US20060099127A1 - New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer - Google Patents

New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer Download PDF

Info

Publication number
US20060099127A1
US20060099127A1 US10/519,644 US51964405A US2006099127A1 US 20060099127 A1 US20060099127 A1 US 20060099127A1 US 51964405 A US51964405 A US 51964405A US 2006099127 A1 US2006099127 A1 US 2006099127A1
Authority
US
United States
Prior art keywords
hydrogen
metal
powder
hydride
milling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/519,644
Other languages
English (en)
Inventor
Alicja Zaluska
Leszek Zaluski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of US20060099127A1 publication Critical patent/US20060099127A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/121—Metal hydrides
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0026—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof of one single metal or a rare earth metal; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J35/30—
    • B01J35/40—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to new catalytic materials of specific composition and molecular structure, which are able to catalyze and improve efficiency of chemical reactions involving hydrogen transfer.
  • heterogeneous catalysts are in the same phase as the basic reactants, and heterogeneous catalysts are in the different phase, for example: solid catalysts in the gaseous reactions.
  • the development and current understanding of catalysis allows us to distinguish two essential catalytic mechanisms, i.e. acidic catalysis and basic catalysis, where reactants act either as bases toward catalysts which in turn act as acids, or as acids toward basic catalysts.
  • acidic catalysis and basic catalysis
  • reactants act either as bases toward catalysts which in turn act as acids, or as acids toward basic catalysts.
  • acids or as acids toward basic catalysts.
  • basic catalysts the following are the most common: (H. Hattori “Heterogeneous Basic Catalysts”, Chem. Rev. 1995, 95, 537)
  • the simplest catalysts are single-phase materials, such as metals, oxides, sulfides, carbides, borides and nitrides.
  • Metal particles are among the most important catalysts, being used on a large scale for refining petroleum, conversion of automobile exhaust, hydrogenation of carbon monoxide, hydrogenation of fats and many other processes.
  • Multiphase catalysts usually consist of an active phase (e.g. metal particles or clusters) dispersed on a carrier (support). It is generally assumed that metal particles act most probably as active centers for the hydrogen dissociation, but the role of the support is so far still not fully understood. In practice the metal is often expensive (for example Pt) and may constitute only about 1 wt.
  • catalytic materials usually require “activation” i.e. some special treatment, before they could become active as catalysts, for example high-temperature annealing in vacuum or hydrogen atmosphere. Even then, however, in certain cases, the effect of annealing in hydrogen can indeed improve the catalyst's activity, but for other catalytic materials, the same treatment can actually have an adversary effect.
  • activation i.e. some special treatment
  • the effect of annealing in hydrogen can indeed improve the catalyst's activity, but for other catalytic materials, the same treatment can actually have an adversary effect.
  • catalysts become rapidly deactivated when exposed to air. They should be therefore handled under protective atmosphere, and pretreated at high temperatures after exposures to air in order to regain their catalytic properties.
  • the invention presents a practical and cost-efficient solution to this problem, by introducing a new type of catalytic materials, their manufacture and use as catalysts in chemical reactions.
  • the present invention provides a composition of matter prepared in accordance with a method comprising the steps of:
  • the present invention provides a composition of matter prepared in accordance with a method comprising:
  • each of the milling steps is conducted in a substantially inert gaseous environment.
  • the milling step is carried out in a gaseous environment having an insufficient concentration of an oxidizing agent to effect deleterious oxidation of the metal or metalloid component, or the alloy thereof, or the homogeneous or inhomogeneous combination of at least two of the metal or metalloid.
  • the milling step is carried out in a gaseous environment having an insufficient concentration of a reducing agent to effect deleterious reduction of the intermediate product.
  • the metal or metalloid is selected from the group consisting of Li, Na, K, Be, Mg, Ca, Y, Sc, Ti, Zr, Hf, V, Nb, Ta, Pt, Pd, Ru, Rh, Ge, Ga, In, La, Ce, Pr, Nd, Dy, Al, Si, B, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu, Ag, Au, Zn, Sn, Pb, Sb, and Bi.
  • the electronegative element is selected from the group consisting of O, F, N, Cl, S, P, C, Te, and I.
  • compositions have a particulate form consisting of a plurality of particles, and having a particle size of less than 100 microns. In even a further aspect, 80% of the particles have a particle size of less than 50 microns, and the grains present in the particles are characterized by a size less than 100 nm.
  • the composition has an X-ray diffraction pattern that exhibits a characteristic Bragg's reflection of a co-ordination of (i) metal or metalloid and (ii) hydrogen.
  • the milling imparts an impact energy sufficient to effect the formation of the new atomic co-ordinations.
  • the milling can be carried out in a high energy ball mill.
  • the present invention also provides, in another broad aspect, a composition of matter prepared in accordance with a method comprising the steps of:
  • the present invention provides a composition of matter prepared in accordance with a method comprising effecting reaction between (i) a metallic substance selected from the group consisting of: hydrogenated, metal or metalloid, or an alloy thereof, or a compound thereof, or an homogeneous on inhomogeneous combination of at least two of the hydrogenated, metal or metalloid, or the alloy thereof, or the compound thereof, and (ii) an electronegative element, by milling.
  • a metallic substance selected from the group consisting of: hydrogenated, metal or metalloid, or an alloy thereof, or a compound thereof, or an homogeneous on inhomogeneous combination of at least two of the hydrogenated, metal or metalloid, or the alloy thereof, or the compound thereof, and (ii) an electronegative element, by milling.
  • each of the above enumerated compositions of matter can function as hydrogen transfer facilitators.
  • each of the above-enumerated compositions can combine with metallic substance selected from the group consisting of: (a) a hydride of a metal or metalloid, or an alloy thereof, or a compound thereof, or a homogeneous or inhomogeneous combination of at least two of the metal or metalloid, the alloy thereof, or the compound thereof, or (b) a metal or metalloid capable of absorbing hydrogen to form a hydride, or an alloy thereof, or a compound thereof, or an homogeneous or inhomogeneous combination of at least two of the metal or metalloid, the alloy thereof, or the compound thereof, such combining effecting sufficient contact between the hydrogen transfer facilitator and the second metallic substance so that the hydrogen transfer facilitator is configured to effect absorption or desorption of hydrogen by the second metallic substance.
  • the hydrogen transfer facilitator is mechanically alloyed to the second metallic substance.
  • Such mechanical alloying can be effected by milling.
  • compositions can effect a process of hydrogenating and dehydrogenating a hydrogen storage composition comprising the steps of:
  • steps (b) and (b) effecting desorption of the absorbed hydrogen from the hydrogen storage composition; wherein steps (a) and (b) are carried out in any order.
  • the present invention provides a hydrogen storage composition comprising:
  • a metallic substance selected from the group consisting of: (a) a hydride of a metal or metalloid, or an alloy thereof, or a compound thereof, or a homogeneous or inhomogeneous combination of at least two of the metal or metalloid, the alloy thereof, or the compound thereof, or (b) a metal or metalloid capable of absorbing hydrogen to form a hydride, or an alloy thereof, or a compound thereof, or an homogeneous or inhomogeneous combination of at least two of the metal or metalloid, the alloy thereof, or the compound thereof; and
  • a hydrogen transfer facilitator having an atomic co-ordination characterized by one of the following structural formula: (M+M1)-H--E (a) or (M)-H--E (b) wherein the hydrogen transfer facilitator is disposed in sufficient contact with the metallic substance so that the hydrogen transfer facilitator is configured to effect absorption or desorption of hydrogen by the second metallic substance.
  • the hydrogen transfer facilitator can also have other atomic co-ordinations, including: M--H-E; or (1) M-H—H.
  • FIG. 1 illustrates x-ray diffraction patterns referred to in Example 1 of a Ti-based catalyst ntion and that of comparative materials
  • FIG. 2 illustrates x-ray diffraction patterns referred to in Example 1 of comparative materials to the Ti-based catalyst
  • FIG. 3 illustrates hydrogen absorption referred to in Example 1 of a Ti/Ti-based catalyst system
  • FIG. 4 illustrates hydrogen absorption referred to in Example 1 of a Ti/Ti-based catalyst system and that of comparative materials
  • FIG. 5 illustrates hydrogen absorption referred to in Example 1 of comparative materials to the Ti/Ti-based catalyst system
  • FIG. 6 illustrates x-ray diffraction patterns referred to in Example 1 of a hydrogenated Ti/Ti-based catalyst system and that of comparative materials;
  • FIG. 7 illustrates x-ray diffraction patterns referred to in Example 2 of Zr-based catalysts and that of comparative materials
  • FIG. 8 illustrates x-ray diffraction patterns referred to in Example 2 of Zr/Zr-based catalyst systems and that of comparative materials, before and after hydrogenation;
  • FIG. 9 illustrates hydrogen absorption referred to in Example 2 of Zr/Zr-based catalyst systems and that of comparative materials
  • FIG. 10 illustrates hydrogen absorption referred to in Example 2 of a Zr/Zr-based catalyst system under different hydrogen pressures
  • FIG. 11 illustrates hydrogen absorption referred to in Examples 2 and 3 of various Zr/Zr-based catalyst systems
  • FIG. 12 illustrates x-ray diffraction patterns referred to in Example 3 of Zr/CuO based catalysts and that of comparative materials
  • FIG. 13 illustrates x-ray diffraction patterns referred to in Example 3 of Ti/CuO based catalysts and that of comparative materials
  • FIG. 14 illustrates x-ray diffraction patterns referred to in Example 3 of Zr/FeO based catalysts and that of comparative materials
  • FIG. 16 illustrates x-ray diffraction patterns referred to in Example 7 of ZrN based catalysts and that of comparative materials
  • FIG. 17 illustrates x-ray diffraction patterns referred to in Example 4 of CuO based catalysts and that of comparative materials
  • FIG. 18 illustrates x-ray diffraction patterns referred to in Example 3 of Mg-based system before and after hydrogenation
  • FIG. 19 illustrates hydrogen absorption referred to in Examples 3 of Mg-based system
  • FIG. 21 illustrates hydrogen desorption referred to in Examples 6 of NaAlH4-based system
  • FIGS. 22 and 23 illustrate dehydrogenation kinetics referred to in Example 6 of NaAlH4-based system.
  • FIG. 24 illustrates hydrogen desorption referred to in Examples 6 of NaAlH4-based system.
  • the present invention relates to a composition of matter characterized by a particular atomic configuration.
  • the composition of matter is useful for effecting improved hydrogen transfer kinetics in various kinds of chemical reactions which depend on the efficiency of hydrogen relocation or exchange.
  • such composition of matter of the present invention can be described as a “hydrogen transfer facilitator”.
  • the hydrogen transfer facilitator can also be described as a catalyst.
  • suitable metals and metalloids include: Li, Na, K, Be, Mg, Ca, Y, Sc, Ti, Zr, Hf, V, Nb, Ta, Pt, Pd, Ru, Rh, Ge, Ga, In, La, Ce, Pr, Nd, Dy, Al, Si, and B.
  • M1 is an optional other metal, or an alloy thereof, or a compound thereof, or a homogeneous or inhomogeneous combination of at least two of the metal, or the alloy thereof, or the compound thereof.
  • suitable metals include: Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu, Ag, Au, Zn, Sn, Pb, Sb, and Bi.
  • the hydrogen transfer facilitator has two further atomic co-ordinations which effects improved hydrogen transfer, and that such atomic co-ordinations can be described in accordance with the following structural formulae: M--H-E (2) M-H—H (3) wherein M, H, and E have the same meanings as in (1), and wherein in (2), hydrogen bonding exists between M and H, and wherein in (3), hydrogen bonding exists between H and H.
  • composition of matter of the present invention can be made by, firstly, combining (i) a metallic substance selected from the group consisting of: a metal or metalloid, or an alloy thereof, or a compound thereof, or an homogeneous or inhomogeneous combination of at least two of the metal or metalloid, or the alloy thereof, or the compound thereof, with (ii) a source of hydrogen, to form a first intermediate.
  • the first intermediate is then milled to effect reaction between the metallic substance and the hydrogen.
  • the hydrogen becomes bonded to the metallic substance as a second intermediate.
  • the second intermediate is then combined with a source of an electronegative element. Such combination is then milled to effect reaction between the second intermediate and the electronegative element to form the resultant composition.
  • a mechanical grinding or milling can be carried out in a high energy ball mill.
  • Suitable ball mills include tumbler ball mills, planetary ball mills, and attrition ball mills.
  • the mechanical treatment imparted by such milling operations provides enhanced reactivity of the reagents, by means of the continuous creation of fresh surfaces unaffected by oxides and hydroxides, and introduces local stress and deformation which is believed to enhance the rate of reaction.
  • each of the above described reactions is preferably carried out in a substantially inert gaseous environment in order for the desired reaction between the metallic substance and hydrogen to take place.
  • the reaction between the metal substance and hydrogen is preferably carried out in a gaseous environment having an insufficient concentration of an oxidizing agent to effect deleterious oxidation of the metallic substance.
  • the presence of the oxidizing agent interferes with the reaction between the metallic substance and hydrogen.
  • Deleterious oxidation of the metallic substance occurs when the metallic substance reacts to an unacceptable degree with an oxidizing agen (eg. oxygen) so as to significantly interfere with reactivity of the metallic substance with hydrogen. Unacceptable degree of reaction varies depending on the circumstance.
  • the reaction between the metallic substance-hydrogen intermediate with the electronegative element is preferably be carried out in a gaseous environment having an insufficient concentration of a reducing agent to effect deleterious reduction of the subject intermediate product.
  • a reducing agent would otherwise interfere with the reaction between the electronegative element and the intermediate.
  • Deleterious reduction of the metallic substance occurs when the metal-hydrogen co-ordination of a reactive intermediate (a precursor to the hydrogen transfer facilitator) reacts to an unacceptable degree with a reducing agent so as to significantly interfere with the reactivity between the intermediate and the electronegative element.
  • reduction becomes unacceptable where the resultant composition does not possess sufficient catalytic activity to justify the space it is occupying.
  • the composition of matter may also be prepared from a hydrogenated metallic substance. Hydrogenated metallic substances can be directly reacted with the electronegative element to form the composition of matter of the subject invention without having to first undergo a reaction with hydrogen.
  • the present invention also provides a composition of matter prepared in accordance with a method comprising: (a) combining a hydrogenated metallic substance with a source of an electronegative element, to form a first intermediate; and (b) milling the first intermediate to effect reaction between (i) the hydrogenated metallic, and (ii) the electronegative component.
  • the composition of matter may be prepared by milling the metallic substance with a liquid, such as water or an alcohol or mixtures thereof.
  • the present invention further provides a composition of matter prepared in accordance with a method comprising: (a) combining a metal or metalloid, or an alloy thereof, or a compound thereof, or an homogeneous or inhomogeneous combination of at least to the metal or metalloid, or the alloy thereof, or the compound thereof, with the liquid selected from the group consisting of water and alcohols and mixtures thereof, to form a first intermediate, and (b) milling the first intermediate.
  • excess of liquids relative to metal substances should be avoided.
  • the molar ratio of the liquid to the metallic substance is less than 1:1.
  • the hydrogen transfer facilitator may also be formed by contacting the metallic substance with gaseous reagents to effect the necessary transformations which form the desired atomic co-ordination.
  • the solid metallic component can be exposed to hydrogen and oxygen (or chlorine, or fluorine, or nitrogen) in the gas phase.
  • oxygen or chlorine, or fluorine, or nitrogen
  • a sequence of gas admission steps is applied. The process involves, for example, exposure to hydrogen under certain conditions of temperature and pressure, which results in hydrogen adsorption or absorption, through the metal surface. It is then followed by the admission of the other gas under certain conditions of temperature and pressure.
  • either complete oxidation or complete reduction of the metallic component should be avoided in the process, in order for both basic components (hydrogen and the electronegative element) to be present in the metallic complex.
  • the hydrogen transfer facilitator may even further be formed by contacting the metallic substance with solid reagents to effect the necessary transformations which form the desired atomic co-ordination.
  • a solid compound for example a solid hydrocarbon, such as solid polymer, or oxide, chloride, fluoride, sulfide, carbide, telluride or iodide, alkoxide etc. Hydrides, hydroxides, solid acids, bases, or other compounds can be also used as hydrogen- and electronegative element-sources. These compounds can also contain metals or metalloids either different or the same as the main (M+M1) components.
  • the most effective way of producing the required catalytic complexes is to use a high-energy ball mill, providing a solid-state reaction between the metallic element (either previously hydrogenated or not) and the solid source of the electronegative element and hydrogen.
  • the hydrogen source for example a solid hydrocarbon, a hydride
  • a source of an electronegative element is added in a second stage, for example, an oxide.
  • a specific combination of solid carriers supplying the hydrogen and/or the electronegative element can be used, for example a mixture of an oxide and a hydride, a mixture of alkoxides, oxides, chlorides, etc.
  • a specific example of the process in the solid state is when a solidified source of hydrogen and of the electronegative element is introduced, for example water in the form of ice, which can also be performed at adequately low temperatures.
  • solid hydride can be milled under gaseous oxygen
  • liquid fluoride can be milled with a hydrogenated metallic alloy
  • gaseous hydrogenation can be performed in a ball mill, then followed by ball milling with water, or with a solid hydrocarbon.
  • compositions of matter of the present invention which function as hydrogen transfer facilitators, are preferably in particulate form, having a particle size less than 100 microns, and also being characterized by the fact that 80% of the particles have a particle size less than 50 microns.
  • the particles possess nanocrystalline characteristics, such that the grain size of the particles is less than 100 nm.
  • composition of matter of the present invention can be used as a hydrogen transfer facilitator for effecting the hydrogenation and dehydrogenation of a metal hydride or hydrogenation of unsaturated organic compounds.
  • a hydrogen storage composition of the present invention can be prepared by combining the hydrogen transfer facilitator, as described above, to a metallic substance selected from the group consisting of (a) a hydride of a metal or metalloid, or an alloy thereof, or a compound thereof, or a homogeneous or inhomogeneous combination of at least two of the metal or metalloid, the alloy thereof, or the compound thereof, or (b) a metal or metalloid capable of absorbing hydrogen to form a hydride, or an alloy thereof, or an homogeneous or inhomogeneous combination of at least two of the metal or metalloid, or the alloy thereof, or the compound thereof, such combining effecting sufficient contact between the hydrogen transfer facilitator and the second metallic substance so that the hydrogen transfer facilitator is configured to effect absorption or desorption of hydrogen by the
  • the hydrogen transfer facilitator can also be intermixed with the metal hydride or hydridable metal using other methods such as mixing, spraying, deposition, condensation, compaction, sintering, and co-sintering.
  • the hydrogen transfer facilitator can enhance the kinetics of hydrogen and dehydrogenation of the hydrogen storage composition.
  • Hydrogenation is the process whereby hydrogen is absorbed by the hydrogen storage composition. Hydrogenation is not intended to indicate that complete hydrogenation of the hydrogen storage composition has necessarily occurred, and contemplates both a complete hydrogenation and a partial hydrogenation resulting from the absorption of hydrogen by the hydrogen storage composition. Similarly, dehydrogenation is not intended to indicate that complete dehydrogenation has necessarily occurred, and contemplates both a complete dehydrogenation and a partial dehydrogenation resulting from the desorption of at least a part of the hydrogen content of the hydrogen storage composition.
  • Absorption of hydrogen by the metallic substance refers to the association of hydrogen with a metallic substance.
  • mechanisms for association include dissolution, covalent bonding, or ionic bonding.
  • Dissolution describes a process where hydrogen atoms is incorporated in the voids of a lattice structure of a metal or intermetallic alloy.
  • metal hydrides include vanadium hydrides, titanium hydrides and hydrides of vanadium-titanium alloys.
  • An example of a covalently bonded hydride is magnesium hydride.
  • Example of ionically bonded hydrides are sodium hydride and lithium hydride.
  • One method of controlling the exact amount of the electronegative element in the preparation process is to use additional components that have the ability to either provide the electronegative element (e.g. being oxygen donors through their in-situ reduction) or eliminate the excess of the electronegative element (through in-situ oxidation which prohibits detrimental oxidation of the metallic component).
  • additional components that have the ability to either provide the electronegative element (e.g. being oxygen donors through their in-situ reduction) or eliminate the excess of the electronegative element (through in-situ oxidation which prohibits detrimental oxidation of the metallic component).
  • oxygen-donating components could be, for example, copper oxide (which becomes reduced to copper during the process of the catalyst preparation) or zinc or aluminum (which become oxidized when necessary, instead of the destructive oxidation of the main metallic component).
  • a Ti-based catalyst was produced both from titanium powder and titanium hydride. Both methods gave equally good catalytic capability of the resulting catalyst so long as deleterious oxidation of titanium was prevented.
  • TiH 2 titanium hydride
  • Aldrich purity 98%, powder ⁇ 325 mesh
  • X-ray diffraction pattern of this hydride was created using a Bruker D8 Discover X-ray diffraction system (as was the case for all X-ray diffraction results discussed herein) and is shown in FIG. 1 a .
  • the X-ray diffraction pattern exhibits a characteristic set of Bragg's reflections consistent with the International Centre for Diffraction Data database PDF-2, card number 65-0934.
  • One gram of titanium hydride was loaded into a stainless steel vial together with approximately 1 ml of methanol (methyl alcohol HPLC grade 99.9%) and stainless steel balls, giving a ball-to-powder ratio of about 16:1 on a weight basis.
  • the loading was done in a glove box with protective argon atmosphere (less than 1 ppm of oxygen and less than 1 ppm of water).
  • the vial was mounted in a high-energy ball mill (SPEX CentriPrep 8000M Mixer/Mill). This milling device provides violent and complex movements in three mutually perpendicular directions, with frequency of about 1200 cycles/minute. Ball milling was performed for 9 hours, with particular care about perfect sealing of the vial.
  • FIG. 1 b shows x-ray diffraction pattern of the resulting powder (i.e. the “new catalyst”).
  • the pattern shows no apparent transformation of the basic crystallographic structure of the hydride (all Bragg's reflections remain at similar 20 positions as those characteristic for the original hydride structure). Also, no additional phase can be seen in the diffraction pattern (no additional Bragg's reflections). In particular, none of the normally expected reaction products, namely oxide phase or alkoxide phase, appeared to be present.
  • x -ray diffraction patterns for commercial TiO purchased from Alfa Aesar, purity 99.5%, ⁇ 325 mesh powder
  • titanium methoxide Ti(OCH 3 ) 4 purchased from Alfa Aesar, purity 95% powder
  • the only apparent difference in the x-ray diffraction pattern of the new catalyst is a significant widening of the Bragg's reflections, which is usually interpreted as a result of increased level of strain, defects, and formation of the nanocrystalline structure.
  • X-ray diffraction data for the new Ti-based catalyst was compared to that of materials comprising similar elements, with a view to understanding the structure and co-ordination of the Ti-based catalyst.
  • the following comparative materials were prepared: TiH 2 ball milled without any additions, ball milled TiO, a mixture of TiH 2 and TiO ball milled without additions, the same mixture of TiH 2 and TiO but ball milled with methanol, and Ti milled with excess of water and under oxygen-containing atmosphere. All these materials were prepared under identical ball milling conditions as for the formation of the Ti-based catalyst, with the same parameters as above, and using the same technique of loading and handling.
  • titanium hydride can be formed by direct reaction with H 2 gas, but “must be heated to 400-600° C. to activate” and can be “easily deactivated by impurities such as O 2 and H 2 O”.
  • Titanium powder was purchased from Alfa Aesar, with 99.5% purity, ⁇ 325 mesh powder. Titanium powder was mixed with 10 wt. % of the new Ti-based catalyst (prepared as above) and ball milled for a short period of time (less than 1 hour) in order to provide good distribution of the catalyst over titanium powder.
  • Hydrogen absorption capabilities of the material were measured in an automated, computer controlled gas titration system, which allows precise evaluation of hydrogen uptake and release by measuring pressure changes in a closed system.
  • titanium powder catalyzed by the new titanium-based catalyst exhibited very fast (within about 20 seconds) formation of titanium hydride at room temperature, without any activation or preheating, as shown in FIG. 3 .
  • the hydrogen pressure used for hydrogenation was relatively very low, less than 1 bar, and decreased to about 0.4 bars due to hydrogen consumption during absorption.
  • hydrogen pressure used for absorption was as low as 300 mbars, and the formation of titanium hydride occurred within less than 30 minutes, as shown in FIG. 3 b , again without any activation or preheating.
  • FIG. 6 shows x-ray diffraction patterns which confirm the hydrogenation measurements of Ti in the Ti-systems studied above.
  • FIG. 1 a illustrates x-ray diffraction pattern of the initial Ti powder (consistent with the International Centre for Diffraction Data database PDF-2, card number 89-5009).
  • FIGS. 6 b and 6 d illustrate x-ray diffraction patterns for (i) Ti intermixed (by using short ball milling described above) with dry, ball milled TiH 2 after hydrogenation ( FIG. 6 b ), and (ii) Ti intermixed (by using short ball milling described above) with the new catalyst ( FIG. 6 d ).
  • Zirconium-based catalysts according to the invention can be produced from both zirconium and zirconium hydride. In general, it involves formation of the Zr—H atomic configuration, complemented by introduction of the electronegative element.
  • the electronegative element can be derived from a liquid such as water or alcohol, or from, for example, metal oxides. Similar to the above examples using titanium, a variety of processes can be effectively applied in the preparation of the Zr-based catalysts.
  • zirconium powder was purchased from Alfa Aesar (with purity 95+%, average powder size 2-3 micron, packaged in water).
  • the disadvantage of metallic zirconium is that it is very sensitive to oxidation. Since normally zirconium does not react with water, packaging in water is the most common method of protecting Zr from deterioration in air.
  • water can be used as a reagent in the process of preparation of Zr-based catalyst, dried zirconium was always used as a starting material in order to fully control the amount of water added.
  • the first step of the experiment was to dry commercial zirconium powder overnight under vacuum, with continuous pumping.
  • FIG. 7 a shows x-ray diffraction pattern of the dried commercial zirconium powder.
  • Zr The structure of Zr is reflected in its characteristic set of Bragg's reflections, which is consistent with the International Centre for Diffraction Data database PDF-2, card number 894892.
  • Prepared zirconium powder was subsequently used as starting material for the formation of new Zr-based catalysts, which involved ball milling of Zr with water or alcohol, and also with metal oxides or metals.
  • Zr powder alone was subjected to ball milling under similar conditions as in the catalyst preparation experiments (described below).
  • FIG. 7 b which shows x-ray diffraction pattern of the ball-milled zirconium, the effects of ball milling are limited to the usual features of Bragg's reflection broadening, caused by introduction of stress, defects and nanocrystalline structure.
  • FIG. 7 c shows x-ray diffraction pattern of the resulting material (i.e. the new Zr-based catalyst).
  • the pattern clearly shows a crystallographic structure different from that of zirconium ( FIGS. 7 a and 7 b ) and can be interpreted as a zirconium hydride crystallographic configuration, since all Bragg's reflections occur at similar 20 positions as those characteristics for the zirconium hydride structure, in accordance with the International Centre for Diffraction Data database PDF-2, card number 65-0745.
  • a very similar pattern (although with relatively sharper Bragg's reflections, as shown in FIG.
  • FIG. 7 d shows x-ray diffraction patterns for the commercial ZrH 2
  • FIG. 7 f shows x-ray diffraction pattern for commercial zirconium oxide, ZrO 2 (purchased from Alfa Aesar, purity 95% powder).
  • Catalytic properties of the Zr-based catalyst were evaluated in the process of hydrogenation of zirconium, i.e. in the process of formation of zirconium hydride.
  • formation of zirconium hydride is performed at temperatures around 400° C., and according to “Compilation of IEA/DOE/SNL Hydride Databases” by G. Sandrock and G. Thomas http://hydpark.ca.sandia.gov, zirconium exhibits good reaction rates at these temperatures.
  • zirconium powder purchased from Alfa Aesar, with purity 95.+%, average powder size 2-3 micron
  • zirconium powder was mixed with 10 wt. % of the new Zr-based catalyst (prepared from each of zirconium metal and zirconium hydride, as described above) and ball milled (in SPEX CentriPrep 8000M Mixer/Mill) for a short period of time (less than 1. hour) in order to provide good distribution of the catalyst over zirconium powder.
  • FIG. 8 a shows x-ray diffraction pattern of the starting commercial powder
  • FIG. 8 b presents x-ray diffraction pattern of Zr after introducing the catalyst by ball milling. Broader Bragg's reflections as compared to the starting material reflect the effects of strain, defects and nanocrystalline structure introduced by ball milling.
  • Hydrogen absorption of the material was measured in an automated, computer controlled gas titration system. Zirconium powder catalyzed by the new zirconium-based catalyst was transferred from the ball milling vial into the titration system holder and after evacuation of the apparatus (without any preheating or conditioning), hydrogen gas was introduced at room temperature under the pressure of about 1 bar. A very fast reaction of hydrogen absorption was immediately observed, which was substantially complete in under 10 seconds, as shown in FIG. 9 .
  • zirconium powder without additions, and zirconium powder intermixed by short ball milling (1 hr) with additions of the before-mentioned comparative materials were applied to the corn zirconium powder (i.e. dry, ball-milled ZrH 2 , ball-milled ZrO 2 , and their mixture), and similar hydrogenation experiments to those involving the new Zr-based catalyst were carried out.
  • zirconium hydride was not formed within a comparable period of time, as shown in FIG. 9 .
  • zirconium-based catalyst was produced from zirconium hydride (ZrH 2 ) and copper oxide (CuO), in a process of ball milling with a mixture of water and methanol.
  • 400 mg of zirconium hydride ZrH 2 (Alfa Aesar, purity 99.7%, ⁇ 10 micron powder) was placed in a stainless steel vial with 400 mg of copper oxide CuO (Alfa Aesar, purity 99.7%, ⁇ 200 mesh powder) and 0.4 ml of a 1:1 molar ratio mixture of water and methanol (methyl alcohol HPLC grade 99.9%), together with stainless steel balls, giving a ball-to-powder ratio of about 20:1 on a weight basis.
  • the loading was done in a glove box with protective argon atmosphere. Subsequently, the vial was mounted in a high-energy ball mils (SPEX CentriPrep 8000M Mixer/Mill). Ball milling was performed for 9 hours. After the process, there was no visual presence of the liquid phase, and the product was a black; fine powder, with very small reddish particles, visible under magnifying glass. X-ray diffraction pattern of this material ( FIG. 12 c ) indicates that at least a portion of CuO was reduced during the milling process, and Bragg's reflection characteristic for metallic copper appeared in the spectrum (x-ray diffraction pattern of commercial Cu is shown in FIG. 12 d for comparison).
  • FIG. 11 illustrates the hydrogenation kinetics characteristic of the Zr-based catalyst prepared, as above, from a mixture of ZrH 2 and CuO, and then intermixed with zirconium powder to render the system which then was hydrogenated.
  • FIG. 11 also comparatively illustrates the hydrogenation kinetics characteristic of the Zr-based catalyst prepared from ZrH 2 and CuO versus Zr-based catalysts prepared from Zr and ZrH 2 (as per Example 2). Each catalyst appears to be substantially equally effective in improving the kinetics of the hydrogenation.
  • a further zirconium-based catalyst was produced from zirconium hydride ZrH 2 and iron oxide FeO, in a process of ball milling with a mixture of water and methanol.
  • 400 mg of zirconium hydride ZrH 2 (Alfa Aesar, purity 99.7%, ⁇ 10 micron powder) was placed in a stainless steel vial with 400 mg of iron oxide FeO (Alfa Aesar, purity 99.5%, ⁇ 10 mesh powder) and 0.4 ml of a 1:1 molar ratio mixture of water and methanol (methyl alcohol HPLC grade 99.9%), together with stainless steel balls, giving a ball-to-powder ratio of about 20:1 on a weight basis.
  • the loading was done in a glove box with protective argon atmosphere. Subsequently, the vial was mounted in a high-energy ball mill (SPEX CentriPrep 8000M Mixer/Mill). Ball milling was performed for 9 hours. After the process, there was no visual presence of the liquid phase, and the product was a black, fine powder. X-ray diffraction pattern of this material ( FIG. 14 c ) indicates that at least a portion of FeO was reduced during the milling process, and Bragg's reflection characteristic for metallic iron appeared in the spectrum (x-ray diffraction pattern of commercial Fe is shown in FIG. 14 d for comparison).
  • Titanium-based catalyst was produced from titanium hydride TiH 2 and copper oxide CuO, in a process of ball milling with a mixture of water and methanol, 450 mg of titanium hydride TiH 2 (Aldrich, purity 98%, powder ⁇ 325 mesh) was placed in a stainless steel vial with 350 mg of copper oxide CuO (Alfa Aesar, purity 99.7%, ⁇ 200 mesh powder) and 0.5 ml of a 1:1 molar ratio mixture of water and methanol (methyl alcohol HPLC grade 99.9%), together with stainless steel balls, giving a ball-to-powder ratio of about 20:1 on a weight basis.
  • Magnesium was purchased from Alfa Aesar, with 99.8% purity. As with the experiments described above, magnesium powder (with x-ray diffraction pattern shown in FIG. 18 , consistent with International Centre for Diffraction Data database PDF-2, card number 89-5003) was mixed with 10 wt. % of the new catalyst (prepared from TiH 2 and CuO, and ball milled for a short period of time (less than 1 hour)) in order to provide good distribution of the catalyst over magnesium powder.
  • FIG. 19 shows formation of magnesium hydride from the catalyzed magnesium at 40° C., without any activation or preheating.
  • the material after hydrogenation, the material exhibits x-ray diffraction pattern characteristic for MgH 2 , consistent with the International Centre for Diffraction Data database PDF-2, card number 72-1687. As can be seen in this diffraction pattern, the presence of small amount of the catalyst is still visible after hydrogenation, which had not been consumed or significantly transformed in the hydrogenation process and remains effective in the subsequent hydrogenation/dehydrogenation cycles.
  • Catalyst formation was observed in a series of experiments of ball-milling of copper oxide CuO with water, alcohol or their mixtures. Depending on the milling conditions, specifically the amount of water/alcohol added, and milling time, different stages of reduction of CuO were observed, namely various mixtures of CuO+Cu 2 0, or Cu 2 0+Cu, or CuO+Cu 2 O+Cu. These materials exhibited exemplary catalytic abilities, although no obvious indication of any particular M-H coordination was seen in the diffraction patterns.
  • LiAlH 4 Decomposition (i.e. dehydrogenation) of LiAlH 4 was catalyzed by an embodiment of a catalyst composition of the present invention.
  • This hydride is known to be very sensitive to any traces of H 2 O and has to be stored with great care, under protective atmosphere of dry gas (MSDS datasheet from the material supplier).
  • MSDS datasheet from the material supplier.
  • LiAlH 4 is relatively stable, even at elevated temperatures and decomposes slowly with hydrogen release up to 5.6 wt. % when heated up to at least 140-160° C.
  • LiAlH 4 (lithium tetrahydridoaluminate) was purchased from Alfa Aesar, with purity 95+%. Two samples were prepared under similar conditions; one from LiAlH 4 without any addition, and the other—with a catalyst prepared from ZrH 2 +CuO+Zn+water/methanol mixture, in analogous way as the catalysts described in previous examples). Subsequently, LiAlH 4 powder was mixed with 10 wt. % of the new catalyst and ball milled (in SPEX CentriPrep 8000M Mixer/Mill) for a short period of time (less than 1 hour) in order to provide good distribution of the catalyst over zirconium powder. The comparative sample of LiAlH 4 was also ball milled in the same way.
  • Hydrogen desorption of the material was measured in an automated, computer controlled gas titration system.
  • the material was transferred from the ball milling vial into the titration system holder and after evacuation of the apparatus, hydrogen gas release was measured.
  • the system was heated up to 95° C., and then kept at constant temperature, while measuring hydrogen release from the sample.
  • the non-catalyzed (but ball milled) sample of LiAlH 4 did not show any significant hydrogen release in this temperature/time scale, but the catalyzed LAlH 4 exhibited fast dehydrogenation, which started at temperatures about 70-80° C. and was completed with good kinetics without exceeding 100° C. It is important to note that in this case hydrogen desorption occurs below the melting temperature of LiAlH 4 (125° C.), which emphasizes the efficiency of the catalyst.
  • NaAlH 4 Hydrogenation/dehydrogenation of NaAlH 4 , (which is a sodium analog of LiAlH 4 ) was catalyzed by an embodiment of a catalyst composition of the present invention.
  • NaAlH 4 has also similar sensitivity to moisture and H 2 O traces as LiAlH 4 , and normally can be decomposed (dehydrogenated) only at temperatures close to its melting temperature, i.e. 180° C.
  • NaAlH 4 sodium aluminum hydride
  • Aldrich purity 90%, dry
  • two samples were prepared under similar conditions: one from NaAlH 4 without any addition, and the other—with a catalyst prepared from TiH 2 +CuO+water/methanol mixture, in similar way as the catalysts described in previous examples).
  • NaAlH 4 sample was mixed with 10 wt. % of the new catalyst and ball milled (in SPEX CentriPrep 8000M Mixer/Mill) for a short period of time (less than 1 hour) in order to provide good distribution of the catalyst.
  • the comparative sample of NaAlH 4 was also ball milled in the same way.
  • the catalyst did not lose its catalytic ability and remained visible in the diffraction pattern in a similar way as shown in the example of hydrogenated magnesium ( FIG. 18 ).
  • FIGS. 22 and 23 show dehydrogenation kinetics of NaAlH 4 catalyzed with a catalyst prepared from TiH 2 +NiO+methanol (shown in FIG. 15 b ). Dehydrogenation was performed at various temperatures: 140, 120 and 100° C., showing unsurpassed kinetics.
  • FIG. 24 shows hydrogen desorption from NaAlH 4 catalyzed by a catalyst prepared from TiH 2 +MgO+methanol (X-ray diffraction shown in FIG. 15 c ).
  • reducing elements or compounds are easily oxidized when necessary, can protect the metallic substance against oxidation.
  • suitable additions include aluminium, magnesium, zinc, rare earth metals or carbon.
  • an addition is used that could act either as a reducing addition or as part of the required M-H configuration, depending on the process specifics.
  • Such additions could be for example vanadium or manganese, which can act as protectors against oxidation for example in water-containing process, but can also form their own hydride-type configurations in ball milling with, for example, methanol.
  • a zirconium-based catalyst was produced from zirconium hydride (ZrH 2 ) and vanadium, in a process of ball milling with methanol, 350 mg of zirconium hydride (Alfa Aesar, purity 99.7%, powder ⁇ 10 micron powder) was placed in a stainless steel vial with 450 mg of vanadium (Alfa Aesar, purity 99.5%, ⁇ 20 mesh granules) and 0.5 ml methanol (methyl alcohol HPLC grade 99.9%), together with stainless steel balls, giving a ball-to-powder ratio of about 20:1 on a weight basis. The loading was done in a glove box with protective argon atmosphere.
  • the vial was mounted in a high-energy ball mill (SPEX CentriPrep 8000M Mixer/Mill). Ball milling was performed for 9 hours. After the process, the resulting product was a black, fine powder.
  • X-ray diffraction pattern of this material ( FIG. 16 c ) indicates that vanadium transformed into hydride-type coordination (at least partially) during the milling process, and Bragg's reflection characteristic for vanadium hydride (according to International Centre for Diffraction Data database PDF-2, card number 891890 appeared in the spectrum).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US10/519,644 2002-06-25 2003-06-25 New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer Abandoned US20060099127A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA2,389,939 2002-06-25
CA002389939A CA2389939A1 (fr) 2002-06-25 2002-06-25 Nouveaux materiaux catalytiques a base de complexes actifs metal-hydrogene-compose electronegatif pour les reactions de transfert d'hydrogene
PCT/CA2003/000960 WO2004000453A2 (fr) 2002-06-25 2003-06-25 Nouveau type de materiaux catalytiques a base de complexes metal actif-hydrogene-element electronegatif permettant un transfert d'hydrogene

Publications (1)

Publication Number Publication Date
US20060099127A1 true US20060099127A1 (en) 2006-05-11

Family

ID=29783882

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/519,644 Abandoned US20060099127A1 (en) 2002-06-25 2003-06-25 New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer
US10/746,742 Active 2026-06-29 US7811957B2 (en) 2002-06-25 2003-12-24 Type of catalytic materials based on active metal-hydrogen-electronegative element complexes involving hydrogen transfer

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/746,742 Active 2026-06-29 US7811957B2 (en) 2002-06-25 2003-12-24 Type of catalytic materials based on active metal-hydrogen-electronegative element complexes involving hydrogen transfer

Country Status (13)

Country Link
US (2) US20060099127A1 (fr)
EP (1) EP1534625B1 (fr)
JP (1) JP2005535546A (fr)
KR (1) KR20050053532A (fr)
CN (1) CN1688505A (fr)
AT (1) ATE459573T1 (fr)
AU (1) AU2003245771A1 (fr)
BR (1) BR0312112A (fr)
CA (1) CA2389939A1 (fr)
DE (1) DE60331553D1 (fr)
MX (1) MXPA04012975A (fr)
RU (1) RU2005101871A (fr)
WO (1) WO2004000453A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070039474A1 (en) * 2005-08-22 2007-02-22 Narula Chaitanya K Borazine-boron nitride hybrid hydrogen storage system
US20090123325A1 (en) * 2004-12-07 2009-05-14 The University Of Queensland Magnesium Alloys For Hydrogen Storage
US9435489B2 (en) 2010-02-24 2016-09-06 Hydrexia Pty Ltd Hydrogen release system
WO2021125990A1 (fr) * 2019-12-17 2021-06-24 Qatar Foundation For Education, Science And Community Development Catalyseurs pour cargen, procédés de préparation, et utilisations de ceux-ci
US11141784B2 (en) 2015-07-23 2021-10-12 Hydrexia Pty Ltd. Mg-based alloy for hydrogen storage

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6780218B2 (en) * 2001-06-20 2004-08-24 Showa Denko Kabushiki Kaisha Production process for niobium powder
US8414718B2 (en) * 2004-01-14 2013-04-09 Lockheed Martin Corporation Energetic material composition
CA2529427C (fr) * 2004-12-17 2011-03-15 University Of New Brunswick Synthese, recharge et traitement de materiaux pour le stockage de l'hydrogene au moyen de fluides supercritiques
US8697598B2 (en) * 2005-04-21 2014-04-15 China Petroleum & Chemical Corporation Hydrogenation catalyst and use thereof
CN100388977C (zh) * 2005-04-21 2008-05-21 中国石油化工股份有限公司 以氧化硅-氧化铝为载体的含氟、磷加氢催化剂及其制备
US7837976B2 (en) * 2005-07-29 2010-11-23 Brookhaven Science Associates, Llc Activated aluminum hydride hydrogen storage compositions and uses thereof
CA2619691A1 (fr) * 2005-08-17 2007-02-22 Hydrogen Link Inc. Generation d'hydrogene au moyen de reactions faisant intervenir des mecanismes de sorption
KR100708402B1 (ko) * 2005-10-27 2007-04-18 한국과학기술연구원 금속알루미늄수소화물 탈수소화반응 나노촉매 제조 및 분산방법
CN1308268C (zh) * 2005-12-08 2007-04-04 天津师范大学 一氧化碳电催化加氢还原制备甲醛和乙烯
US7829157B2 (en) * 2006-04-07 2010-11-09 Lockheed Martin Corporation Methods of making multilayered, hydrogen-containing thermite structures
US7842639B2 (en) * 2006-05-19 2010-11-30 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds
US7659227B2 (en) 2006-05-22 2010-02-09 University Of Notre Dame Du Lac Catalysts for hydrogen production
US8250985B2 (en) 2006-06-06 2012-08-28 Lockheed Martin Corporation Structural metallic binders for reactive fragmentation weapons
US7886668B2 (en) * 2006-06-06 2011-02-15 Lockheed Martin Corporation Metal matrix composite energetic structures
US20080236032A1 (en) * 2007-03-26 2008-10-02 Kelly Michael T Compositions, devices and methods for hydrogen generation
CN101642703B (zh) * 2009-09-03 2011-07-20 浙江大学 铝氢化钠配位氢化物的催化剂及其制备方法
US9949416B2 (en) 2010-12-15 2018-04-17 Advanced Bionics Ag Protection for implanted gold surfaces
US20120164449A1 (en) * 2010-12-23 2012-06-28 Stephen Woodrow Foss Fibers with improving anti-microbial performance
FR2985670A1 (fr) * 2012-01-12 2013-07-19 Centre Nat Rech Scient Procede ameliore pour le stockage d'un gaz
DE102013211106A1 (de) * 2013-06-14 2014-12-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Kompositmaterial, Vorrichtung sowie Verfahren zur hydrolytischen Erzeugung von Wasserstoff sowie Vorrichtung zur Erzeugung von elektrischer Energie und Verwendungsmöglichkeiten
KR101971731B1 (ko) * 2017-04-25 2019-04-25 한국과학기술연구원 세륨알루미나이드 분말의 제조 방법
CN108217596B (zh) * 2018-01-29 2021-03-30 吉林大学 使用非氢源溶液法制备铌氢化物和钽氢化物的方法
CN108467064A (zh) * 2018-06-11 2018-08-31 佛山腾鲤新能源科技有限公司 一种低温放氢型储氢复合材料的制备方法
CN111604498B (zh) * 2020-06-29 2022-04-08 宁夏东方钽业股份有限公司 一种铌锆合金粉末的制备方法
CN113151860B (zh) * 2021-04-28 2023-09-29 安徽大学 一种硫掺杂碳包裹铱纳米颗粒及其制备、应用
CN114890442B (zh) * 2022-06-29 2023-06-23 理道新材(北京)科技有限公司 一种氘化铝锂生产过程中氯化锂的回收利用方法
CN115992319B (zh) * 2022-12-19 2024-03-29 包头稀土研究院 稀土储氢合金及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4368143A (en) * 1978-11-14 1983-01-11 Battelle Memorial Institute Composition for the storage of hydrogen and method of making the composition
US4507263A (en) * 1982-08-15 1985-03-26 Moshe Ron Method for preparing improved porous metal-hydride compacts
US5763363A (en) * 1994-03-07 1998-06-09 Hydro-Quebec And Mcgill University Nanocrystalline Ni-based alloys and use thereof for the transportation and storage of hydrogen
US5906792A (en) * 1996-01-19 1999-05-25 Hydro-Quebec And Mcgill University Nanocrystalline composite for hydrogen storage
US5964965A (en) * 1995-02-02 1999-10-12 Hydro-Quebec Nanocrystalline Mg or Be-BASED materials and use thereof for the transportation and storage of hydrogen
US6251349B1 (en) * 1997-10-10 2001-06-26 Mcgill University Method of fabrication of complex alkali metal hydrides
US6342318B1 (en) * 1998-12-16 2002-01-29 Sanyo Electric Co., Ltd. Hydrogen absorbing alloy electrode and process for producing same

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5411095A (en) 1977-06-27 1979-01-26 Matsushita Electric Ind Co Ltd Hydrogen occluding material
US4555395A (en) * 1982-09-27 1985-11-26 Standard Oil Company Hydride compositions
US6528441B1 (en) * 1992-10-28 2003-03-04 Westinghouse Savannah River Company, L.L.C. Hydrogen storage composition and method
US5514353A (en) * 1994-06-28 1996-05-07 Af Sammer Corporation Demand responsive hydrogen generator based on hydride water reaction
US5962165A (en) 1994-07-22 1999-10-05 Kabushiki Kaisha Toshiba Hydrogen-absorbing alloy, method of surface modification of the alloy, negative electrode for battery and alkaline secondary battery
SE9702189D0 (sv) * 1997-06-06 1997-06-06 Hoeganaes Ab Powder composition and process for the preparation thereof
US6130006A (en) 1997-06-17 2000-10-10 Kabushiki Kaisha Toshiba Hydrogen-absorbing alloy
EP1017864B1 (fr) * 1997-08-30 2001-11-07 Honsel GmbH & Co. KG Alliage destine a la production de corps metalliques en mousse a l'aide d'une poudre ayant des adjuvants formant des germes
US6268084B1 (en) 1997-11-28 2001-07-31 Kabushiki Kaisha Toshiba Hydrogen-absorbing alloy and secondary battery
DE19758384C2 (de) * 1997-12-23 2002-08-01 Geesthacht Gkss Forschung Verfahren zur Herstellung nanokristalliner Metallhydride
JPH11264041A (ja) 1998-03-17 1999-09-28 Toshiba Corp 水素吸蔵合金
JPH11269501A (ja) * 1998-03-20 1999-10-05 Shin Etsu Chem Co Ltd 水素吸蔵合金粉末の製造方法及び水素吸蔵合金電極
AU4997299A (en) * 1998-08-06 2000-02-28 University Of Hawaii Novel hydrogen storage materials and method of making by dry homogenation
JP2000080429A (ja) 1998-08-31 2000-03-21 Toshiba Corp 水素吸蔵合金および二次電池
US6531704B2 (en) * 1998-09-14 2003-03-11 Nanoproducts Corporation Nanotechnology for engineering the performance of substances
JP4121711B2 (ja) * 1999-03-26 2008-07-23 ゲーカーエスエス フオルシユングスツエントルーム ゲーエストハフト ゲーエムベーハー 水素吸蔵金属含有材料及びその製造方法
CA2301252A1 (fr) * 2000-03-17 2001-09-17 Hydro-Quebec Methode de production d'hydrogene gazeux par reaction chimique avec des metaux ou des hydrures metalliques soumis a des deformations mecaniques intenses
JP2001303160A (ja) 2000-04-27 2001-10-31 Sumitomo Metal Ind Ltd 水素吸蔵合金
US6652619B2 (en) * 2000-08-10 2003-11-25 Showa Denko K.K. Niobium powder, sintered body thereof, and capacitor using the same
JP3752987B2 (ja) 2000-09-18 2006-03-08 日本重化学工業株式会社 水素吸蔵合金
EP1340235B1 (fr) * 2000-11-30 2006-08-09 Showa Denko K.K. Poudre pour condensateur, corps fritte et condensateur utilisant ce corps fritte
TWI260344B (en) * 2001-01-12 2006-08-21 Safe Hydrogen Llc A method of operating a hydrogen-fueled device
JP2003342006A (ja) * 2002-05-23 2003-12-03 Honda Motor Co Ltd 水素貯蔵粉末およびその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4368143A (en) * 1978-11-14 1983-01-11 Battelle Memorial Institute Composition for the storage of hydrogen and method of making the composition
US4507263A (en) * 1982-08-15 1985-03-26 Moshe Ron Method for preparing improved porous metal-hydride compacts
US5763363A (en) * 1994-03-07 1998-06-09 Hydro-Quebec And Mcgill University Nanocrystalline Ni-based alloys and use thereof for the transportation and storage of hydrogen
US5964965A (en) * 1995-02-02 1999-10-12 Hydro-Quebec Nanocrystalline Mg or Be-BASED materials and use thereof for the transportation and storage of hydrogen
US5906792A (en) * 1996-01-19 1999-05-25 Hydro-Quebec And Mcgill University Nanocrystalline composite for hydrogen storage
US6251349B1 (en) * 1997-10-10 2001-06-26 Mcgill University Method of fabrication of complex alkali metal hydrides
US6342318B1 (en) * 1998-12-16 2002-01-29 Sanyo Electric Co., Ltd. Hydrogen absorbing alloy electrode and process for producing same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090123325A1 (en) * 2004-12-07 2009-05-14 The University Of Queensland Magnesium Alloys For Hydrogen Storage
US9234264B2 (en) 2004-12-07 2016-01-12 Hydrexia Pty Limited Magnesium alloys for hydrogen storage
US20070039474A1 (en) * 2005-08-22 2007-02-22 Narula Chaitanya K Borazine-boron nitride hybrid hydrogen storage system
US7361213B2 (en) * 2005-08-22 2008-04-22 Ut-Battelle, Llc Borazine-boron nitride hybrid hydrogen storage system
US9435489B2 (en) 2010-02-24 2016-09-06 Hydrexia Pty Ltd Hydrogen release system
US10215338B2 (en) 2010-02-24 2019-02-26 Hydrexia Pty Ltd. Hydrogen release system
US11141784B2 (en) 2015-07-23 2021-10-12 Hydrexia Pty Ltd. Mg-based alloy for hydrogen storage
WO2021125990A1 (fr) * 2019-12-17 2021-06-24 Qatar Foundation For Education, Science And Community Development Catalyseurs pour cargen, procédés de préparation, et utilisations de ceux-ci

Also Published As

Publication number Publication date
CA2389939A1 (fr) 2003-12-25
ATE459573T1 (de) 2010-03-15
US20050002856A1 (en) 2005-01-06
WO2004000453A8 (fr) 2005-04-21
AU2003245771A1 (en) 2004-01-06
EP1534625B1 (fr) 2010-03-03
AU2003245771A8 (en) 2004-01-06
WO2004000453A3 (fr) 2004-05-06
JP2005535546A (ja) 2005-11-24
KR20050053532A (ko) 2005-06-08
US7811957B2 (en) 2010-10-12
BR0312112A (pt) 2005-03-29
WO2004000453A2 (fr) 2003-12-31
CN1688505A (zh) 2005-10-26
DE60331553D1 (de) 2010-04-15
EP1534625A2 (fr) 2005-06-01
MXPA04012975A (es) 2005-09-12
RU2005101871A (ru) 2005-08-27

Similar Documents

Publication Publication Date Title
EP1534625B1 (fr) Nouveau type de materiaux catalytiques a base de complexes metal actif-hydrogene-element electronegatif permettant un transfert d'hydrogene
Fichtner et al. Small Ti clusters for catalysis of hydrogen exchange in NaAlH4
Bulut et al. Carbon dispersed copper-cobalt alloy nanoparticles: A cost-effective heterogeneous catalyst with exceptional performance in the hydrolytic dehydrogenation of ammonia-borane
US9981845B2 (en) Catalyst for producing hydrogen and method for producing hydrogen
Zhang et al. Highly active multivalent multielement catalysts derived from hierarchical porous TiNb 2 O 7 nanospheres for the reversible hydrogen storage of MgH 2
US6471935B2 (en) Hydrogen storage materials and method of making by dry homogenation
Singh et al. Nickel-palladium nanoparticle catalyzed hydrogen generation from hydrous hydrazine for chemical hydrogen storage
Xue et al. Reversible hydrogenation and dehydrogenation of N-ethylcarbazole over bimetallic Pd-Rh catalyst for hydrogen storage
Wang et al. One-pot synthesis of Au/Pd core/shell nanoparticles supported on reduced graphene oxide with enhanced dehydrogenation performance for dodecahydro-N-ethylcarbazole
Bobet et al. Hydrogen sorption of Mg-based mixtures elaborated by reactive mechanical grinding
Duman et al. Ceria supported manganese (0) nanoparticle catalysts for hydrogen generation from the hydrolysis of sodium borohydride
Patel et al. Improved dehydrogenation of ammonia borane over Co-PB coating on Ni: A single catalyst for both hydrolysis and thermolysis
Arzac et al. New insights into the synergistic effect in bimetallic-boron catalysts for hydrogen generation: The Co–Ru–B system as a case study
CA2339656A1 (fr) Nouveaux materiaux de stockage de l'hydrogene et leur procede de fabrication par homogeneisation a sec
Baguc et al. Nanocrystalline metal organic framework (MIL-101) stabilized copper Nanoparticles: Highly efficient nanocatalyst for the hydrolytic dehydrogenation of methylamine borane
Asim et al. Synergetic effect of Au nanoparticles and transition metal phosphides for enhanced hydrogen evolution from ammonia-borane
Kojima et al. Hydrogen release of catalyzed lithium aluminum hydride by a mechanochemical reaction
Wang et al. A triphasic nanocomposite with a synergetic interfacial structure as a trifunctional catalyst toward electrochemical oxygen and hydrogen reactions
EP2519349A1 (fr) Méthode d'élaboration de compositions bimétalliques de cobalt et de palladium sur un support de type matériau inerte et compositions pouvant être obtenues par ladite méthode
Asim et al. Pt@ Ni2P/C3N4 for charge acceleration to promote hydrogen evolution from ammonia-borane
Salman et al. Doping and Structure-Promoted Destabilization of NaBH4 Nanocubes for Hydrogen Storage
Pukazhselvan et al. Metal oxide additives incorporated hydrogen storage systems: Formation of in situ catalysts and mechanistic understanding
El-Bahy et al. CO oxidation and 4-nitrophenol reduction over ceria-promoted platinum nanoparticles impregnated with ZSM-5 zeolite
Pukazhselvan et al. A highly active additive for magnesium hydride from the MgO–TiO2 mixed oxide family: Magnesium dititanate
CA2493316A1 (fr) Nouveau type de materiaux catalytiques a base de complexes metal actif-hydrogene-element electronegatif permettant un transfert d'hydrogene

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION