[go: up one dir, main page]

WO2013016841A1 - Nanoparticules - Google Patents

Nanoparticules Download PDF

Info

Publication number
WO2013016841A1
WO2013016841A1 PCT/CN2011/001251 CN2011001251W WO2013016841A1 WO 2013016841 A1 WO2013016841 A1 WO 2013016841A1 CN 2011001251 W CN2011001251 W CN 2011001251W WO 2013016841 A1 WO2013016841 A1 WO 2013016841A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
particle
confinement space
confined
component
Prior art date
Application number
PCT/CN2011/001251
Other languages
English (en)
Inventor
Xinhe Bao
Zhiqiang Yang
Xiulian Pan
Shujing GUO
Original Assignee
Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
Bp P.L.C.
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 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences, Bp P.L.C. filed Critical Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
Priority to PCT/CN2011/001251 priority Critical patent/WO2013016841A1/fr
Publication of WO2013016841A1 publication Critical patent/WO2013016841A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/062—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • 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
    • C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • compositions including nanoparticles relate to compositions including nanoparticles. Aspects of the invention relate to nanoparticles in a confined environment.
  • the nanoparticles are encapsulated inside nanostructures, for example fullerene nanostructures.
  • a confined environment is provided by carbon nanotubes (CNT).
  • Examples described herein relate to the use of confined nanoparticles in some applications. For example use of confined nanoparticles as a catalyst in chemical processes is described. Other uses and applications for the confined nanoparticles are also possible.
  • Carbon nanotubes are carbon materials having a generally cylindrical structure.
  • CNTs can be envisioned as being formed of rolled-up graphene layers which roll into a cylindrical structure forming well-defined tubes or channels.
  • the diameters of the CNT channels are typically of the order of 1 nm or less to about 100 nm.
  • These channels enable encapsulation of nanomaterials as described in "Probing the Electronic Effect of Carbon Nanotubes in Catalysis: NH 3 Synthesis with Ru Nanoparticles" S. Guo, X. Pan, H. Gao, Z. Yang, J. Zhao and X. Bao, Chem.-Eur. J , 2010, 16, 5379-5384 in which the investigation of confinement in the inside of the channels CNTs of a Ru-based ammonia synthesis catalyst is described.
  • composition comprising a component including at least one nano-sized confinement space, the composition further comprising at least one particle confined within the confinement space, the at least one particle comprising a metal nitride.
  • the particles are nano particles.
  • the particles have a size such that at least one dimension is not more than 100 nm, preferably not more than 50 nm, for example less than 20 nm.
  • the metal nitride comprises iron nitride.
  • the at least one particle comprises iron nitride.
  • the particles may have a different composition. The inventors have identified that confinement of the particles inside the nano-sized confinement spaces of the component can have benefits.
  • the confinement of the particles comprising iron nitride may stabilize a cubic phase of the iron nitride.
  • the confined particles may include cubic phase iron nitride.
  • the presence of the cubic phase may be beneficial in some applications.
  • the confinement of the particles inside the component may enable control or restriction of the particle size of the particles in the confinement space.
  • the performance of the catalytically active material may be improved by confinement of the particles in the component.
  • the particles are preferably retained within the confinement space, although they may or may not be bound within the space.
  • the particles may be free or partially free to move in the containment space.
  • the confinement space may be enclosed or partially enclosed.
  • the confinement space may be formed by a tube or channel.
  • the confinement space may have at least one dimension which is 100 nm or less, preferably between from 0.1 and 100 nm.
  • the confinement space may have at least two dimensions each being 100 nm or less, preferably between from 0.1 and 100 nm.
  • the confinement space may have three dimensions less than about 100 nm, for example between 0.1 and 100 nm.
  • the confinement space may be nano-sized in fewer than all dimensions.
  • the confinement space may comprise a nano-tube, or a nano-channel.
  • the component may be of any appropriate composition.
  • the component may comprise any material, structure or composition which includes one or more nano-sized formations which are suitable for confining a particle.
  • Such component includes, but not exclusively, materials having pores, or cage or shell structures in which openings are present in the structure, which openings are suitable for confining one or more particles.
  • the particles may be confined on fewer than all sides.
  • the confinement space may comprise a tube or channel.
  • the component may have any structure which includes openings or spaces suitable for confining a particle, for example the component may comprise a laminate material comprising a layer structure, confinement spaces being provided by spaces between the layers.
  • the component may for example include a zeolite or other molecular cage structure, or for example a clay or nano-porous material, or mesoporous material for example mesoporous silica and mesoporous carbon materials such as MCM-41, SBA-15, CMK-3.
  • a zeolite or other molecular cage structure or for example a clay or nano-porous material, or mesoporous material for example mesoporous silica and mesoporous carbon materials such as MCM-41, SBA-15, CMK-3.
  • a component being for example nano-sized
  • the dimensions of the component is for example not more than 100 nm , for example between from 0.1 nm and 100 nm.
  • the component may have more than one dimension being not more than 100 nm, for example between from 0.1 nm and 100 nm.
  • the component may include a nanostructure which contains the confinement space.
  • the component may comprise a nanostructure.
  • An aspect of the invention provides particles of a metal nitride, for example iron nitride, for example cubic phase iron nitride confined within a nanostructure. Aspects of the invention are applicable for other metal nitrides, for example cobalt or molybdenum nitrides.
  • the nanostructure may include any structure having one or more nano-sized spaces for containment of the particles.
  • the nanostructure may include a nanomesh, nanoshell, nanotube, nanosphere and/or nanocage or other similar structure.
  • the component may comprise a fullerene.
  • the component may comprise a material including a graphene structure.
  • the graphene structure may for example include spheres, balls, ellipsoids and/or tubes.
  • the component comprises a carbon nanotube.
  • the component comprises a carbon nanotubes and at least one particle is confined in a space in the nanotube.
  • an aspect of the invention provides a composition comprising carbon nanotubes, and particles confined in the nanotubes, wherein preferably the particles include metal nitride, for example iron nitride.
  • the carbon nanotubes (CNT) may be any appropriate type, for example single walled, double walled or multiwalled.
  • the fullerene may include substituents, modifiers, contaminants, and/or other components.
  • the graphene for example may have substituents, or modifications.
  • the component, for example the nanostructure may include endohedral or exohedral substituents or modifications.
  • the at least one particle confined in the space preferably has an average particle size not more than 50 nm, preferably not more than 20 ran.
  • the average particle size of the confined particles is not more than about
  • At least 90 number % of particles have a size less than 15 nm, for example less than 1 Onm.
  • composition may further include some particles outside of the confinement space. Preferably only a relatively small number of the particles are outside of
  • At least 50 number % of the particles, for example nanoparticles, of the composition are confined in one or more spaces of the component.
  • at least 70% of the particles, for example 80% or more of the particles, may be confined in spaces in the nanostructure.
  • compositions comprising a component including at least one nano-sized confinement space, the composition further comprising at least one particle confined within the confinement space, the at least one particle comprising a metal nitride, metal carbide or metal phosphide.
  • the particles comprise metal carbide and/or metal phosphide.
  • aspects of the invention may be applied to metal nitrides other than iron nitrides.
  • the component may include carbon nanotubes.
  • confinement of iron nitride particles can have particular benefits. For example, confinement of iron nitride inside CNTs may benefit stabilization of the cubic FeN phase of the nitride particles. As discussed further below, the inventors have also identified that confined particles may exhibit higher catalytic activity compared with non-confined particles. For example, CNT-confined nitride particles (for example iron nitride) may in some cases exhibit a higher activity in CO hydrogenation compared with nitride particles which are not confined, for example particles on the outer walls of CNTs. The confined nitride particles may also have improved activity compared with CNT-confined reduced iron catalyst. In examples described, cubic FeN nanoparticles were synthesized through
  • CNT carbon nanotube
  • compositions described herein may find application in a chemical process, and may for example be used as a catalyst.
  • Other applications are also envisaged, for example in relation to fuel cell and energy storage, for example lithium battery and supercapacitor technology.
  • compositions are comprised in a catalyst for CO hydrogenation.
  • the compositions may be comprised in other catalysts. For example they may be utilised in water gas shift catalysts (WGS).
  • WGS water gas shift catalysts
  • FTS Fischer-Tropsch synthesis
  • iron nitride transforms from fee y'-Fe 4 N to hep s-Fe x N (2 ⁇ x ⁇ 3) and to orthorhombic ⁇ - ⁇ 2 ⁇ .
  • These nitrides have been reported to have a significantly enhanced catalytic activity in FTS with respect to the reduced iron (see A A Hummel et al, J Catalysis, (1988) 1 13, 236-249).
  • the resistance to oxidation has been proposed to be responsible for their higher activity upon incorporation of nitrogen into the Fe lattice.
  • a cubic FeN phase with a higher nitrogen content of 50 at.% N was theoretically predicted and recently synthesized in the form of a thin film by reactive magnetron sputtering, molecular beam epitaxial growth and ion bombardment.
  • a further aspect of the invention provides a catalyst composition comprising a component including at least one nano-sized confinement space, the composition further comprising at least one particle confined within the confinement space, the at least one particle comprising a metal nitride.
  • the at least one particle may comprise an iron nitride.
  • the invention also provides a process for the hydrogenation of CO, comprising the steps of passing a feed stream over a catalyst, the catalyst comprising a composition as described herein.
  • the invention further provides a process for the hydrogenation of CO, the process including the step of passing a feed stream over a catalyst, the catalyst including a composition comprising a component including at least one nano-sized confinement space, the composition further comprising at least one particle confined within the confinement space, the at least one particle comprising a metal nitride.
  • composition may have further features as described herein in relation to other aspects of the invention.
  • the composition may include a metal nitride confined in a nanostructure, for example a carbon-based nanostructure, for example a fullerene. Without wishing to be bound by any particular theory, it is considered that interaction between the walls of the nanostructure and the particles may give improved catalytic properties.
  • the component may comprise carbon nanotubes.
  • the particle may comprise iron nitride, for example cubic- iron nitride.
  • At least 50% by number of particles of metal nitride may be confined in the component.
  • the invention also provides a method of producing a composition as defined herein.
  • the invention further provides a method of producing a confined metal nitride, the method including the steps of introducing a composition comprising the metal to a component including at least one nano-sized confinement space such that at least one particle including the metal is confined within the confinement space.
  • the method may further include the step of carrying out a nitriding treatment to form a metal nitride in the confinement space.
  • the introduced composition may for example include a metal oxide, metal chloride, metal acetate or metal complexes.
  • the introduced composition may include a metal salt.
  • the metal nitride formed may for example comprise iron nitride.
  • the metal nitride includes cubic- iron nitride.
  • cubic iron nitride is formed in the confinement space, for example during the nitriding treatment.
  • the confinement space may have at least one dimension 100 nm or less, preferably between from 0.1 and 100 nm.
  • the component may include a nanostructure including the confinement space.
  • the component may comprise a fullerene.
  • the component for example may comprise a carbon nanotube, wherein at least one particle is confined in the nanotube.
  • the introduction of the metal in to the component may be carried out at elevated temperature.
  • the nitriding treatment may include treatment using a source of nitrogen, for example ammonia or nitrogen.
  • the nitriding treatment may be carried out at elevated temperature.
  • the elevated temperature for the nitriding treatment may be at least 400 degrees C, for example at least 450 degrees C, for example 500 degrees C or more.
  • the nitriding step may include increasing the temperature at a first predetermined rate in a first heating period, and increasing the temperature at a second predetermined rate in a second heating period.
  • the first predetermined rate may be for example at least 5 degrees C per minute, for example at least 7 degrees C per minute.
  • the second predetermined rate may be for example at least 5 degrees C per minute, for example at least 7 degrees C per minute.
  • predetermined rate may be for example not more than 5 degrees C per minute, for example less than 2 degrees C per minute, for example 1 degree C per minute or less.
  • the temperature may be held at a predetermined elevated temperature.
  • the method may further include a pre-treatment of the component.
  • This pre- treatment may effect opening or partial opening of one or more confinement spaces in the component.
  • This pre-treatment may for example facilitate subsequent introduction of the particles into the confinement spaces.
  • the pretreatment may effect removal or partial removal of end caps on some or all of the carbon nanotubes to open ends of the nanotubes. This treatment may not be necessary in some cases.
  • the invention extends to compositions, products, methods, processes and/or apparatus substantially as herein described optionally with reference to one or more of the accompanying drawings.
  • composition aspects may be applied to method or process aspects, and vice versa.
  • Figures 1(a), 1(b), 1(c) and 1(d) show TEM images of (a) Fe x N-in-450; (b) Fe x N-in-500; (c) Fe x N-out-400; (d) Fe x N-out-500, respectively.
  • the insets in the TEM images show graphically the particle size distribution of Fe x N measured from over 260 particles;
  • Figures 2(a), 2(b), 2(c), and 2(d) show TEM images of CNT-supported iron nitride prepared at different nitridation temperatures, (a) Fe x N-in-350; (b) Fe x N-in-400; (c) Fe x N- out-350; (d) Fe x N-out-450;
  • Figures 3(a) and 3(b) show room temperature 57Fe Mossbauer spectra of (a) FexN-in-450 (top panel) and (b) FexN-out-400 (lower panel) with the dotted line representing the measured data while solid lines donate the fitted data.
  • Line Sum (S) is the sum of fitted lines;
  • Figure 4(a) shows XRD patterns of fresh FexN-in-500, used FexN-in-500 and used Fe-in catalysts (from bottom to top);
  • Figure 4(b) shows room temperature 57Fe Mossbauer spectra of used FexN-in-450 (top panel) and used FexN-out-400 (lower panel);
  • Figure 8 shows the room temperature 57 Fe Mossbauer spectra of 10% Fe x N/Si0 2 .
  • the following example describes the preparation of CNTs including iron nitride nanoparticles in the CNT channels (FeN-in). Then, an example of the use of FeN-in as a catalyst is described.
  • Multi-walled carbon nanotubes having an internal diameter of 4-8nm and external diameter of 10-20nm were obtained from Chengdu Organic Chemicals Co., Ltd China (MFG code M12020702R). For these nanotubes, it was found that there was a relatively high proportion of closed tipped CNTs (c-CNTs). Therefore, a treatment was carried out to open the tips in order to facilitate filling of nanoparticles inside.
  • the o-CNTs were first mixed with water. A weighted amount of Fe(N0 3 ) 3 .9H 2 0 was added to the mixture under stirring followed by ultrasonic treatment and simultaneous stirring for 4 h. Then the solvent was evaporated slowly under ambient conditions. Then the sample was heated at ramp of 0.2-4 °C to 140 °C and kept at this temperature for 6 h.
  • the Fe 2 0 3 -m was nitrided using a temperature-programmed reaction method in ammonia atmosphere.
  • First stage temperature raised from room temperature to 300°C at 7°C/min
  • Second stage temperature raised from to 300°C to the final temperature T at a rate of rC/min
  • the prepared nitride sample was then passivated at room temperature for 12 hours in a mixture of 1% 0 2 /N 2 (v/v).
  • the resulting product was labeled as Fe x N-z ?-T, where T represents the final nitridation temperature.
  • Fe x N-owt Samples of Fe x N-owt were prepared for comparison with Fe x N-m. Fe x N-owt included
  • the o-CNTs were mixed with water and sonicated for 90 min.
  • An ammonia water solution (1.7 wt% of NH 3 ) was added to the mixture under stirring.
  • the aqueous solution of Fe(N0 3 ) 3 .9H 2 0 was slowly introduced to the mixture under vigorous stirring, followed by sonication for 30 min. Afterwards, it was heated in a water bath at 70 °C until dried. It was then heat treated at 140 °C for 6 hours.
  • the resulting Fe 2 0 3 -owt was nitrided using a temperature-programmed reaction (TPR) method in ammonia atmosphere.
  • TPR temperature-programmed reaction
  • First stage temperature raised from room temperature to 300°C at 7°C/min
  • Second stage temperature raised from to 300°C to the final temperature T at a rate of l°C/min
  • the prepared nitride sample was then passivated at room temperature for 12 hours in a mixture of 1 % 0 2 /N 2 (v/v).
  • the resulting product was labeled as Fe x N-owt-T, where T represents the final nitridation temperature.
  • samples of CNTs including metallic Fe in the channels were prepared by reducing the CNT-confmed Fe 2 0 3 directly in H 2 for 6 h at 350 °C, by a method for example as described in Chen W et al, J. Am. Chem. Soc. 2008, 130, 9414- 9419. Analysis of Samples Produced
  • the locations of the Fe 2 0 3 particles in Fe 2 0 3 -w and Fe 2 0 3 -owt catalysts were confirmed with Transmission electron microscopy (TEM) by tilting the samples to different angles.
  • TEM Transmission electron microscopy
  • the TEM was carried out on an FEI Tecnai G microscope at an accelerating voltage of 120 kV.
  • the images taken at different tilt angles indicate that most of the Fe 2 0 3 nanoparticles of Fe 2 0 3 -w catalyst are located inside the channel of CNTs.
  • ICP-AES Inductively coupled plasma atomic emission spectrometry
  • Fe x N-m-450 was seen to have increased to about 4-10 nm (as shown in Figure 1(a) and further to 6-12 nm for Fe x N-m-500 (as shown in Figure 1(b).
  • the outside particles were seen to aggregate more severely due to absence of the space restriction provided by the CNT channels for the Fe x N-in samples.
  • the Fe x N-out particles were seen to retain a relatively spherical shape.
  • the particle size of Fe x N-owt-400 was seen to be about 8-15 nm and was seen to have increased to about 10-20 nm upon nitridation at 500 °C (Fe x N-out-500).
  • a new and broad peak around 20 36° was identified for samples subject to nitridation at or above 450°C from XRD. This peak may also be present at lower temperature, but it was difficult to distinguish from the peak for Fe 3 0 4 in this example.
  • Mossbauer spectroscopy was carried out. 57 Fe Mossbauer spectroscopy analysis was conducted on a Topologic 500A spectrometer with a proportional counter. 57 Co(Rh) was used as the radioactive source and the Doppler velocity of the spectrometer was calibrated with an a-Fe foil. The spectra were fitted with appropriate superpositions of Lorentzian lines using the Moss Winn 3.0i program.
  • the spectrum for Fe x N-w-450 is shown in Figure 3.
  • the spectrum of Figure 3 can be fitted with a singlet line (Fe-I) and a quadrupole doublet (Fe-II), similar to thin iron nitride films.
  • the Fe-I line is attributed to the ⁇ ''-FeN phase with a ZnS-type structure and the Fe-II doublet to ⁇ ''-FeN or ⁇ '''-FeN with vacancies.
  • ⁇ '''-FeN has a NaCl-type structure.
  • Fe x N-owt was considered to contain more ⁇ - ⁇ 2 ⁇ but less FeN species than for Fe x N- «.
  • CO hydrogenation was carried out in a fixed bed microreactor at 300 °C, 5 bar and a gas hourly space velocity (GHSV) of 15000 h "1 (based on the volume of syngas passed through per volume of the catalyst per hour).
  • GHSV gas hourly space velocity
  • a H 2 /CO/Ar mixture (47.5/47.4/5.1 vol.%, purity of 99.99%) was taken as the feeding gas with Ar as an internal standard.
  • lOOmg catalyst was loaded into the reactor and pre-treated in-situ for 2 h in syngas (1 bar) at 260 °C. All gas lines after the reactor were kept at 150 °C.
  • the effluents were analyzed by an online GC (Agilent 7890A), which was equipped with a thermal conductivity detector (TCD) and a flame ionization detector (FID).
  • TCD thermal conductivity detector
  • FID flame ionization detector
  • the activity of the catalyst was expressed as Iron-Time Yield (ITY, ⁇ ⁇ ⁇ 1(: ⁇ 8 ⁇ 1 ⁇ ' 1 ⁇ 6) ⁇
  • the ITY for Fe x N-w-500 in this case reached 927.8 ⁇ 1 ⁇ : ⁇ 3 ⁇ 1 ⁇ " 1 ⁇ , which is 1.4 times higher than for the outside catalyst Fe x N-o «t-500 (Table 1).
  • iron nitride (10wt% iron loading) supported on Si0 2 yields an activity of 75 ⁇ mol ys '1 -g ' 1 Fe (Table S3), which is significantly lower than that on Fe x N-m-500 and Fe x N-o «t-500.
  • Figure 8 shows the room temperature 57 Fe Mossbauer spectra of 10% Fe x N/Si0 2 . Nitridation was carried out in ammonia at 500 °C via the same temperature-programmed reaction method as CNTs supported iron nitride catalysts. The isomer shift (IS) is 0.33 mm/s, the quadrupole splitting (QS) is 0.44 mm/s and the iron species exist as £-Fe 2 iN in Fe x N/Si0 2 .
  • Table 1 also shows that the nitride catalysts are significantly more active than Fe-m.
  • the activities of both Fe x N-/ ' « and Fe x N-owt are 5-7 times higher in this example.
  • Fe x N catalysts exihibit higher C0 2 selectivities indicating higher activities of the nitrides than Fe-w but significantly lower than the K promoted iron catalyst for water gas shift reaction.
  • Iron carbides are generally accepted being a catalytically active phase for FTS.
  • Fe 3 0 4 which usually results from oxidation of iron and iron carbide by the product H 2 0, has frequently been blamed of for such catalyst deactivation.
  • XRD and Mossbauer spectroscopy in the present examples reveal that Fe x N catalysts do not exhibit significant oxide phase after reaction. Without wishing to be bound by any particular theory, the lower activity of Fe-in could be attributed to the instability of iron and iron carbide under CO hydrogenation conditions.
  • the Mossbauer spectra shown in Figure 4b and the corresponding fitting parameters in Table S2 suggest the presence of iron carbonitride (Fe 2 C x Ni -x ) (Fe-I), FeC x Ni -x (Fe-II) and ⁇ ''-FeN (Fe-III) on both Fe x N-w and Fe x N-owt catalysts during CO hydrogenation. This could be attributed to surface carbon forming from dissociative adsorbed CO which diffuses into the lattice of iron nitride and replaces some nitrogen atoms.
  • x-Fe 5 C 2 , 0-Fe 3 C and s-Fe 2 C have been reported to be present for reduced iron catalyst.
  • x-Fe 5 C 2 which was the main carbidic species under typical FTS condition was highly susceptible to oxidation during reaction.
  • 0-Fe 3 C which usually formed at high reaction temperature, showed a low activity and selectivity due to the carbonaceous deposits on the catalyst surface.
  • e-Fe 2 C was enthalpically most stable under typical FTS conditions, however kinetic and entropic factors may inhibit their formation in large amounts.
  • Figure 4b shows a higher concentration of FeC x Ni -x and lower content of Fe 2 C x N 1-x on Fe x N- «- 450 catalyst than those on Fe x N-owt-400. This implies that the confined catalyst has a stronger retention of nitrogen in the lattice than the outside nitride. Without wishing to be bound by any particular theory, this may be related to the higher FTS and WGS activity of Fe x N-/ ' « than Fe x N-ow/.
  • the CNT-confined FeN catalyst of the examples above exhibited an activity 1.4 times higher than the nitride particles located on the CNT exterior walls in CO
  • Cubic FeN particles of a few nanometer size have been synthesized by encapsulation inside carbon nanotube (CNT) channels.
  • CNT carbon nanotube
  • Such an FeN catalyst exhibits in some examples a 5-7 times higher activity than a reduced Fe catalyst and a Si0 2 supported iron nitride in CO hydrogenation.
  • the confined FeN catalyst is also more active than iron nitride particles dispersed on the CNT exterior walls in some examples.
  • the particle may comprise metal carbide and/or metal phosphide. This feature may be applied to any aspect of the invention as appropriate.
  • Each feature disclosed in the description, and (where appropriate) the claims and drawings may be provided independently or in any appropriate combination.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne une composition qui comprend un composant comprenant au moins un espace de confinement de taille nanométrique, et la composition comprend en outre au moins une particule confinée au sein de l'espace de confinement. Dans certains exemples, la particule comprend du nitrure de fer. La composition peut être utilisée dans un procédé d'hydrogénation du CO, le procédé comprenant l'étape consistant à faire passer un courant de charge sur un catalyseur comprenant la composition.
PCT/CN2011/001251 2011-08-01 2011-08-01 Nanoparticules WO2013016841A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2011/001251 WO2013016841A1 (fr) 2011-08-01 2011-08-01 Nanoparticules

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2011/001251 WO2013016841A1 (fr) 2011-08-01 2011-08-01 Nanoparticules

Publications (1)

Publication Number Publication Date
WO2013016841A1 true WO2013016841A1 (fr) 2013-02-07

Family

ID=47628603

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/001251 WO2013016841A1 (fr) 2011-08-01 2011-08-01 Nanoparticules

Country Status (1)

Country Link
WO (1) WO2013016841A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104707638A (zh) * 2013-12-13 2015-06-17 中国科学院大连化学物理研究所 一种具有核-壳结构的含氮无定形碳层包裹碳纳米管一维材料及其制备方法和应用
WO2015193689A1 (fr) * 2014-06-21 2015-12-23 Inventure Fuels Limited Synthèse d'hydrocarbures
CN113745502A (zh) * 2021-06-28 2021-12-03 福州大学 一种碳纳米管包覆的氮化三铁及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1607979A (zh) * 2001-10-29 2005-04-20 海珀里昂催化国际有限公司 改性的含碳化物和碳氧化物的催化剂及其制造方法和应用
CN101062478A (zh) * 2006-04-26 2007-10-31 中国科学院大连化学物理研究所 用于氧化氢气中一氧化碳的催化剂及其制备方法
CN101583425A (zh) * 2005-02-17 2009-11-18 孟山都技术公司 含过渡金属的催化剂、包含含过渡金属的催化剂的催化剂组合物、它们的制备方法和作为氧化催化剂的用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1607979A (zh) * 2001-10-29 2005-04-20 海珀里昂催化国际有限公司 改性的含碳化物和碳氧化物的催化剂及其制造方法和应用
CN101583425A (zh) * 2005-02-17 2009-11-18 孟山都技术公司 含过渡金属的催化剂、包含含过渡金属的催化剂的催化剂组合物、它们的制备方法和作为氧化催化剂的用途
CN101062478A (zh) * 2006-04-26 2007-10-31 中国科学院大连化学物理研究所 用于氧化氢气中一氧化碳的催化剂及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104707638A (zh) * 2013-12-13 2015-06-17 中国科学院大连化学物理研究所 一种具有核-壳结构的含氮无定形碳层包裹碳纳米管一维材料及其制备方法和应用
WO2015193689A1 (fr) * 2014-06-21 2015-12-23 Inventure Fuels Limited Synthèse d'hydrocarbures
CN113745502A (zh) * 2021-06-28 2021-12-03 福州大学 一种碳纳米管包覆的氮化三铁及其制备方法和应用
CN113745502B (zh) * 2021-06-28 2023-03-14 福州大学 一种碳纳米管包覆的氮化三铁及其制备方法和应用

Similar Documents

Publication Publication Date Title
Wang et al. Iron–potassium on single-walled carbon nanotubes as efficient catalyst for CO2 hydrogenation to heavy olefins
An et al. Pyrolysis of metal–organic frameworks to Fe3O4@ Fe5C2 core–shell nanoparticles for Fischer–Tropsch synthesis
Zhao et al. Highly active and controllable MOF-derived carbon nanosheets supported iron catalysts for Fischer-Tropsch synthesis
Zhao et al. Ultrasmall Ni nanoparticles embedded in Zr-based MOFs provide high selectivity for CO 2 hydrogenation to methane at low temperatures
Sun et al. Preparation and catalysis of carbon‐supported iron catalysts for Fischer–Tropsch synthesis
Lu et al. Promotion effects of nitrogen doping into carbon nanotubes on supported iron Fischer–Tropsch catalysts for lower olefins
Saraswat et al. Ni–Cu–Zn/MCM-22 catalysts for simultaneous production of hydrogen and multiwall carbon nanotubes via thermo-catalytic decomposition of methane
Figueira et al. Nanoparticles of Ce, Sr, Co in and out the multi-walled carbon nanotubes applied for dry reforming of methane
Guo et al. Effects of Cu/Fe ratio on structure and performance of attapulgite supported CuFeCo-based catalyst for mixed alcohols synthesis from syngas
KR101424963B1 (ko) 다중벽 탄소 나노튜브 생산 공정을 위한 촉매 시스템
Dong et al. Preparation and characterization of carbon nanotube-promoted Co–Cu catalyst for higher alcohol synthesis from syngas
Jiang et al. Hydrogen production by chemical looping steam reforming of ethanol using NiO/montmorillonite oxygen carriers in a fixed-bed reactor
Xiong et al. Fischer–Tropsch synthesis over model iron catalysts supported on carbon spheres: The effect of iron precursor, support pretreatment, catalyst preparation method and promoters
Xing et al. Controllable encapsulation of cobalt clusters inside carbon nanotubes as effective catalysts for Fischer–Tropsch synthesis
Gil et al. Synthesis and characterization of Au supported on carbonaceous material-based catalysts for the selective oxidation of glycerol
Shen et al. Novel Fe–Ni nanoparticle catalyst for the production of CO-and CO2-free H2 and carbon nanotubes by dehydrogenation of methane
Shi et al. Synergistic effect of nitrogen-doped carbon-nanotube-supported Cu–Fe catalyst for the synthesis of higher alcohols from syngas
Park et al. Selective Formation of Hägg Iron Carbide with g‐C3N4 as a Sacrificial Support for Highly Active Fischer–Tropsch Synthesis
Dongil et al. Hydrodeoxygenation of guaiacol: Tuning the selectivity to cyclohexene by introducing Ni nanoparticles inside carbon nanotubes
Ciftci et al. Nanostructured ceria supported Pt and Au catalysts for the reactions of ethanol and formic acid
Wang et al. A comparison study of catalytic oxidation and acid oxidation to prepare carbon nanotubes for filling with Ru nanoparticles
Qin et al. In-situ FTIR study of CO2 adsorption and methanation mechanism over bimetallic catalyst at low temperature
Carrales-Alvarado et al. Effect of N-doping and carbon nanostructures on NiCu particles for hydrogen production from formic acid
Ghogia et al. Hydrogen spillover in the Fischer‐Tropsch synthesis on carbon‐supported cobalt catalysts
Xie et al. Effect of catalyst confinement and pore size on Fischer-Tropsch synthesis over cobalt supported on carbon nanotubes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11870324

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11870324

Country of ref document: EP

Kind code of ref document: A1