WO1999019724A1 - Activation de rayonnement et criblage de bibliotheques de catalyseurs permettant d'evaluer un catalyseur et reacteurs correspondants - Google Patents

Activation de rayonnement et criblage de bibliotheques de catalyseurs permettant d'evaluer un catalyseur et reacteurs correspondants Download PDF

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WO1999019724A1
WO1999019724A1 PCT/GB1998/003023 GB9803023W WO9919724A1 WO 1999019724 A1 WO1999019724 A1 WO 1999019724A1 GB 9803023 W GB9803023 W GB 9803023W WO 9919724 A1 WO9919724 A1 WO 9919724A1
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Prior art keywords
catalyst
product
reactant
zone
screening
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PCT/GB1998/003023
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English (en)
Inventor
Martin Philip Atkins
Selim Mehmet Senkan
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Bp Chemicals Limited
Laser Catalyst Systems Inc.
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Priority claimed from GBGB9807836.3A external-priority patent/GB9807836D0/en
Application filed by Bp Chemicals Limited, Laser Catalyst Systems Inc. filed Critical Bp Chemicals Limited
Priority to AU94494/98A priority Critical patent/AU736438B2/en
Priority to PL98339834A priority patent/PL339834A1/xx
Priority to NZ503731A priority patent/NZ503731A/en
Priority to BR9812909-0A priority patent/BR9812909A/pt
Priority to CA002306256A priority patent/CA2306256A1/fr
Priority to EP98947652A priority patent/EP1019713A1/fr
Priority to JP2000516226A priority patent/JP2001520380A/ja
Priority to KR1020007003828A priority patent/KR20010031021A/ko
Publication of WO1999019724A1 publication Critical patent/WO1999019724A1/fr
Priority to NO20001787A priority patent/NO20001787L/no

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/162—Direct photo-ionisation, e.g. single photon or multi-photon ionisation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00306—Reactor vessels in a multiple arrangement
    • B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00527—Sheets
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00585—Parallel processes
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00596—Solid-phase processes
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/0068—Means for controlling the apparatus of the process
    • B01J2219/00702—Processes involving means for analysing and characterising the products
    • B01J2219/00707—Processes involving means for analysing and characterising the products separated from the reactor apparatus
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B01J2219/00747—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B30/00—Methods of screening libraries
    • C40B30/08—Methods of screening libraries by measuring catalytic activity
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/18—Libraries containing only inorganic compounds or inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

  • This invention relates to rapid screening for activities and selectivities of heterogeneous and homogeneous catalyst libraries.
  • This invention provides simultaneous screening of gaseous, liquid or solid products from all catalyst sites in a catalyst library by selective resonance enhanced multiphoton ionisation (REMPI).
  • REMPI selective resonance enhanced multiphoton ionisation
  • Combinatorial chemistry in which a large number of chemical variants are produced rapidly and a chemical library generated which is then screened for desirable properties using a suitable technique, is a particularly attractive approach for the discovery of new catalysts as described in Chem. Eng. News, 12 Feb. 1996.
  • Combinatorial synthesis was initially used to synthesize large libraries of biological oligomers, such as peptides and nucleotides, however, the creation of small molecule libraries which can be used for drug testing is growing. Nielsen, J., Chem. & Indus., 902, 21 Nov. 1994.
  • combinatorial diversity synthesis has been extended to solid-state compounds used in superconducting as described by Xiang, X-D et al in "A Combinatorial Approach to Materials Discovery",
  • Catalyst screening requires the unambiguous detection of the presence of a specific product molecule in the vicinity of a small catalyst site on a large library, unlike superconductivity or magnetoresistivity which can both be easily tested by conventional contact probes, or luminescence that can be tested by light emission.
  • This invention provides a microreactor and a high-throughput method to rapidly screen the activities and selectivities of homogeneous and heterogeneous catalyst libraries generated by combinatorial synthesis.
  • Solid and liquid state catalyst libraries can be generated using a variety of techniques and can involve the combination a large number of chemical elements and compounds.
  • Detection methods in situ in the reactor use the high sensitivity, specificity and real-time features of resonance-enhanced multiphoton ionisation, REMPI, in which pulsed and tunable ionising light sources are used to selectively photoionise desired reaction products without ionising reactants and/or other background species.
  • REMPI resonance-enhanced multiphoton ionisation
  • Photoions or photoelectrons generated by a tunable light beam in a reaction product plume from reactants in contact with a specific catalyst library site are detected by an array of microelectrodes positioned in close proximity to the library sites. While this invention will be described using a tunable ionising beam, any radiation beam of an energy level to promote formation of specified photoions and/or photoelectrons may be used.
  • reaction products are solids or liquids, they can be ablated using a pulsed laser beam followed by selective photoionisation of the products using a suitable UV laser.
  • the process of this invention can provide information on catalyst selectivity by detecting several reaction product species.
  • the process of this invention is broadly applicable and can be used to simultaneously screen an entire catalyst library.
  • the process of this invention can also be used to study operational lifetimes, resistance to poisoning, regeneration and loss of catalysts in tests or in full scale chemical plant processes.
  • the process of this invention for rapid screening of potential catalyst libraries for catalytic properties broadly comprises; forming a potential catalyst library having potential catalysts at a plurality of addressable sites, passing a reactant gas in contact with the potential catalysts at the plurality of addressable sites, and screening gas plumes of products of reaction at the addressable sites, the screening comprising passing a radiation beam of an energy level sufficient to form specified ions and electrons, such as, for example, a laser beam of a frequency to promote formation of specified photoions and/or photoelectrons and detecting the formed photoions and/or photoelectrons by microelectrode collection in situ in proximity to the addressable sites.
  • the present invention is a microreactor for radiation activation screening of reaction products, said microreactor comprising: an inert substrate body, a reactor passageway extending from a first opening on one side of said substrate body to a second opening on the opposite side of said substrate body, a reaction zone in the central portion of said reactor passageway to enable contact of reactants with a catalyst in said reaction zone, a reactant zone of said reactor passageway extending from said reaction zone serving as a reactant feed passage, and a product zone of said reactor passageway extending from said reaction zone to said second opening serving as a product exit passage; a radiation beam passageway extending through said substrate body generally perpendicular to and intersecting said product zone, said radiation beam passageway having radiation beam access windows providing passage of a radiation beam and fluid isolation of said radiation passageway from said product zone, and a microelectrode in said product zone in proximity to the intersection of said radiation beam passageway with said product zone.
  • Fig. 1 is a schematic showing the principles of REMPI microelectrode detection of product species
  • Fig. 2 is a schematic showing REMPI microelectrode detection of products formed by reactant contact of a catalyst library with physical masking
  • Fig. 3 is a schematic showing REMPI microelectrode detection of products formed by reactant contact of a catalyst library through a dedicated reactant teed tube;
  • Fig. 4 is a schematic showing similar to Fig. 3 having a tilted test site
  • Fig. 5 is a schematic showing REMPI microelectrode detection of products formed by reactant contact of a catalyst library with flow through porous sites;
  • Fig. 6 is a schematic showing REMPI microelectrode detection of products formed by reactant contact of a catalyst library of catalyst coating on a monolithic structure
  • Fig. 7 is a schematic showing of a monolithic catalyst library with expansion cooling of products for REMPI microelectrode detection
  • Fig. 8 is a schematic showing of a reactor with a flat plate solid catalyst library with row REMPI microelectrode detection
  • Fig. 9 is a schematic showing of a reactor with a flat plate catalyst library having reactant flow through porous sites and row REMPI microelectrode detection;
  • Fig. 10 is a schematic top view of a reactor as shown in Fig. 9 having simultaneous REMPI detection of all sites;
  • Fig. 1 1 is a schematic showing of a reactor with a monolith solid catalyst library having reactant flow through with row REMPI microelectrode detection;
  • Fig. 12 is a schematic showing of a reactor with a monolith catalyst library having simultaneous REMPI detection of all sites;
  • Fig. 13 is a schematic showing of a catalyst library with reactant contact for homogeneous catalyst sites with REMPI microelectrode detection of products
  • Fig. 14 is a schematic showing of a reactor with a homogeneous catalyst library with reactant flow through with row REMPI microelectrode detection of products
  • Fig. 15 Is a schematic showing of a catalyst library using solid catalyst particles for gas distribution and for catalyst contact with REMPI microelectrode detection of products;
  • Fig. 16 is a schematic showing of a heterogeneous catalyst library with reactant flow through with expansion cooling of products for REMPI microelectrode detection
  • Fig. 17 is a schematic showing of a catalyst library using an ablation laser for gasification of solid and/or liquid products for REMPI microelectrode detection of products;
  • Fig. 18 is a molecular beam REMPI spectra for benzene and cyclohexane by TOF-MS;
  • Fig. 19 is a microelectrode REMPI spectra for benzene and cyclohexane
  • Fig. 20 is microeectrode REMPI signals from screening of catalyst library site activity for benzene production.
  • Fig. 21 is a schematic showing of one embodiment of a single microreactor system of this invention.
  • Fig. 22 is a schematic showing of another embodiment of a single microreactor system of this invention suitable for solution deposition
  • Fig. 23 is a schematic showing of an array of microreactors in a single body
  • Fig. 24 is a schematic showing of another embodiment of an array of microreactors in a single body with a cover wafer;
  • Fig 25 is a schematic showing of a catalyst library in vertical stacked arrays of microreactors as shown in Fig. 24;
  • Fig. 26 is a schematic showing a microreactor array as shown in Fig. 24 fitting into a frame;
  • Fig. 27 is a schematic showing of arrays of microreactors in frames as shown in Fig. 26 arranged in adjacent side-by-side configuration; and Figures 28A and 28B are diagrams summarising combinatorial catalyst library preparation and screening according to one embodiment of this invention.
  • Coatings by Pulsed-Laser Deposition can be used to create large solid state catalyst libraries. These techniques provide good control of surface chemistry and are ideally suited to generate a wide spectaim of solid materials. Other well established preparation techniques, such as co-precipitation and impregnation, can also be used to generate catalyst libraries according to Satterfield, CN. in "Heterogeneous Catalysts in Practice", 2nd Ed., Chap. 4, 87, McGraw Hill, New York, 1991.
  • a large variety of co-precipitates can be synthesised in parallel and the resulting slurries/pastes can be applied on suitable substrates using, for example, multichannel pipettes or solenoid inkjet valves to generate spatially addressable sites according to Lemmo, AN. et al in "Characterisation of an Inkjet Chemical Microdispenser for Combinatorial Library Synthesis", Anal. Chem., 69, 543, 1997.
  • Catalyst libraries can also be prepared by impregnating suitable carrier materials, such as, for example, porous silica or alumina, that were previously applied to addressable sites on a substrate by a suitable liquid solution containing a catalyst.
  • Porous catalyst libraries can also be prepared by coating porous carriers, for example, silica or alumina, with thin films of catalytic materials using various film deposition techniques described above. AJI important aspect of this approach is prevention of excessive deposition to prevent pores becoming plugged by the catalytic materials. Reactant contact with the porous libraries can be accomplished either by passing reactants over or through the catalyst sites. In testing for catalysis, however, chemical composition is not the sole determinant of activity.
  • Heterogeneous catalyst libranes can also be prepared by using monolithic, or honeycomb, structures according to Sattei f ield, C N , 1991, supra These materials provide parallel, uniform, straight and nonconnecting channels, thereby providing a convenient matrix foi creating large catalyst libraries
  • a variety of cell shapes and sizes with cell densities varying from about 10 to about 500 cells per square inch can be produced with catalyst library sites
  • a wide variety of desired custom cell densities can be fabricated within and beyond the above ranges
  • Monolithic structui es can be made from metals oi they can be extruded from inoi anic dough, such as magnesia-alumina silicate, through a die followed by drying and filing
  • Catalyst libraries can also be prepared by coating metal monoliths with inoiganic substrates, wherein the metal inlay serves as a barrier to prevent intercell diffusion of species Catalysts can then be incorporated into the library substrate using any of the variety of methods described above Monolith
  • the catalyst sites must be sufficiently separated from each other so that product formation from each site and its unambiguous detection can be achieved
  • Monolithic, or honeycomb, structures offer advantages by providing clear physical separation of the library sites
  • Screening of large libraries for desired catalytic activity is based upon the fact that when a laser frequency is tuned to a real electronic intermediate state of a gaseous molecule, the cross section for ionization of that molecule is significantly enhanced This process is the so-called resonance- enhanced multiphoton ionisation, or REMPI When the laser wavelength is not tuned to a real electronic state, the probability for photoionisation is very small.
  • the ionisation cross section reflects the absorption-excitation spectrum of the intermediate electronic state of the molecule
  • REMPI specific catalytic reaction products can be selectively ionised with high efficiency using a suitable laser frequency, while avoiding the simultaneous photoionisation of reactants and/or background gases
  • any radiation beam of a suitable energy level to promote formation of specified ions and electrons from reaction products may be used, thereby allowing detection of the formed ions and/or electrons by microelectrode collection in downstream proximity to the radiation beam.
  • the process of this invention may be used in detection of directly related products.
  • reaction product molecules may be fragmented into smaller daughter products by a suitable energy source, such as, for example, a pulsed laser beam or by a plasma arc.
  • the fragments may be stable molecules, radicals or ionic species.
  • the daughter product can be selectively photoionised using the REMPI process and detected by a microelectrode as described herein. Quantification of reaction products by detection of their fragmentation products requires additional calibration to account for the efficiencies of fragmentation.
  • reaction products or their fragmentation products may emit unique radiation signatures involving, for example, luminescence, fluorescence or phosphorescence. These emissions can then be used to rapidly screen the catalyst libraries using, for example, monochromators and diode array and charge coupled device (CCD) detectors.
  • CCD charge coupled device
  • acrylonitrile (C 2 H 3 CN) when produced by the reaction of propane (C 3 Hs), ammonia (N ⁇ 3 ) and oxygen may be detected by detection of either of the products resulting from the fragmentation C 2 H 3 CN + hv — » C 2 H 2 + CN which gives unique information about the level of acrylonitrile in a product mixture.
  • R2PT resonant 2-photon ionisation
  • one photon, hv ⁇ energises the molecule to an excited electronic state
  • the second photon, ?v 2 ionises the molecule as described in Lubman, D M, "Lasers and Mass Spectrometry", Oxford Univ. Press, New York, 1990, Chap. 16 by Lubman, D.M. et al entitled “Resonant Two-Photon Ionisation Spectroscopy of Biological Molecules in Supersonic Jets Volitalised by Pulsed Laser Desorption", page 353.
  • the absorption of two or more photons in each step can also be used for REMPI.
  • Ionisation occurs if (/7V ⁇ +/7v 2 )>IP, where IP is the ionisation potential.
  • the two photons used can have the same or different energies and can be obtained from the same or different lasers. Higher energy UV photons may also be used to photoionise species in a single photon proces.
  • P the product
  • P* the real electronic excited state of the product
  • P + the photoion of the product
  • e is the photoelectron.
  • each photon in a successful REMPI must possess an energy of about 1/2 the IP in the R2P1 process using a single laser beam.
  • each photon energy must be about 1/3 the IP in a 2 + 1 process and 1/4 the IP in a 2 + 2 process, etc.
  • each photon energy can be independently selected to optimise the resulting REMPI signals.
  • Laser wavelengths covering the range from deep ultraviolet, UV, such as 150 nanometers, nm, to visible light, such as 700 nm, can be used to induce REMPI using a variety of multiphoton processes.
  • REMPI is inherently a high resolution technique in which ion absorption features of any molecule can be determined with high precision. Also, molecules are ionised from a vibrational level of an electronically excited state, thereby providing specific photoionisation of only target molecules. This can be used to distinguish between isomers, for example dichlorotoluenes, due to their different electronic structures according to Zimmerman, R. et al in "Three-dimensional Trace Analysis: Combination of Gas Chromatog aphy, Supersonic Beam UV Spectroscopy and Time-of-Flight Mass Spectrometry", Euro. Mass Spectrom., 1, 341, 1995.
  • the REMPI process can be sequentially used to detect different products using different laser frequencies, thus also providing the determination of catalyst selectivities.
  • REMPI is a high sensitivity technique with real-time detection of species at low parts per billion as described by Senkan, S.M. et al in "Real-Time Quantitative Analysis of Combustion Generated Polycyclic Aromatic Hydrocarbons by Resonance Enhanced Multiphoton lonization Time of Flight Mass Spectometry", Anal. Chem., 69, 287, 1997, and high parts per trillion already demonstrated by Senkan, S. M et al in "Real-time Ultrasensitive Monitoring of Air Toxics by Laser Photoionisation Time of Flight Mass Spectrometry", J. Air and Waste Mgmnt. Assoc, 48, 77, 1998.
  • Fig. 1 is a generalized illustration of the REMPI method of selective detection of a gaseous product generated by contacting a catalytic site with reactants.
  • gaseous reaction products form a gaseous plume 22 when catalyst 21 mounted on substrate 20 is contacted by the reactants.
  • the gaseous products are photoionized by pulsed UV laser beam 23 formed from tunable laser source 24 and/or using second tunable laser source 25 directed by mirror 26 through the central portion of gaseous product plume 22 generating photoions, P ⁇ and photoelectrons e " , as indicated in Fig. 1.
  • Microelectrode 27 is positioned a few millimeters above laser beam 23 to collect the photoelectrons or photoions, depending upon the voltage bias applied by DC power source 30 to cathode 28 and anode 29.
  • the electrical signal collected by microelectrode 27 is then amplified and detected by detector 31 , such as a digital oscilloscope. If the measured electrical signal is higher than reference sites which do not have catalysts, the site can be tagged catalytically active. Otherwise, the site must be considered catalytically inactive. It is apparent that selection of a suitable laser frequency, or frequencies for detection of multiple products, is critical to ensure that the electrical signals generated by the laser beam are exclusively due to photoionisation of the specified product gas and not from the reactants and/or background gases.
  • the suitable laser frequency for a specific material may be identified by laser photoionisation mass spectrometry studies, using for example, a tunable laser and time-of-flight mass spectrometer as described by Senkan, S.M.etal in 1997, supra and by Senkan, S.M et al in 1998, supra.
  • a gas mixture containing the species of interest is introduced into a vacuum chamber using, for example, a pulse valve
  • the expanding gas jet is then intercepted by UV photons at a specific energy from a tunable laser generator.
  • the resulting REMPI signals are then recorded by the time-of-flight mass spectrometer system.
  • the photoionisation spectra of the reactants products, by-products and background gases can be determined.
  • the photoionisation spectra of each isomer must be determined individually.
  • specific UV frequencies can be identified which would lead to the exclusive generation of the REMPI ions of specific product isomers desired to be evaluated.
  • the REMPI spectra broadens at elevated temperatures due to the overlapping transitions from a large number of rovibronic levels.
  • This identification process is expedited when the product gases are structurally different from the reactant and background gases, for example, in the production of benzene, an aromatic compound, from hexane, an aliphatic compound, in Ar carrier gas with H2 as the only by-product.
  • Potential problems associated with spectral congestion of REMPI signals can be effectively solved by the use of supersonic jet expansion as described by Parker, D.H.
  • the product photoions and photoelectrons generated above the catalyst site can be collected using a microelectrode, which can be either anode or cathode or both
  • the substrate upon which the catalyst library is deposited can also serve as the cathode or the anode, or another microelectrode can be placed within the substrate for this purpose
  • High temperature REMPIelectrode approach has previously been used to determine the concentration of gaseous species containing only a few atoms, such as PO, NO, H and O as desc ⁇ bed by Smyth, K C and Mallard, W G , "Two Photon Ionisation Processes of PO in a C 2 H 2 /air Flame", J Chem Phys , 77, 1779, 1982, Cool, T A in "Quantitative Measurement of NO
  • the solid state catalysts may be arranged in rows of catalyst clusters on a flat sheet to expedite the screening process
  • monolithic, or honeycomb, structures with well defined channels can also be used to generate suitable catalyst libraries
  • the catalyst sites can also be created to be porous or non-porous depending upon the catalyst and method of preparation
  • Fig 2 illustrates a non-porous, flat sheet catalyst library with reactant contact with the catalyst achieved by flowing reactant gases over the library followed by row screening of product plumes
  • Test catalyst site 21 with upstream catalyst site 2 lu and downstream catalyst site 21d are shown on substrate 20 with mask 32 shielding upstream catalyst site 21 u from the reactant gas stream indicated by reactant velocity profile 33
  • the gases containing products must be removed from the library after their emanation from the sites to minimise product circulation in the reactor In the arrangement shown in Fig.
  • the catalyst sites upstream from the test catalyst site, 21, must be masked to prevent signal crossover from different sites If the upstream sites are not masked and if some of these sites are catalytic, products formed at these sites would be transported downstream and interfere with the row screening process
  • Masking can be accomplished by using a physical mask to cover upstream catalysts sites, as shown in Fig 2, or by introducing reactant gases directly onto the catalyst sites using dedicated gas reactant feed tubes, shown as 34 in Fig. 3.
  • the solid state library of catalyst sites 5 mm long by 5 mm wide Assuming a gas feed line diameter of
  • test sites 21t can be tilted, as shown in Fig 4, during the screening process to promote the transport of products away from the catalyst surface
  • reactant gases can also be passed through the sites in the library generating a product plume above the test catalyst sites, as shown in Fig 5
  • the reactants pass through all of the catalyst sites thereby rendering simultaneous screening of all sites on the library feasible
  • reactants are passed through reactant plenum 36 to and through porous test sites 21 p forming product plumes 35 which are measured in the same manner as described above
  • Catalyst libraries may also be created, as shown in Fig 6, using monolithic structures 40 wherein reactant gases will also pass through channels 37 over catalyst coatings 38 forming product gases which pass through laser beam 23 and over microelectrodes 27
  • simultaneous screening of the entire library is readily accomplished Microelectodes 27 may be inserted into channels 37, as shown in Fig.
  • Gas flow into a vacuum chamber can also be pulsed to improve the pumping requirements.
  • ⁇ c,,/c v
  • Ti, Pi and T 2 , P 2 are the initial and final temperatures and pressures, respectively.
  • ⁇ 1.4 and an initial temperature of 800 K and 760 Torr pressure
  • T 2 800 ( 10 " 7760) ( “1 ) 4 - 16.7 K This temperature is suitable for generation of an excellent REMPI spectra.
  • Fig. 8 schematically shows a flat plate solid state catalyst library containing seventy two test sites 21 , arranged 8 rows wide by 9 rows axially which are sufficiently separated from one another to result in minimal intersite diffusion of product gases, within reactor 45.
  • Contact of reactants with the catalytic test sites is achieved by use of reactant feed tubes 34, as described with reference to Fig. 3, which effectively mask the upstream catalyst sites.
  • Each of the test sites in a row being screened has a dedicated microelectrode 27 for product gas detection, eight as shown in Fig 8, for screening by row Arranging the test sites in rows expedites screening in a row-by-row fashion using a single laser beam and provides simultaneous screening of eight sites Any row size can be accommodated using this invention.
  • any library pattern having specific addresses for individual test sites can be screened by moving the library with a computer controlled two-dimensional translation device
  • the smallest site size, providing the highest library density is determined by the gas phase dispersion rate of product gas between test sites Consequently, different products can allow the generation and testing of different library densities
  • laser beams 23 pass through window 39 of reactor 45 and through the product gases above the test sites 21 , perpendicular to the reactant gas flow from reactant feed tubes 34 and passes through the product gas plumes of all of the sites in a row, as indicated by the dotted line, and exits reactor 45 to laser beam dump 46
  • Reactant feed tubes 34 are supplied by reactor gas supply manifold 48
  • two lasers are indicated, however, any number of lasers may be used in a given application.
  • the laser beam may be placed anywhere in the product plume to maximise signal generation It is apparent that if the test site is not catalytic, no product formation and therefore no photoionisation will take place.
  • microelectrodes 27 Photoions and photoelectrons generated are collected by the microelectrodes 27 positioned in close position above the laser beam Based upon the above numerical design example, microelectrodes can be positioned anywhere beyond 5 mm above the test site surface and close to the laser beam to maximise signal intensity However, microelectrodes can be placed at different positions above the test sites to maximise signal collection in conjunction with the local fluid dynamics of the product plume.
  • the library substrate can also serve as the ground or cathode, or a microelectrode can be placed through a nonconductive substrate, if necessary, or microelectrodes can include both the anode and cathode as shown in Fig.
  • microelectrodes are powered from DC power source 30 through a multichannel switch and the measured signal of each microelectrode fed to detector 31. After testing of a particular row, the library can be moved either upstream or downstream, using library translator 47, to position the next row of sites for catalytic screening
  • FIG. 9 Another embodiment of this invention to exemplify the row screening process is shown in Fig 9.
  • the embodiment shown in Fig 9 is similar to Fig 8 except that porous catalyst libraries having porous test sites 21 p are fed a reactant gas from 7 a plenum beneath them which in turn is supplied reactant gas through reactant gas supply inlet 50.
  • the reactant gas passes through porous test sites 21 p forming a plume above each test site simultaneously as indicated by the arrows
  • the reactor can be rotated 1800 around the x-axis, if desired, to enhance product detection by altering the natural convection processes in the reactor vessel
  • screening is done on a row-by-row basis in similar manner as described with respect to Fig 8
  • screening of all sites simultaneously may be done by equipping each site with a dedicated microelectrode and providing the ionising laser beam 23 to pass all sites simultaneously using turning mirrors 26 as shown in the top view of Fig 10
  • Optical fibres may also be used to direct the laser beam to all sites simultaneously Signals from the microelectrodes are then detected and recorded by a dedicated detector for each site on catalyst library 51 or by use of a computerised multichannel switching system 65 to rapidly and sequentially detect the signal coming from each site It is apparent that any catalyst library size and shape can be accommodated and operated In this simultaneous screening mode as long as each site is individually addressable
  • Fig 1 1 schematically shows a 16 by 16 or 256 site monolith structure 40 as described with respect to Fig 7 forming a solid state catalyst library
  • Any monolith cell density can be used.
  • Reactant gases are provided through reactant gas supply inlet 50 to a manifold beneath the library and pass upwardly through the channels, passing over or through catalysts, generating product plumes which may be measured within the channels as shown in Fig 6, above the exit from the channels as shown in Fig. 91 or following cooling by a supersonic jet into a vacuum chamber as shown in Fig. 7.
  • Catalyst screening may be accomplished using row-by-row method as shown in Fig. 1 1 or by screening all sites simultaneously as described with respect to Fig. 10.
  • FIG. 12 Another embodiment of a monolith supported catalyst library screening structure within a reactor is shown in Fig 12, generally using the arrangement as described with respect to Fig 6 As shown in Fig 12, a separate catalyst library monolith 55 having 72 sites and a separate catalyst screening monolith 56 forms the catalyst screening structure within reactor 45 A dedicated microelectrode 27 is provided inside of each monolith channel Upstream of each microelectrode 27, optical access to each channel is provided by laser access windows 39 Reactant gases are introduced by reactant gas flow distributor and enter each of the individual library channels, as indicated by the arrows, to pass over the catalyst sites Products are detected downstream inside the screening monolith 56 Lasers emanating from tunable laser sources 24 and/or 25 are directed to each row of the screening monolith 56 via beam splitters 52 and through laser windows 39 to pass through each of the channels in the row through the internal laser windows as shown This arrangement provides simultaneous screening of all sites in the library Different laser beams can be directed to different rows in the screening monolith 56 to screen for different products This technique can also be applied for screening other library configurations Fiber optic lines
  • the entire catalyst library is first isolated from the reactant gases by a physical mask
  • the test chamber is then purged and filled with fresh reactant gases
  • the chamber contents are allowed to reach thermal equilibrium which can be monitored by thermocouples placed within the test chamber.
  • the physical mask is then removed exposing either a specified section or the entire catalyst library to reactant gases. Since there is no forced convection, diffusion and natural convection are the major modes of gas transport in the test chamber.
  • the sites that are catalytic then generate reaction products which diffuse into the bulk gas phase generating a product concentration plume.
  • the concentration penetration depth must be kept less than the intersite spacing to prevent overlapping of concentration plumes from adjacent sites resulting in signal crossover.
  • ⁇ c 1 and 0.1 cm 2 /sec for gas diffusivity
  • the REMPI measurements for the entire library must be completed in about 1 second to avoid overlap of concentration boundary layers.
  • Commercially available fast electronic equipment can meet these requirements. Larger site dimensions and/or placing physical barriers between sites can significantly decrease intersite diffusion-mixing rates, thereby providing longer times for measurements.
  • Gas dispersion through the liquid catalyst can be achieved in any suitable fashion as will be apparent to one skilled in the art, for example, pressurised reactant gases can be fed through reactant plenum 36 and forced through a controlled porosity distribution plate at the bottom of the sample site, as shown on the left in Fig. 13.
  • reactant gases from reactant plenum 36 may be bubbled through a capillary sparger 60 at each sample site, as shown on the right in Fig. 13.
  • Gaseous products 22 formed leave the liquid catalyst solution, as indicated by the arrows in Fig. 13, and product gas and product gas detection performed in any of the manners described earlier.
  • Fig. 14 is a schematic showing of catalyst library screening using a homogeneous liquid catalyst library, as described with respect to Fig. 13, within reactor 45.
  • REMPI catalyst screening can be either on a row by row basis as illustrated in Fig. 14, or the entire catalyst library can be screened simultaneously, using the method as described with respect to Fig. 10.
  • the reactor system exemplified in Fig. 14 may also be used to screen solid catalyst powders which can be placed in the container, as will be described in further detail with respect to Fig. 15.
  • Solid particles may be incorporated into the liquid catalyst library to achieve three phase, gas-liquid-solid, operating conditions.
  • the introduction of solid particles 60 to the liquid in container 58 enhances gas dispersion, forms smaller gas bubbles 61 to provide better gas-liquid contact and improves reactant conversion, thereby increasing the speed of library screening, is shown in the left hand portion of Fig. 15.
  • the catalyst bed can also be fluidised, partially or fully, under the screening conditions.
  • Product gases 22, indicated by arrows, emanate from container 58 and may be analysed by any of the REMPI methods previously described.
  • the solid particles used may be catalytic, thereby providing the opportunity of screening multi-phase catalytic reactions.
  • Homogeneous liquid catalysts may also be placed into porous particles, for example to immobilise proteins or molten salt catalysts, in the systems as shown in Fig. 15.
  • Solid catalytic particles 62 may be introduced into container 58, without liquid, to achieve gas- solid operating conditions, as shown in the right hand portion of Fig. 15.
  • Catalyst powders, prepared in a number of different manners, can be placed within the container shown in Fig. 15 to create a micro packed bed reactor library. Reactant gases may be introduced to the packed bed reactors through plenum 36. and products formed detected using the REMPI microelectrode systems previously described.
  • Fig. 16 is a schematic showing of another catalyst screening method using catalyst particles in a monolithic library.
  • Catalyst particles or powders 62 prepared in a number of different ways, can be placed into the cells of monolithic structure 40.
  • the reactant gases are then passed through the packed bed of catalyst particles 62 and are discharged through a small channel/orifice 43 into vacuum chamber 42.
  • the product jets then undergo expansion cooling and are subjected to laser beam 23 for the generation of photoions and photoelectrons.
  • the photoions or photoelectrons generated are then detected by microelectrodes 27, as described above.
  • the magnitude of the REMPI signals produced by the photoionisation of product species will be proportional to their concentration.
  • the generated signals are also influenced by the operational parameters, such as, the power of the UV laser used, the DC bias voltage applied to collect the photoions/photoelectrons, the separation distance of the anode and cathode and the position of the microelectrode relative to the laser beam.
  • the operational variables can be fixed so that the measured REMPI signals can be directly attributed to product concentrations generated by the catalyst sites. Consequently, in addition to the qualitative, active versus inactive, screening of catalyst libraries, the REMPI microelectrode technique of this invention can be used to quantitatively rank the activities and selectivities of catalysts.
  • Catalytically more active sites will produce higher concentration of products in the product plume and thereby generate larger REMPI signals, and likewise, less active catalyst sites will generate lower concentrations of products and thereby lower REMPI signals.
  • gas mixtures containing known concentrations of product gases are first passed sequentially over the library under conditions at which no reactions take place and the microelectrode responses noted.
  • microelectrode responses to known product concentrations
  • calibration of each site and microelectrode may be achieved. These calibration functions are hen used to determine the quantitative concentrations of products formed during the active catalyst screening process. If the catalyst loading is different at different library sites, this also must be accounted for in ranking of the catalytic activity of the sites.
  • internal standards can be added to the reactant feed stream during the screening process to expedite the quantification of the activities and selectivities of catalyst sites.
  • the catalyst screening techniques disclosed can be utilised to obtain a greater spectrum of objectives.
  • Two or more laser beam energies can be used sequentially to monitor two or more reaction products in a product plume, which is important to establish catalyst selectivity and to discover multifunctional catalysts.
  • the development of catalysts which not only maximises the formation of specific products but also minimises the formation of by-products or pollutants is an increasingly important objective in environmentally conscious manufacturing.
  • a series of laser pulses each pulse specifically photoionising a selected molecule, can be used to sequentially monitor different products. Since laser photoionisation and product detection are fast processes, having time scales in microseconds, rapid screening of large potential catalyst libraries for multifunctional catalytic activity can be accomplished even with the sequential detection of a large number of species.
  • the products formed by the catalytic reaction may be in the liquid or solid state, for example, reactions of high molecular biomolecules catalysed by enzymes, thus the direct application of REMPI is not suitable to screen catalytic activity and selectivity.
  • the REMPI method can be applied if the reaction products are first gasified. This can be accomplished by using a pulsed ablation laser, such as a pulsed CO 2 or excimer laser, to rapidly gasify product molecules from a liquid or solid surface.
  • a pulsed ablation laser such as a pulsed CO 2 or excimer laser
  • ablation laser source 63 generates ablation laser beam 64 to rapidly gasify product molecules from the surface of liquid catalyst solution 57 into gaseous product plume 22 which may be intercepted by ionisation laser beam 23 and produced photoions and photoelectrons detected by any of the microelectrode methods described above.
  • reaction intermediates as well as reaction products using the REMPI microelectrode methods of this invention.
  • the ability to monitor reaction intermediates, as well as products greatly enhances the range of applicablility of the methods of this invention.
  • measurements according to this invention can be undertaken in real time without any delay, fast transient processes can be monitored. This capability then leads to better understanding of the catalyst function and thus aids in the development of new and improved catalysts.
  • the following specific example is set forth in detail to specifically demonstrate this invention and should not be taken to limit the invention in any way.
  • the catalyst screening method of this invention was used in the catalytic dehydrogenation of cyclohexane into benzene according to the reaction C ⁇ n C ⁇ H ⁇ + 3 H 2 .
  • This is a well established reaction which is catalyzed by transition and precious metals in the temperature range of 250° to 350°C according to Rebhan, D.M. et al in "A Kinetic and Mechanistic Study of Cyclohexane Disproportionation: An Example of Irreversible Hydrogen Transfer", J. Catalysis, 111, 397, 1988.
  • the catalyst library was then placed into a reactor and heated to 300°C in the presence of an argon gas flow. Following establishment of the steady state operating temperature, which was determined by thermocouples inside the reactor, a cyclohexane reactant stream was introduced.
  • the reactant stream composition was 13% cyclohexane in argon gas which was prepared by bubbling argon gas through cyclohexane liquid at about 25°C by using a sparger.
  • the library screening process demands the unambiguous detection of benzene in a cyclohexane, hydrogen and argon mix.
  • a suitable liv laser wave length for selectively producing benzene REMPI ions was identified in separate tests using a laser photoionization time of flight mass spectromer, TOF-MS.
  • Gas pulses of cyclohexane and benzene, each at a concentration of about 50 ppm in argon, were expanded into the vacuum chamber of the TOF-MS using a pulsed valve and the resulting jet/molecular beam was crossed by a pulsed UV laser beam in the 258-262 nm range to generate their photoionisation and mass spectra.
  • the UV laser had about lOO ⁇ J/pulse energy and was obtained from the dye laser using Coumai ⁇ n 500 dye.
  • REMPI spectra of benzene and cyclohexane were also determined at 1 atm and ambient temperature using the microelectrode process cyclohexane and benzene in argon carrier gas were photoionized by passage of a pulsed liv laser beam in the 258-262 nm range within 1 -2 mm of the probe tip A DC bias of +500 V from a power source was applied to the anode to collect the photoelectrons
  • the resulting REMPI spectra aie shown in Fig 19 and are similar to the spectra obtained by the TOF-MS shown in Fig 18, with expected spectral broadening observed in the ambient temperature and 1 atm pressure conditions This shows that use of the 259 7 laser results in the exclusive and efficient production of benzene REMPI ions in the presence of cyclohexane, argon and
  • the reactor system shown in Fig 9 was used passing cyclohexane in argon carrier gas through the eight library sites in a row, as identified above
  • the 259 7 nm laser beam was passed through the product plume from the library sites and the benzene REMPI signals detected in the vicinity of each of the eight sites are shown in Fig 20
  • These measurements correspond to data acquired by one laser shot and the signals exhibited fast rise and decay time, in the order of microseconds
  • microelectrodes located at sites 2, 4, 7 and 8 picked up appreciable benzene signals, consistent with the presence of Pt and Pd catalysts at these sites While some REMPI signals were also detected at sites 1, 3, 5 and 6, they were significantly lower, consistent with the absence of catalysts at these sites.
  • Fig 19 shows that the method of this invention rapidly and clearly distinguished between active and inactive sites in the library
  • the reactor exhaust gases were also analyzed by the TOF-MS using the 259 7 nm laser beam during screening to ascertain whether species other than benzene could have contributed to the measured microelectrode signals No photoions other than those with mass 78 were detected
  • reaction temperature can easily be varied from room temperature, such as 25°C , to higher temperatures, such as 1000°C
  • pressure can be varied from vacuum, such as 10 "4 Torr, to high pressures, such as 500 atmospheres
  • the screening process can easily accomodate a wide range of reactant feed concentrations from pure components, 100%, to very dilute streams, such as a few hundred parts per million, 100 ppm
  • Combinatorial catalyst libraries can also be generated by machining miniature reactors using integrated circuit manufacturing steps such as thin film deposition, lithography, Etching, plasma processing and the like This approach has been used recently to make a reactor on a chip for the catalytic oxidation of ammonia, as described by Srinivasan, R et al
  • Figs 21 and 22 are simplified schematic showings of bases for single microreactor systems according to this invention
  • Fig 21 shows a microreactor suitable for thin film or solid particle catalyst deposition processes
  • Fig. 22 shows a microreactor additionally suitable for solution based catalyst deposition processes.
  • inert microreactor body 70 has reactant feed passage 71 leading to a catalyst zone, shown in Fig 21 as zone 72 and in Fig.
  • baffle structure 74 may be located in reservoir 73 Such baffle structures may have a number of effects, such as, providing additional exposed surface area for the catalyst and for inducing mixing to benefit some reactions
  • Products exit the reaction volume through exit passage 75 Reactant feed and product flow are shown by the arrows
  • Activating radiation passages 76 having optical access windows for isolation of exit passage 75, are provided to direct passage of activating radiation beam 77 through the product stream passing through exit passage 75
  • Fig 21 shows external microelectrode 78 and
  • Fig 22 shows internal microelectrode positioned in exit passage 75 in proximity to the activating radiation beam 77 to, collect photoelectrons or photoions for detection, as previously described
  • Internal microelectrode 84 is attached to microreactor body 70, such as embedded to the bottom, side or top walls of the product exit passage, and is thus an integral part of the microreactor body
  • These internal microelectrodes may be flush with the product exit passage walls or may protrude from them
  • Fig 23 schematically shows an array of microreactors in a single inert microreactor body 70 Any number of microreactois may be present in the array, depending upon the size of the microreactors and the physical characteristics of the substrate wafer
  • Each microreactor 72 can be of any size, however, reactor channels in the order of about 0 1 to 2 millimeters wide are most suitable for fabrication and subsequent screening processes
  • Reactant plenum 79 is in fluid communication with each reactant feed passageway 72 to distribute reactants to each microreactor
  • Reactant plenum 79 is sufficiently large to insure the establishment of similar fluid flow rates through each microreactor, provided that the pressure drop characteristics of the microreactors are similar
  • flow sensors and actuators may be fabricated in each microreactor to independently control fluid flow through each of the microreactors
  • a different catalyst may be placed in each microreactor-using, for example, any of the techniques described
  • the physical forms of these catalysts can be films, as indicated by numeral 86, or
  • FIG. 24 shows internal microelectrodes 87 attached to or embedded in cover wafer 80 in similar manner as described with respect to internal microelectrodes 84 attached to microreactor body 70, as disclosed above.
  • Internal wiring 88 leads from each microelectrode 87 to external connector 89 for powering each microelectrode and for passage of detection signals from each microelectrode to a detection device.
  • separate electrodes can be embedded to the base 70 for signal detection and/or for power supply.
  • individual flat microreactor arrays as shown in Fig.
  • microreactor arrays may have any suitable fasteners for maintaining adjacent arrays in fixed relationship with each other.
  • the microelectrodes are powered by DC power source and the signal from each microelectrode fed through a multi-channel selector to measurement device.
  • Fig. 26 shows a microreactor array 91 , as shown in Fig. 24, may be placed in microreactor array frame 92 for easy handling and connection for catalyst screening.
  • the microreactor array fits into an opening in the frame as indicated by the reversible arrow.
  • Reactant feed is provided through the frame to the reactant feed manifold of the microreactor array, as indicated by the arrows, and product exits through the frame, as indicated by the arrows.
  • Radiation passages 93 are provided through frame 92 for entry and exit of radiation beam 77 aligned to pass through radiation passages 76 in microreactor body 70, as described above.
  • the frame also has internal wiring 94 for connection at one end to internal wiring 88 of the microreactor array and at the opposite end to a power source and a detection measurement device.
  • the internal wiring of a plurality of microreactor array frames may connect through a single connector to external wiring.
  • the frames may also have reactant feed manifolds arranged so that a single feed supply can provide reactant to a plurality of microreactor array - frame assemblies.
  • the frames may also provide temperature control for the microreactor array through heating elements built into the frames.
  • Microreactor array - frames may have any suitable means for connection of adjacent microreactor array frame assemblies.
  • a plurality of microreactor - frame assemblies may be joined in a vertical fashion similar to that shown in Fig 25 In another embodiment, shown in Fig. 27, microreactor array -frame assemblies 95 may be joined horizontally in side-by-side relation. Alignment of radiation passages 93 makes it possible to use one radiation beam 77 in the evaluation of large catalyst libraries
  • Screening is accomplished by passing a known amount of reactant gases through the microreactor array in contact with the potential catalysts forming reaction products which are activated by passing a suitable tunable radiation beam through activating radiation passages 76, having access windows providing fluid isolation, to form product REMPI ions in the product exit passages 75
  • product REMPI ions are detected by the microelectrodes within the exit passages and measured in manners described above
  • the microreactor arrays may be placed in a furnace for temperature control of the entire array or the temperature of each microreactor may be independently controlled using sensors and heating elements built into the microreactors during the microreactor fabrication process Alternatively, temperature control can be provided by the frame.
  • FIGs 28 A and 28B summarise another example of combinatorial catalyst library preparation and screening method using a different microreactor array and microdrop/microjet technology according to this invention
  • Step 1 shows preparation of the catalyst library inert substrate using a plug to form desired passageways and to retain liquid during solution deposition
  • Step 2 shows catalyst precursor solution deposition into reservoirs of catalyst reaction zones
  • Step 3 shows drying and calcining of the catalyst by methods well known in the art
  • Step 4 shows opening of the product exit passages by removal of the plugs used to form the passages
  • Step 5 shows formation and/or activation of the catalyst by passage of a suitable gas through the microreactor array
  • Step 6 shows screening of the catalysts within the array of microreactors by passing reactant gas(s) in contact with the catalyst in each microreactor, passing a radiation beam of an energy level to promote formation of specified ions through each reaction product stream, and detecting the formed ions or electrons by microelectrode collection in proximity to the activating radiation beam

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Abstract

La présente invention concerne le criblage rapide d'activités et de sélectivités de bibliothèques de catalyseur possédant des sites de tests adressables, effectué en mettant en contact des catalyseurs potentiels au niveau de sites de test avec des flux de réactif qui forment des panaches de produit au niveau des sites de test adressables. Ces panaches de produit sont criblés par passage d'un faisceau de rayonnement d'un niveau d'énergie quelconque de façon à promouvoir la formation de photoions et de photoélectrons détectés par un groupe de microélectrodes in situ à proximité du site de test adressable respectif. Les panaches de produit peuvent être criblés rangée par rangée et tous les panaches de produit émanant de la bibliothèque complète de catalyseur peuvent être criblés simultanément. La présente invention concerne également des réacteurs et des microréacteurs adaptés pour un triage d'activation de ryonnement.
PCT/GB1998/003023 1997-10-10 1998-10-08 Activation de rayonnement et criblage de bibliotheques de catalyseurs permettant d'evaluer un catalyseur et reacteurs correspondants WO1999019724A1 (fr)

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Application Number Priority Date Filing Date Title
AU94494/98A AU736438B2 (en) 1997-10-10 1998-10-08 Radiation activation and screening of catalyst libraries for catalyst evaluation and reactors therefor
PL98339834A PL339834A1 (en) 1997-10-10 1998-10-08 Radiant activation and screening of catalyst libraries for evaluation of catalysts and reactors therefor
NZ503731A NZ503731A (en) 1997-10-10 1998-10-08 Radiation activation and screening of catalyst libraries for catalyst evaluation and reactors therefor
BR9812909-0A BR9812909A (pt) 1997-10-10 1998-10-08 Processo e microreator para classificação rápida de coletâneas de catalisador em potencial quanto as propriedades catalìticas
CA002306256A CA2306256A1 (fr) 1997-10-10 1998-10-08 Activation de rayonnement et criblage de bibliotheques de catalyseurs permettant d'evaluer un catalyseur et reacteurs correspondants
EP98947652A EP1019713A1 (fr) 1997-10-10 1998-10-08 Activation de rayonnement et criblage de bibliotheques de catalyseurs permettant d'evaluer un catalyseur et reacteurs correspondants
JP2000516226A JP2001520380A (ja) 1997-10-10 1998-10-08 触媒評価のための触媒ライブラリの照射活性化およびスクリーニング並びにそのための反応器
KR1020007003828A KR20010031021A (ko) 1997-10-10 1998-10-08 촉매 평가용 촉매 라이브러리의 방사선 활성화와 스크리닝및 그 반응장치
NO20001787A NO20001787L (no) 1997-10-10 2000-04-06 StrÕlingsaktivering og sortering av katalysatorbibliotek for katalysatorevaluering og reaktorer for disse

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US8741798A 1998-05-29 1998-05-29
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WO2000029844A1 (fr) * 1998-11-12 2000-05-25 Bp Chemicals Limited Procede et dispositif permettant d'explorer des bibliotheques de catalyseurs
DE19952764A1 (de) * 1998-11-09 2000-05-31 Hewlett Packard Co Vorrichtung zur Hochdurchsatz-Proben-Verarbeitung, -Analyse und -Sammlung und Verfahren zur Verwendung derselben
EP1108467A2 (fr) 1999-12-15 2001-06-20 Uop Llc Réacteur combinatoire catalytique
WO2001043866A1 (fr) * 1999-12-13 2001-06-21 Hte Ag Procede pour la production de bibliotheques de materiaux par deposition electrochimique
EP1129773A2 (fr) * 2000-03-01 2001-09-05 Symyx Technologies, Inc. Méthode de synthese in-situ d'une bibliotheque combinatoire de matières catalytiques supportés
US6342185B1 (en) 1999-12-15 2002-01-29 Uop Llc Combinatorial catalytic reactor
WO2002014854A1 (fr) * 2000-08-14 2002-02-21 Chevron U.S.A. Inc. Utilisation de reacteurs a microcanaux en chimie combinatoire
GB2366793A (en) * 2000-09-13 2002-03-20 Imperial College Chemical processing system
US6368865B1 (en) 1999-12-15 2002-04-09 Uop Llc Combinatorial process for performing catalytic chemical reactions
US6426226B1 (en) 1997-10-10 2002-07-30 Laboratory Catalyst Systems Llc Method and apparatus for screening catalyst libraries
US6576196B1 (en) 1999-12-15 2003-06-10 Uop Llc Multiple parallel catalytic reactor assembly
US6602714B1 (en) 1999-11-09 2003-08-05 Sri International Viscosity and mass sensor for the high-throughput synthesis, screening and characterization of combinatorial libraries
US6627445B1 (en) 1999-12-15 2003-09-30 Uop Llc Process for simultaneously evaluating a plurality of catalysts
WO2004010147A1 (fr) * 2002-07-16 2004-01-29 Consejo Superior De Investigaciones Cientificas Support rotatif et appareil de caracterisation multiple spectroscopique d'echantillons de matieres solides
DE10234564A1 (de) * 2002-07-25 2004-02-12 Senslab-Gesellschaft Zur Entwicklung Und Herstellung Bioelektrochemischer Sensoren Mbh Biosensor
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US6923939B1 (en) 2001-07-05 2005-08-02 Uop Llc Heat activated membrane introduction apparatus and method for screening materials
US6949267B2 (en) 2002-04-08 2005-09-27 Engelhard Corporation Combinatorial synthesis
US6974665B2 (en) 2001-09-06 2005-12-13 University Of Nebraska In situ screening to optimize variables in organic reactions
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US7063982B1 (en) 2002-03-12 2006-06-20 Uop Llc Process of vaporizing and reacting a liquid feed
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US7267987B2 (en) 2003-01-06 2007-09-11 Uop Llc Process and assembly for simultaneously evaluating a plurality of catalysts
US7344891B2 (en) 2002-03-12 2008-03-18 Uop Llc Process vessel with integral evaporator
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DE19952764A1 (de) * 1998-11-09 2000-05-31 Hewlett Packard Co Vorrichtung zur Hochdurchsatz-Proben-Verarbeitung, -Analyse und -Sammlung und Verfahren zur Verwendung derselben
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WO2001043866A1 (fr) * 1999-12-13 2001-06-21 Hte Ag Procede pour la production de bibliotheques de materiaux par deposition electrochimique
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US6368865B1 (en) 1999-12-15 2002-04-09 Uop Llc Combinatorial process for performing catalytic chemical reactions
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US6770245B2 (en) 1999-12-15 2004-08-03 Uop Llc Multiple parallel processing assembly
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US6873414B2 (en) 2000-02-04 2005-03-29 Hte Aktiengesellschaft Method and apparatus for the combinatorial preparation and testing of material libraries by photoacoustic analytical methods
US6875717B2 (en) 2000-03-01 2005-04-05 Symyx Technologies, Inc. Method and system for the in situ synthesis of a combinatorial library of supported catalyst materials
US6627571B1 (en) 2000-03-01 2003-09-30 Symyx Technologies, Inc. Method and system for the situ synthesis of a combinatorial library of supported catalyst materials
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US7374942B2 (en) 2000-03-16 2008-05-20 Basf Aktiengesellschaft Process and apparatus for the combinatorial production and testing of catalyst material libraries by using at least two analytical methods
US7503515B2 (en) 2000-07-07 2009-03-17 Symyx Technologies, Inc. Methods and apparatus for mechanical treatment of materials such as catalysts
DE10036633B4 (de) * 2000-07-27 2005-03-10 Hte Ag The High Throughput Exp Anordnung in modularer Bauweise und Verfahren zur paralellen Testung einer Mehrzahl von Bausteinen einer Materialbibliothek
EP1305110B1 (fr) * 2000-07-27 2009-12-16 hte Aktiengesellschaft the high throughput experimentation company Agencement d'essai parallele de materiaux
US6806087B2 (en) * 2000-08-14 2004-10-19 Chevron U.S.A. Inc. Use of microchannel reactors in combinatorial chemistry
WO2002014854A1 (fr) * 2000-08-14 2002-02-21 Chevron U.S.A. Inc. Utilisation de reacteurs a microcanaux en chimie combinatoire
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US6923939B1 (en) 2001-07-05 2005-08-02 Uop Llc Heat activated membrane introduction apparatus and method for screening materials
US7229832B2 (en) 2001-07-05 2007-06-12 Uop Llc Heat activated membrane introduction apparatus and method for screening materials
US6974665B2 (en) 2001-09-06 2005-12-13 University Of Nebraska In situ screening to optimize variables in organic reactions
US7070999B1 (en) 2001-09-17 2006-07-04 Uop Llc Apparatus and method for generating a plurality of isolated effluents
US7129092B2 (en) 2001-09-17 2006-10-31 Uop Llc Apparatus and method for generating a plurality of isolated effluents
US6808685B2 (en) 2001-09-17 2004-10-26 Uop Llc Apparatus and method for generating a plurality of isolated effluents
US6989131B2 (en) 2002-03-12 2006-01-24 Uop Llc Catalytic reactor with integral evaporator
US7063982B1 (en) 2002-03-12 2006-06-20 Uop Llc Process of vaporizing and reacting a liquid feed
US7588729B2 (en) 2002-03-12 2009-09-15 Uop Llc Process vessel with integral evaporator
US7344891B2 (en) 2002-03-12 2008-03-18 Uop Llc Process vessel with integral evaporator
US6949267B2 (en) 2002-04-08 2005-09-27 Engelhard Corporation Combinatorial synthesis
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WO2004010147A1 (fr) * 2002-07-16 2004-01-29 Consejo Superior De Investigaciones Cientificas Support rotatif et appareil de caracterisation multiple spectroscopique d'echantillons de matieres solides
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AU736438B2 (en) 2001-07-26
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KR20010031021A (ko) 2001-04-16
EP1019713A1 (fr) 2000-07-19
BR9812909A (pt) 2002-02-05
PL339834A1 (en) 2001-01-02
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