma.
• the method of the invention provides the advantage of avoiding (( electro ) chemical , and/or physical) pre-treatment (or functionalization) of the substrates, when compared to the processes known in the art .
• “functionalization of the substrate” refers to introducing chemical functional groups to a substrate (or allowing to attach a number of groups to the substrate) using for example acids, or crosslinking .
• the method of the invention also avoids high- temperature heating, when compared to the processes known in the art .
• the method of the invention avoids high-temperature plasma treatment, when compared to the processes known in the art.
• a "high- temperature plasma” is a plasma having a temperature higher than (about) 300°C, preferably higher than (about) 600°C, more preferably higher than (about) 1000°C.
• the method of the present invention provides the preparation of (nano ) hybrids by using precursors being in a liquid or a solid phase, and a plasma with (very) low temperature (i.e. a plasma temperature being lower than (about) 300°C) .
• the plasma temperature is lower than (about) 300°C, preferably lower than (about) 200°C.
• the plasma temperature can be close to ambient temperature.
• the method of the present invention has the advantage over existing methods in prior art that the (significantly) degradation (or melting) of the substrate is avoided.
• hybrid refers to a microscopic substrate on which nanoparticles are deposited.
• nanohybrid refers to a nanoscopic substrate on which nanoparticles are deposited.
• a method for (simultaneously forming and) depositing nanoparticles (or nanoclusters ) on a substrate comprising the steps of:
• the temperature of the plasma during the step of exposing said mixture of said precursor and said substrate to a plasma is lower than (about) 300°C.
• the plasma is a low temperature plasma (or a cold plasma, or a non-thermal plasma) (i.e. with a plasma temperature being lower than (about) 300°C) .
• a "low temperature plasma” refers to a plasma where the temperature of the neutral gas particles (or atoms, or molecules) is much lower than the temperature of the ions, which in turn is much lower than the temperature of the electrons (i.e. T g ⁇ Ti ⁇ T e , wherein T g is close to the ambient temperature) .
• the temperature of the plasma during the step of exposing (or subjecting) said mixture of said precursor and said substrate to a plasma is lower than (about) 200°C, and more preferably comprised between (about) 50 °C and (about) 150 °C.
• reactor refers to a plasma reactor, reaction chamber, plasma chamber, or post discharge region.
• no (( electro ) chemical , and/or physical) pre-treatment (or functionalization) of the substrate is performed.
• no gas- comprising (or containing) precursor flow is used.
• no injection e.g. by using a carrier gas
• no injection e.g. by using a carrier gas
• the substrate is not (significantly) degraded (or melted) .
• said precursor and said substrate are mixed in said mixing step, said mixing step being performed outside or inside said reactor, thereby forming (or preparing) a mixture of said precursor and said substrate.
• the precursor (s) and the substrate do not react with each other during said mixing step (or by performing said mixing step) .
• the precursor (s) and the substrate do not undergo any changes (e.g. decomposition, degradation, or melting) during said mixing step (or by performing said mixing step) .
• the precursor (s) is (are) (only) in (physical) contact with (or touches) the substrate after having performed said mixing step, and before performing said step of plasma exposure (or plasma activation, or plasma treatment) .
• the substrate is not coated by the precursor (s) during said mixing step (or by performing said mixing step) .
• the mixing step is performed for (physically) "bringing together" the precursor (s) and the substrate in a recipient or a reactor, without (chemical) reaction between said precursor (s) and said substrate, or without coating said substrate by said precursor (s) .
• the mixing step is performed at ambient temperature.
• the mixing step is performed at atmospheric pressure .
• the mixing step is performed by any mixing process known in the art, more particularly, by sonication (using an ultrasonic bath) , by stirring, or by contacting the precursor with the substrate .
• the step of introducing said mixture into said reactor, or the step of introducing said precursor and said substrate to be mixed into said reactor is performed at atmospheric pressure.
• the step of introducing said mixture into said reactor, or the step of introducing said precursor and said substrate to be mixed into said reactor is performed using a chemical dish comprising said mixture, or comprising said precursor and said substrate to be mixed, said chemical dish being placed into the reactor through the introduction chamber, or directly through the window in the plasma reactor .
• a low pressure of (about) 10E-2 mbar or less is formed .
• a “liquid precursor” refers to a precursor being present in a liquid phase (or state, or form) . In other words, no solid particles of said precursor are present.
• a “solid precursor” refers to solid particles of said precursor, or solid particles of said precursor being dissolved in a solvent (of e.g. isopropanol) forming a solution of solid particles in a solvent (in other words, solid particles of said precursor are present in solution) .
• nanoparticles are (simultaneously) formed (or created) and deposited on (or onto) said substrate during said (one) step of plasma exposure, as a result of precursor decomposition during said step of plasma exposure.
• nanoparticles are (simultaneously) formed (or created) and deposited on (or onto) the substrate during the decomposition of the (microsized) precursor, due to chemical reactions which occur in an electric discharge (or plasma) .
• the nanoparticles are formed (or produced) by (or as a result of) the decomposition of the (microsized) precursor ( s ) , and said nanoparticles are deposited (and attached (or grown) ) on the substrate.
• the (simultaneously created and) deposited nanoparticles (or nanoclusters ) do not agglomerate on the substrate or do not form a continuous film (or layer or coating) on the substrate.
• no agglomeration of nanoparticles (or nanoclusters) or no continuous film (of (agglomerated) nanoparticles or nanoclusters) is formed (or deposited) on the substrate.
• nanocluster refers to a group of atoms (i.e. molecules) .
• the diameter of the (simultaneously created and) deposited nanoparticles can be smaller than (about) 1 ⁇ .
• the diameter of the (simultaneously created and) deposited nanoparticles is comprised between (about) 1 nm and (about) 100 nm, preferably between (about) 1 nm and (about) 30 nm, more preferably between (about) 1 nm and (about) 10 nm.
• the diameter of the (simultaneously created and) deposited nanoclusters is comprised between (about) 1 nm and (about) 30 nm, preferably between (about) 1 nm and (about) 10 nm.
• the (simultaneously created and deposited) nanoparticles comprise (or consist of) metal nanoparticles, or metal oxide nanoparticles.
• the (simultaneously created and) deposited nanoparticles comprise (or consist of) monometallic nanoparticles, bimetallic nanoparticles, or trimetallic nanoparticle ( s ) .
• said substrate comprises (or consists of) microscopic particles (or micropowders ) , nanoscopicparticles (or nanopowders ) , or flat substrates.
• substrate refers to (a surface of) a support.
• the substrate comprises (or consists of) carbon (nano) fibers, carbon nanotubes or inorganic nanotubes, carbon nanorods or inorganic nanorods, metal or polymer micropowders , metal or polymer nanopowders, or porous substrates .
• nanopowder refers to a powder with size of the particles of said powder being less than (about) ⁇ .
• the inorganic nanotubes comprise (or consist of) metal oxides, Tungsten disulfide (WS 2 ) , Boron nitride (BN) , Silicon (Si), Molybdenum disulfide (M0S 2 ) , Copper (Cu) , or Bismuth (Bi) .
• said metal oxides comprise (or consist of) Vanadium pentoxide (V 2 O 5 ) , Vanadium dioxide (VO2) , manganese dioxide ( ⁇ ⁇ ⁇ 2) , or titanium dioxide (T1O2) .
• the carbon nanotubes comprise (or consist of) single-wall carbon nanotubes (SWCNTs), or multi-wall carbon nanotubes (MWCNTs) (i.e. either powders or nanotubes grown on solid substrates) .
• SWCNTs single-wall carbon nanotubes
• MWCNTs multi-wall carbon nanotubes
• the carbon nanotubes comprise (or consist of) closed-ended CNTs (or closed-end CNTs) .
• nanoparticles are (simultaneously formed and) deposited onto (the external walls of) said carbon nanotubes to form (or for forming) (nano ) hybrids .
• the carbon nanotubes comprise (or consist of) carbon nanotubes of various size (in diameter, and/or in length) .
• the outer diameter of the single-wall carbon nanotubes is lower than (about) 5 nm.
• the outer diameter of the multi-wall carbon nanotubes is comprised between (about) 2 nm and (about) 200 nm.
• the inner diameter of the multi-wall carbon nanotubes is comprised between (about) 1 nm and (about) 50 nm.
• the length of the single-wall carbon nanotubes is comprised between (about) 1 ⁇ and (about) 10cm, more preferably between (about) 1 ⁇ and (about) 30 ⁇ .
• the length of the multi-wall carbon nanotubes is comprised between (about) 1 ⁇ and (about) 10cm, more preferably between (about) ⁇ and (about) 50 ⁇ .
• the outer diameter of the carbon (nano) fibers is comprised between (about) 10 nm and (about) 100 ⁇ .
• the length of carbon (nano) fibers is comprised between (about) 1 ⁇ and (about) 1 m. More preferably, between (about) 10 ⁇ and (about) 500 ⁇ .
• said carbon nanotubes or said carbon (nano) fibers comprise (or consist) of graphite.
• the micropowders comprise (or consist of) silicon carbide (SiC), silicon dioxide (S1O 2 ), tungsten carbide (WC) , gold (Au) , eudragit, polycaprolactone, or polystyrene (PS) micropowders.
• the nanopowders comprise (or consist of) silicon carbide (SiC), silicon dioxide (S1O 2 ), tungsten carbide (WC) , gold (Au) , eudragit, polycaprolactone, or polystyrene (PS) nanopowders.
• SiC silicon carbide
• S1O 2 silicon dioxide
• WC tungsten carbide
• Au gold
• eudragit eudragit
• polycaprolactone polystyrene
• PS polystyrene
• the diameter of WC is comprised between (about) 0.1 ⁇ and ⁇ .
• the diameter of PS powders is comprised between (about) lOnm and (about) 30 ⁇ .
• the diameter of PS nanopowders is comprised between (about) lOnm and (about) 500nm.
• a porous substrate refers to a substrate with high porosity (i.e. a porosity of (about) 50% or higher) , or with a continuous network of voids.
• a porous substrate can be flat.
• the porous substrate is selected from the group consisting of microporous material, mesoporous material, or macroporous material.
• the porous substrate comprises (or consists of) clay, nanoporous aluminum powder, porous ceramic powder, or zeolites .
• the porosity of said porous substrate is (about) 50% or higher.
• the porosity of clay is (about) 60%.
• the size of clay is comprised between (about) 50 nm and (about) 5 ⁇ .
• a flat substrate refers to a layer, a sheet, or plate of substrate (or in other words, a flat substrate is not a powder substrate) .
• the flat substrate comprises (or consists of) Highly Ordered (or oriented) Pyrolytic Graphite (HOPG) , graphene (i.e. a single layer or sheet of graphite), flat glass, stainless steel, silicon layers provided with films (or coatings) on the surface of said layers, metal sheets, or polymer sheets.
• HOPG Highly Ordered
• graphite is composed of graphene layers.
• said metal sheets can comprise (or consist of) any metal sheet known in the art, more particularly, said metal sheets comprise (or consist of) an aluminum sheet, a copper sheet, a (stainless) steel sheet, a carbon steel perforated sheet, a brass sheet, or a titanium sheet.
• said polymer sheets can comprise (or consist of) any polymer sheet known in the art, more particularly, said polymer sheets comprise (or consist of) a Polyvinyl chloride (PVC) sheet, a BOPP film (Biaxial-oriented Polypropylene film) , or an acrylic polymer sheet.
• PVC Polyvinyl chloride
• BOPP film Biaxial-oriented Polypropylene film
• the flat substrate comprises (or consists of) Highly Ordered (or oriented) Pyrolytic Graphite (HOPG) , or graphene .
• HOPG Highly Ordered (or oriented) Pyrolytic Graphite
• said “precursor” refers to (microsize) molecules (or precursors) for producing (or forming) nanoparticles .
• said molecules (or precursors) act as a source for producing (or forming) nanoparticles (i.e. nanoparticles are formed as a result of precursor decomposition during the step of plasma exposure) .
• said nanoparticles are (simultaneously) formed and deposited on the substrate during the (one) step of plasma exposure (as a result of precursor decomposition during said step of plasma exposure) .
• said precursor comprises (or consists of) an organometallic compound (or an organometallic precursor, or an organometallic) .
• said precursor has microsize dimensions (or in other words, said precursor has no nanosize dimensions) .
• said organometallic precursor comprises (or consists of) nickel (II) acetylacetonate (Ni (C5H7O2) 2) , bis (methylcyclopentadienyl ) nickel (II) (C 12 H 14 N1), palladium acetylacetonate (Pd (C 5 H 7 O 2 ) 2 ) , palladium (II) propionate ( , rhodium (III) acetylacetonate (Rh (C5H7O2) 3) , ruthenium acetylacetonate, iron acetylacetonate, e t hyny 1 f e r r o c ene (Ci 2 Hi 0 Fe), silver acetylacetonate, zinc acetylacetonate, titanium oxy acetylacetonate, bis (2, 4-cyclopentadien-l
• said organometallic precursor comprises (or consists of) nickel (II) acetylacetonate (Ni (C5H7O2) 2) , bis (methylcyclopentadienyl ) nickel (II) (C 12 H 14 N1), palladium acetylacetonate (Pd (C 5 H 7 O 2 ) 2 ) , palladium (II) propionate (C 6 Hi 0 O 4 Pd) , rhodium (III) acetylacetonate (Rh (C 5 H 7 0 2 ) 3) , ruthenium acetylacetonate, iron acetylacetonate, ethynylferrocene (Ci 2 Hi 0 Fe) , silver acetylacetonate, zinc acetylacetonate, titanium oxy acetylacetonate, bis (2,4- cyclopentadien
• said organometallic precursor comprises (or consists of) metal acetylacetonates .
• said metal acetylacetonates comprise (or consist of) nickel (II) acetylacetonate (Ni (C5H 7 C>2) 2) , palladium acetylacetonate (Pd (CsH 7 02) 2) , rhodium (III) acetylacetonate (Rh (CsH 7 02) 3) , ruthenium acetylacetonate, iron acetylacetonate, silver acetylacetonate, zinc acetylacetonate, titanium oxy acetylacetonate, or any combination of two (or more) thereof .
• two or more organometallic precursors can be combined.
• organometallic precursors can be combined, or three organometallic precursors can be combined .
• bimetallic nanoparticles are deposited on the substrate.
• bimetallic nanoparticles are deposited on SWCNTs or MWCNTs, in case the substrate comprises (or consists of) SW or MW carbon nanotubes.
• a suitable (combination of) (OM) precursor (s) for use in a method according to the invention depends on the substrate, the (nano ) hybrids to be prepared, and/or the use (or type of application) of said prepared (nano ) hybrids .
• the method according to the invention is performed at (very) low temperature.
• the method according to the invention is performed at a temperature lower than (about) 300°C, even more preferably lower than (about) 200°C, and most preferably comprised between (about) 50 °C and (about) 150 °C.
• the plasma (or electric discharge) used (or applied) in a method of the invention can be any plasma (or electric discharge) known in the art, more particularly, Radio-Frequency (RF) glow discharge plasmas, Direct Current (DC) glow discharge plasmas, Dielectric Barrier Discharge (DBD) plasmas, atmospheric Plasma Jet, microwave discharge plasmas, Inductively Coupled RF Plasmas (ICP RF) , Capacitively Coupled RF Plasmas (CCP RF) , hollow cathode glow discharge plasmas, pulsed glow discharge plasmas, or electron cyclotron resonance discharge plasmas can be used.
• RF Radio-Frequency
• DC Direct Current
• DBD Dielectric Barrier Discharge
• ICP RF Inductively Coupled RF Plasmas
• CCP RF Capacitively Coupled RF Plasmas
• hollow cathode glow discharge plasmas pulsed glow discharge plasmas
• pulsed glow discharge plasmas or electron cyclotron resonance discharge plasmas
• the plasma used (or applied) is a Radio-Frequency (RF) glow discharge plasma, a Dielectric Barrier Discharge (DBD) plasma, or an atmospheric Plasma Jet.
• RF Radio-Frequency
• DBD Dielectric Barrier Discharge
• the plasma gas used (or applied) in a method according to the invention can be any plasma gas known in the art .
• the plasma gas used (or applied) in a method according to the invention comprises (or consists of) Argon (Ar) , Helium (He) , Oxygen (O 2 ) , Nitrogen (N 2 ) , Hydrogen (3 ⁇ 4) , Xenon (Xe) , and/or carbontetrafluoride (or tetrafluoromethane ) (CF 4 ) .
• the He (comprising) plasma gas can further comprise air.
• a suitable plasma gas for use in a method according to the invention depends on the (nano ) hybrids to be prepared.
• Finding (or selecting) a suitable plasma gas for use in a method according to the present invention is well within the practice of those skilled in the art .
• a suitable gas flow for preparing (or for forming) the plasma according to a method of the invention depends on the experimental conditions (or set-up configuration) .
• Finding (or selecting) a suitable gas flow for use in a method according to the present invention is well within the practice of those skilled in the art.
• the upper temperature limit (or the maximum temperature) of the applied plasma during the step of exposing (or subjecting) said mixture of said precursor and said substrate to a plasma depends on (or is determined by) the melting temperature of the substrate (or the degradation of the substrate) .
• the lower plasma power limit (or the minimum plasma power) of the applied plasma during the step of exposing (or subjecting) said mixture of said precursor and said substrate to a plasma depends on (or is determined by) the stability of the applied plasma.
• Suitable plasma temperatures for use in the method of the invention will be apparent to those skilled in the art.
• a suitable combination of plasma power, gas flow, pressure of the plasma gas (or partial pressure of plasma gases in case a mixture of gases is used to provide the plasma) , and (type of) plasma gas for use in a method according to the present invention is a combination of plasma power, gas flow, pressure of the plasma gas (or partial pressure of plasma gases in case a mixture of gases is used to provide the plasma) , and (type of) plasma gas being sufficient for decomposing (or degrading, or melting) of the organometallic precursor ( s ) and for (simultaneously) forming and depositing the nanoparticles on the substrate.
• the (lower) plasma power during the step of exposing (or subjecting) said mixture of said precursor and said substrate to a plasma is comprised between (about) 15 W and (about) 200 W, more preferably between (about) 100 W and (about) 200 W.
• the time (or duration) of the plasma exposure is sufficient for (simultaneously) decomposing (or degrading) the organometallic precursor (s) for forming the nanoparticles) and for depositing the (formed) nanoparticles onto the substrate.
• Suitable time (or duration) of the plasma exposure for use in the method of the invention will be apparent to those skilled in the art.
• the pressure in the reactor during the step of exposing (or subjecting) said mixture of said precursor and said substrate to a plasma is comprised between a low pressure and atmospheric pressure.
• the pressure in the plasma (in the reactor) during the step of exposing (or subjecting) said mixture of said precursor and said substrate to a plasma is comprised between (about) 10 Pa and (about) 102000 Pa.
• the frequency of the discharge is comprised between (about) 1 kHz and (about) 20 GHz.
• an organic solvent is added during said mixing step .
• one organic solvent is added during said mixing step.
• one organic solvent is added during said mixing step when combining two precursors .
• two different (types of) organic solvents can be added during said mixing step when combining two precursors in a method of the invention.
• said organic solvent is added to (or mixed with) the organometallic precursor (thereby obtaining a liquid organometallic solution), after which the substrate is added to said solution.
• said organic solvent is added to (or mixed with) the substrate (thereby obtaining a liquid solution) , after which the organometallic precursor is added to said solution.
• the organic solvent depends on (or is determined by) the (OM) precursor.
• the organic solvent comprises (or consists of) n-hexane, ethanol, or isopropanol.
• the mixture of said precursor and said substrate is heated before performing the step of plasma treatment.
• the step of heating said mixture is performed before or after the step of introducing said mixture into the reactor.
• the temperature of the heating of the mixture of said precursor and said substrate depends on (or is determined by) the melting temperature of the organometallic precursor (or the degradation (or decomposition) of the organometallic precursor) .
• the temperature of the heating of the mixture of said precursor and said substrate is lower than or equal to the melting temperature of the organometallic precursor (or the degradation (or decomposition) of the organometallic precursor) .
• the temperature of the heating of the mixture of said precursor and said substrate is lower than the melting point of the substrate (or is chosen to avoid melting, or (significantly) damaging (or degradation, or decomposition) of the substrate) .
• said heating is performed by any type of heating known in the art, more preferably using a heating technique under inert atmosphere, or under air atmosphere and atmospheric pressure, or by using a hot plate.
• Suitable temperatures for heating the mixture of said precursor and said substrate for use in the method of the invention will be apparent to those skilled in the art.
• said heating of said mixture is performed at a temperature lower than (about) 300°C, more preferably lower than (about) 200°C, and most preferably comprised between (about) 50°C and (about) 150°C.
• the duration (or the time) of said heating of said mixture depends on the heating device used for performing said heating .
• the duration (or the time) of said heating of said mixture is comprised between (about) 10 minutes and (about) 120 minutes.
• the present invention is directed to nanostructures (or nanohybrids ) , wherein said nanostructures (or nanohybrids) have different properties (e.g. size, abundance, oxidation state, etc.) when compared with those known in the art.
• the present invention is related to nanostructures (or nanohybrids) obtainable by a method according to the present invention.
• the nanostructures (or nanohybrids) (obtainable by a method) of the present invention may find particular use for various industrial applications.
• nanohybrids of NPs on CNTs can be employed in e.g. composites, catalysis for a variety of reactions, semiconductor devices, xerography, substrates for Surface Enhanced Raman Spectroscopy, or as gas sensors due to the CNT large surface area.
• nanohybrids of NPs on CNTs can be employed in optical electronics, or as electrocatalyst , proton exchange membrane fuel cells (PEMFC) , photovoltaics , UV lasers, light-emitting diodes, or, due to their high emission performance, in X-ray tubes, flat panel displays, or vacuum gauges.
• nanohybrids of bimetallic NPs on CNTs can be employed in methanol fuel cell applications, in hydrogenation of anthracene, as engineering catalysts (e.g. in pollution control, or alcohol oxidation), or as electrodes for hydrogen electro absorption.
• Decorated clay (with NPs) can be employed in catalysis (e.g. in oxidation of benzene), or in hydrogenation of alkenes and alkynes.
• Decorated polystyrene NPs can be employed as substrates for Surface Enhanced Raman Spectroscopy, in calibration of various measuring instruments and techniques, or in various immunoassays on medical diagnostic tests.
• SiC nanopowder decorated with (Ni) NPs improves hydrogen absorption and/or desorption kinetics.
• Pd0/Si0 2 nanopowders are used for visible-light- activated photocatalysis using different bacterial indicators .
• the present invention is related to the use of a method according to the present invention for the manufacture of nanostructures (or nanohybrids) .
• Figure 1 shows an example of an inductively coupled radio-frequency (RF) plasma (1) quartz reactor, (2) inox vacuum chamber, (3) primary pump, (4) turbo pump, (5) mass-flow controller, (6) needle valve for monomers (not used in this work), (7) Baratron gauge, (8) Advenced Energy RFX-600 RF generator (13.56 MHz), (9) ENI Power Systems Matchwork matching unit, (10) atmosphere release valve.
• RF radio-frequency
• FIG. 2 shows an example of a dielectric barrier discharge (DBD) reactor.
• a glass tube and two external electrodes of the reactor are used for the deposition of metal nanoparticles .
• FIG. 3 shows another example of a dielectric barrier discharge (DBD) reactor.
• DBD dielectric barrier discharge
• Figure 4 shows an example of an atmospheric plasma jet reactor.
• Figure 6a represents XPS wide scan of Ni/CNTs prepared in plasma RF chamber.
• Figure 6b represents Ni2p XPS spectrum prepared in plasma RF chamber.
• Figure 7 represents Cls XPS core level spectra recorded on RF-oxygen plasma treated MWCNTs and the result of the fitting analysis. Dotted line stands for untreated MWCNTs .
• Figure 8a represents HRTEM image of PdRh/MWCNTs (nanocylTM MWCNTs) prepared in plasma RF.
• Figure 8b represents a TEM image of PdRh/MWCNTs (SES ( SESResearch) MWCNTs) prepared in plasma RF chamber.
• Figure 9 represents an XPS wide scan spectrum of PdRh/MWCNTs prepared in plasma RF chamber.
• Figure 10a represents XRD patterns of Pd nanoparticles on CNTs (CNTsPd) .
• Figure 10b represents XRD patterns of Pd/Rh bimetals on CNTs (CNTsPdRh) .
• Figure 10c represents XRD patterns of Rh nanoparticles on CNTs (CNTsRh) .
• Figure 11 represents XRD patterns. The inset shows an enlargement of (111) reflection.
• Figure 12 Enlargement of the EDX spectrum of the individual bimetallic nanoparticle (TEM image shown in the inset) attached to the multiwall carbon nanotubes.
• Figure 13 represents a TEM images of Pt metal nanoparticles deposited on MWCNTs in DBD reactor a) in He plasma b) in He (95%) + 0 2 (5%) plasma.
• Figure 14 represents a TEM image of SiC nanopowder decorated by Pt nanoparticles using DBD discharge .
• Figure 15 represents a Pt/Si0 2 nanopowder prepared by DBD discharge.
• Figure 16 represents a TEM image of Pt nanoparticles on tungsten carbide nanopowder prepared in DBD reactor.
• Figure 17 represents a Field Emission Scanning Electron Microscope image of Rh/HOPG prepared by atmospheric plasma jet.
• Figure 18 represents a TEM image of clay decorated by palladium nanoparticles .
• Figure 19 represents a TEM image of polystyrene beads decorated by silver nanoparticles.
• Figure 20 represents a TEM image of graphene decorated by iron nanoparticles.
• the present invention provides a method for (simultaneously forming and) depositing nanoparticles on a substrate, wherein the method comprises the steps of:
• the temperature of the plasma during the step of exposing said mixture of said precursor and said substrate to a plasma is lower than (about) 300°C.
• the step of plasma exposure is performed at low temperature (i.e. with a plasma temperature being lower than (about) 300°C) .
• the step of plasma exposure is performed at a temperature lower than (about) 200 °C, and even more preferably comprised between (about) 50 °C and (about) 150 °C.
• the temperature is close to ambient temperature.
• Said substrate comprises (or consists of) microscopic particles (or micropowders ) , or nanoscopic particles (or nanopowders ) , or flat substrates.
• said substrate comprises (or consists of) carbon (nano) fibers, carbon nanotubes or inorganic nanotubes, carbon nanorods or inorganic nanorods, metal or polymer micropowders , metal or polymer nanopowders, or porous substrates.
• the substrate comprises (or consists of) carbon (nano) fibers, carbon nanotubes or inorganic nanotubes, metal or polymer micropowders, metal or polymer nanopowders, or porous substrates.
• the substrate comprises (or consists of) single-wall carbon nanotubes or multi-wall carbon nanotubes.
• the outer diameter of the single-wall carbon nanotubes is lower than 5 nm, and the outer diameter of the multi-wall carbon nanotubes is comprised between 2 nm and 200 nm.
• the inner diameter of the single-wall carbon nanotubes is 0.7 nm, and the inner diameter of the multi-wall carbon nanotubes is comprised between 1 nm and 50 nm.
• the length of the single-wall carbon nanotubes is comprised between 1 ⁇ and 30 ⁇ , and the length of the multi-wall carbon nanotubes is comprised between 1 ⁇ and 50 ⁇ .
• said nanopowders comprise (or consist of) silicon carbide, silicon dioxide, tungsten carbide, gold, eudragit, polycaprolactone, or polystyrene nanopowders.
• the diameter of SiC is comprised between 20 nm and 50 nm
• the diameter of WC is 0.4 ⁇
• the diameter of PS nanopowders is 0.1 ⁇ .
• the substrate is a porous substrate, such as clay, nanoporous aluminum powder, porous ceramic powder, or a zeolite.
• said porous substrate is clay, having a porosity of 60%, and a size comprised between 50 nm and 5 ⁇ .
• the substrate is a flat substrate, such as Highly Ordered (or Oriented) Pyrolytic Graphite (HOPG) , graphene, flat glass, stainless steel, a silicon layer provided with a film (or a coating) on the surface of said layer, a metal sheet, or a polymer sheet.
• HOPG Highly Ordered (or Oriented) Pyrolytic Graphite
• graphene graphene
• flat glass stainless steel
• silicon layer provided with a film (or a coating) on the surface of said layer
• a metal sheet or a polymer sheet.
• said flat substrate is HOPG, or graphene.
• said (microsize) precursor(s) act(s) as a source for producing nanoparticles .
• said nanoparticles are (simultaneously formed and) deposited on a substrate.
• said precursor comprises (or consists of) an organometallic compound .
• said organometallic precursor preferably comprises (or consists of) n i c ke l ( I I ) a c e t yl a c e t on a t e , b i s ( me t hy 1 c yc 1 op en t a di e ny 1 ) nickel (II) , palladium acetylacetonate, palladium (II) propionate, rhodium (III) acetylacetonate, ruthenium acetylacetonate, iron acetylacetonate, ethynylferrocene, silver acetylacetonate, zinc acetylacetonate, titanium oxy acetylacetonate, bis (2, 4-cyclopentadien-l-yl ) [ ( 4-methylbicyclo
• said organometallic precursor has microsize dimensions.
• said organometallic precursor comprises (or consists of) metal acetylacetonates , said metal being preferably nickel, palladium, rhodium, ruthenium, iron, silver, zinc, or titanium.
• two organometallic precursors can be combined, depositing bimetallic nanoparticles on a substrate.
• three organometallic precursors can be combined, depositing trimetallic nanoparticles on a substrate.
• said mixing step can be performed by any mixing process known in the art, more particularly, by sonication (using an ultrasonic bath) , by stirring, or by contacting the precursor with the substrate, at ambient temperature, and at atmospheric pressure .
• the precursor and the substrate do not react with each other during said mixing step.
• the precursor and the substrate do not undergo any changes during said mixing step .
• the precursor (s) is (are) (only) in (physical) contact with the substrate after having performed said mixing step, and before performing said step of plasma exposure.
• the substrate is not coated by the precursor (s) during said mixing step (or by performing said mixing step) .
• the mixing step is performed for (physically) "bringing together" the precursor (s) and the substrate in a recipient or a reactor, without (chemical) reaction between said precursor (s) and said substrate, or without coating said substrate by said precursor (s) .
• an organic solvent such as n-hexane, ethanol, or isopropanol, is added during said mixing step. Adding said organic solvent improves said mixing process.
• said organic solvent is added to the organometallic precursor, after which the substrate is added to said solution.
• said organic solvent is added to the substrate, after which the organometallic precursor is added to said solution .
• one organic solvent or two different (types of) organic solvents can be added during said mixing step.
• said mixing process is improved by dispersing a powder substrate such as a nanosized substrate in a solvent, such as n-hexane, prior to performing said mixing step .
• the mixture of said precursor and said substrate is heated before performing the step of plasma treatment.
• any type of heating known in the art can be used, such as a heating technique under inert atmosphere, under air atmosphere and atmospheric pressure, or by using a hot plate.
• Performing said heating step before performing the step of plasma treatment results in a more homogeneous distribution of deposited nanoparticles on the substrate, and/or further enhances (or further improves) the yield of the deposited nanoparticles on the substrate.
• a "homogeneous distribution" of the deposited nanoparticles refers to an even (or uniform) distribution (or deposition) of nanoparticles on the surface of the substrate.
• a homogeneous distribution is not a continuous film.
• the step of heating said mixture is performed before or after the step of introducing said mixture into the reactor.
• the temperature of the heating of said mixture is lower than or equal to the melting temperature of the organometallic precursor.
• the temperature of the heating of said mixture is lower than the melting point of the substrate .
• said heating of said mixture is performed at a temperature lower than 300°C, more preferably lower than 200°C, and most preferably comprised between 50°C and 150°C.
• the duration of said heating of said mixture is comprised between 10 minutes and 120 minutes.
• an organic solvent is added during the mixing step, and the mixture of said precursor, said substrate, and said organic solvent is heated before performing the step of plasma treatment.
• the step of introducing said mixture into said reactor, or the step of introducing said precursor and said substrate to be mixed into said reactor is performed using a chemical dish comprising said mixture, or comprising said precursor and said substrate to be mixed, said chemical dish being placed into the reactor through the introduction chamber, or directly through the window in the plasma reactor .
• the step of introducing said precursor and said substrate to be mixed into said reactor is performed by spreading said precursor and said substrate into the glass tube of the treatment module (or reactor) to form a bed with uniform thickness (figure 2) .
• the step of introducing said precursor and said substrate to be mixed into said reactor is performed by solubilising the precursor in an organic solvent, such as isopropanol, and spraying it between the substrate and the plasma torch (figure 4), or by drop deposition directly on the surface (figure 3) .
• an organic solvent such as isopropanol
• the step of introducing said mixture into the reactor, or the step of introducing said precursor and said substrate to be mixed into the reactor and subsequently forming said mixture inside said reactor can be performed at atmospheric pressure, after which said reactor can be pumped down for forming a low pressure in the reactor, such as a pressure of 10E-2 mbar or less.
• the pressure in said reactor can be kept at atmospheric pressure.
• performing said step of plasma exposure results in forming the nanoparticles (by the decomposition of said (microsize) precursor ( s ) ) and depositing said nanoparticles on the substrate, thereby forming (nano ) hybrids .
• the applied plasma gas comprises (or consists of) Argon, Helium, Oxygen, Nitrogen, Hydrogen, Xenon, and/or carbon tetrafluoride .
• the Helium comprising plasma gas can further comprise air.
• the gas flow for preparing the plasma is comprised between 5 slm and 20 slm.
• the plasma is provided by a mixture comprising (or consisting of) Ar gas and O 2 gas, for (further) increasing the nanocluster distribution over the substrate (increasing the number (or yield) of deposited nanoparticles and improving their homogeneous distribution) .
• the amount of said O 2 gas is maximum 10% (v/v) of the total volume of the gas mixture, to avoid (or for avoiding) plasma quenching.
• the plasma is provided by a mixture comprising (or consisting of) He gas and O 2 gas, for (further) increasing the nanocluster distribution over the substrate (increasing the number (or yield) of deposited nanoparticles and improving their homogeneous distribution) .
• the amount of said O 2 gas is maximum 10% (v/v) of the total volume of the gas mixture, to avoid (or for avoiding) plasma quenching.
• the plasma power during the step of plasma exposure is comprised between 15 W and 200 W, more preferably between (about) 100 W and (about) 200 W.
• the pressure in the reactor during the step of plasma exposure is comprised between a low pressure and atmospheric pressure.
• the pressure in the plasma (in the reactor) during the step of plasma exposure is comprised between (about) 10 Pa and (about) 102000 Pa.
• the frequency of the discharge is comprised between 1 kHz and 20 GHz.
• the diameter of the deposited nanoparticles can be smaller than (about) 1 ⁇ .
• the diameter of the deposited nanoparticles can be comprised between 1 nm and 100 nm, more preferably between 1 nm and 30 nm, and even more preferably between 1 nm and 10 nm.
• the deposited nanoparticles can comprise (or consist of) monometallic nanoparticles, bimetallic nanoparticles, or trimetallic nanoparticles.
• the deposited nanoparticles comprise (or consist of) metal nanoparticles, or metal oxide nanoparticles.
• the metal oxide nanoparticles comprise (or consist of) partially oxidized metal oxide nanoparticles, or fully oxidized metal oxide nanoparticles.
• the method is performed at low temperature, more particularly, the temperature is close to ambient temperature .
• the method is preferably performed at a temperature lower than 300°C, even more preferably lower than 200°C, and most preferably comprised between 50 °C and (about) 150 °C.
• a preferred embodiment of the invention comprises as a first step preparing a mixture of organometallic precursors and CNTs.
• said mixing step is performed by sonication.
• the duration of said sonication is comprised between 5 minutes and 10 minutes.
• an organic solvent such as n-hexane, ethanol, or isopropanol, is added during said mixing step.
• the mixture of said precursor and said substrate (and/or said organic solvent) is heated before performing the step of plasma treatment.
• Said heating of said mixture is performed at a temperature lower than 300°C, more preferably lower than 200°C, and most preferably comprised between 50°C and 150°C.
• the duration of said heating of said mixture is comprised between 10 minutes and 120 minutes.
• said organometallic precursors comprise (or consist of) metal acetylacetonates , said metal being preferably nickel, palladium, rhodium, ruthenium, iron, silver, zinc, or titanium.
• Said preferred embodiment comprises as a second step exposing said mixture to a plasma, such as an oxygen, argon, or helium comprising plasma.
• a plasma such as an oxygen, argon, or helium comprising plasma.
• the gas flow for preparing the plasma is comprised between 5 slm and 20 slm.
• the power of said plasma is comprised between 10 W and 200 W.
• the duration of said plasma treatment is comprised between 5 minutes to 30 minutes .
• said plasma treatment is performed at a temperature lower than 300°C, preferably lower than 200°C, and more preferably comprised between 50 °C and 150 °C.
• a method of the invention can be used for improving the deposition of nanoparticles on microscopic and nanoscopic substrates, when compared to processes known in the art.
• a method of the invention is a simplified method, involving fewer steps, when compared to existing methods in prior art.
• carrying out a method of the invention avoids the use of a gas-comprising precursor flow, and the injection of the precursors into the plasma.
• Example 1 Nickel nanoparticles on MWCNTs
• XPS wide scan spectra analysis (figure 6a) of the prepared powder shows that Ni content is about 2 % (with carbon 79 % and oxygen up to 19 % due to the O2 plasma treatment) .
• main peak at 856.1 eV can be assigned to N1 2 O 3 and it is followed by two satellites.
• Small peak observed at 853.3 eV is hardly to assign, it can be either NiO or N13C.
• Preparation of the liquid OM platinum solution includes the mixing of lg of (1,5- Cyclooctadiene ) dimethyl platinum (II) (CH 3 ) 2 Pt (C 8 Hi 2 ) with 10 ml of n-hexane . The resulting solution is then sonicated for 5 minutes at 30°C [0310] 20 mg of MWCNTs were mixed with the desired volume of the OM. The ensemble is then spread into the glass tube of the treatment module to form a bed with uniform thickness.
• the discharge characteristics are as follows (i) the frequency is adjusted at 20 kHz. (ii) the plasma power should be between 100 and 200 W. (iii) Ar or He gas have been tested. The admixture of small amount of oxygen into the plasma gas, leads to the increasing of the nanoclusters distribution over the nanopowder (increasing the number (or yield) of deposited nanoparticles and improving their homogeneous distribution) . A maximum of 5% oxygen (in 95% He) can be used. Further increasing of the oxygen partial pressure leads to the plasma quenching, (iv) the gas flow is fixed at 5 slm; above 10 slm the nanopowders are blown into the exhaust line.
• CNTs are damaged in the case of treatment duration longer than 10 minutes.
• the optimal treatment time was found to be 5 minutes, (v) the OM/CNTs ratio: the amount of nanopowders is kept constant (20 mg) , the quantity of precursor is varied (from 0.25 to 1 ml for the liquid OM) .
• DBD discharge reactor ( Figure 2) described in more details in previous example was used to decorate SiC, S1O 2 , WC using (CH 3 ) 2 Pt (CsH ⁇ ) in solid or liquid form keeping the same experimental conditions as in the example 3.
• SiC substrate 2-3 nm metal platinum NPs homogeneously distributed over the substrate were found ( igure 14 ) .
• Tungsten carbide (WC) nanopowder which is widely used in material research and catalysis, was tested as well as the substrate for the DBD decoration by Pt nanoparticles.
• Pt nanoparticles evidence of agglomerated Pt metal oxide nanoparticles can be seen from figure 16, which can be due to the larger size of the substrate (-400 nm) .
• Rhodium nanoparticles on HOPG Rhodium nanoparticles on HOPG
• Atmospheric plasma jet reactor ( Figure 4) generates electric discharge with an AtomfloTM-250 plasma source from Surfx Technologies LLC. This method has been already used to deposit gold clusters onto HOPG surfaces [F. Demoisson et al, Surface and Interface Analysis, 40, 566-570, 2008.] as well as to deposit Au , Pt, Rh nanoparticles onto MWCNTs.
• the plasma activation and the deposition processes using colloidal solution are described in [F. Reniers et al, PCT/EP2008/060676] .
• the resulting nanomaterials were plunged into the ethanol solution for up to 5 min and were submitted to ultrasonication before characterisation.
• the sample quality was ZYB grade characterized by a mosaic spread angle of 0.8° ⁇ 0.2° and the lateral grain size up to 1 mm.
• the size was 10 mm x 10 mm x 1 mm.
• the fresh surface of HOPG was obtained before each experiment by first pealing off few layers with an adhesive tape and then by soaking the surface in an ethanol solution for up to 5 min.
• Described invention was employed to decorate polystyrene latex beads nanoparticles (diameter of 100 nm) as well. This time silver acetylacetonate was used as a precursor for silver nanoparticles. As in the previous example (example 6) RF plasma was the main driven force to prepare nanohybrids using the same experimental process. 90 mg of Ag(acac) is diluted in 5 ml of isopropanol and sonicated for 20 minutes in ultrasonic bath. However this time the substrate is already in undefined solvent, so 300 microl ( ⁇ ) of the polystyrene beads solution is admixed into the precursor followed by 20 minutes of ultrasonic treatment.
• Nanohybrids of few-layered graphene decorated by iron nanoparticles were prepared by RF discharge at low pressure.
• STXM(NEXAFS) analysis confirmed the presence of iron on graphene sheets (figure 20) .

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